JPH04231324A - Plate-type barium sulfate - Google Patents
Plate-type barium sulfateInfo
- Publication number
- JPH04231324A JPH04231324A JP41478690A JP41478690A JPH04231324A JP H04231324 A JPH04231324 A JP H04231324A JP 41478690 A JP41478690 A JP 41478690A JP 41478690 A JP41478690 A JP 41478690A JP H04231324 A JPH04231324 A JP H04231324A
- Authority
- JP
- Japan
- Prior art keywords
- barium sulfate
- barium
- sulfate
- concn
- soln
- 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 title claims abstract description 56
- 238000002834 transmittance Methods 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 238000002441 X-ray diffraction Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 28
- 238000000149 argon plasma sintering Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 159000000009 barium salts Chemical class 0.000 abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 14
- 239000002537 cosmetic Substances 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 230000005251 gamma ray Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Cosmetics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、使用感がよく、高い光
散乱性と透明性を有し、色むらを抑制する効果に優れた
板状硫酸バリウムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to barium sulfate plates that are comfortable to use, have high light scattering properties and transparency, and are highly effective in suppressing color unevenness.
【０００２】0002
【従来の技術及び発明が解決しようとする課題】硫酸バ
リウムは人体に無害で、隠蔽力が強いため、Ｘ線の造影
剤、γ線吸収材、白色顔料等として工業的に広く使用さ
れている。しかしながら、化粧品用としての利用、その
中でも特にファンデーション等に使用する場合には、従
来の硫酸バリウムでは、伸び、付きが悪く使用感に欠け
ていたり、また、透明感に欠け、化粧後、素肌感覚が劣
るという欠点があった。そこで、これらの欠点を解決す
る手段として、従来、粒径の大きい硫酸バリウム（特開
昭５８−４１７１８号）、板状及び針状結晶の硫酸バリ
ウム（特開昭６２−１７４２３８号）が提案されている
。しかしながら、これらの硫酸バリウムを製造するには
、硫酸バリウムを合成した後に、熱処理、鉱酸処理を必
要とするため製造工程が複雑で、工業生産上好ましくな
いと共に、斯かる合成後の処理を行っても、合成された
硫酸バリウムの形骸を完全に取り除くことが困難であっ
て、板状構造の発達度合も不充分であり、上記目的を完
全に満足する硫酸バリウムは存在しなかった。[Prior Art and Problems to be Solved by the Invention] Barium sulfate is harmless to the human body and has strong hiding power, so it is widely used industrially as an X-ray contrast agent, gamma ray absorbing material, white pigment, etc. . However, when used in cosmetics, especially in foundations, conventional barium sulfate does not spread easily and does not stick well, resulting in a lack of feel when using it. It had the disadvantage of being inferior. Therefore, as a means to solve these drawbacks, barium sulfate with a large particle size (Japanese Patent Application Laid-Open No. 58-41718) and barium sulfate with plate-shaped and needle-like crystals (Japanese Patent Application Laid-Open No. 174238-1982) have been proposed. ing. However, in order to manufacture these barium sulfates, the manufacturing process is complicated because it requires heat treatment and mineral acid treatment after barium sulfate is synthesized, which is not desirable for industrial production, and it is difficult to carry out such post-synthesis treatments. However, it is difficult to completely remove the remains of the synthesized barium sulfate, and the degree of development of the plate-like structure is insufficient, so there has been no barium sulfate that completely satisfies the above objectives.
【０００３】0003
【課題を解決するための手段】斯かる実状において、本
発明者は上記課題を解決せんと鋭意研究を行った結果、
よく発達した板状構造を有する硫酸バリウムが、伸び付
き等の使用感に優れ、かつ高い光散乱性と透明性を有し
、上記条件を具備することを見出し、本発明を完成した
。[Means for Solving the Problems] Under such circumstances, the present inventor conducted intensive research to solve the above problems, and as a result,
The inventors have discovered that barium sulfate, which has a well-developed plate-like structure, has excellent feel when used, such as spreadability, and has high light scattering properties and transparency, and satisfies the above conditions, and has completed the present invention.
【０００４】従って、本発明は、配向試料のＸ線回折に
おいて、結晶の（０２０）と（２００）面の回折ピーク
強度比が１．５〜１００であることを特徴とする板状硫
酸バリウムを提供するものである。Therefore, the present invention provides a plate-like barium sulfate which is characterized in that the diffraction peak intensity ratio of the (020) and (200) planes of the crystal is 1.5 to 100 in X-ray diffraction of an oriented sample. This is what we provide.
【０００５】本発明のＸ線回折において、配向試料とし
ては、硫酸バリウム試料１ｇをエタノール５０ｍｌ中に
分散させ、ガラス板上に厚さ約１５μｍの薄膜を形成さ
せ、乾燥したものが使用される。Ｘ線回折は、理学電機
製（形式：ＲＡＤ−２００）でＣｕＫα線、４０ｋＶ、
８０ｍＶで行われ、当該結晶の（０２０）と（２００）
面の回折ピーク強度を測定し、この強度比〔（０２０）
／（２００）〕を算出する。この強度比が１．５未満の
場合には、粉体の滑り性が乏しく、例えば化粧料に配合
した場合、使用感が悪く、また１００を超えると、厚み
方向の構造が未発達で、機械的強度が不足し、例えば化
粧料、塗料等への配合時あるいは使用時、板状構造が崩
れるという欠点がある。In the X-ray diffraction of the present invention, the oriented sample used is one obtained by dispersing 1 g of barium sulfate sample in 50 ml of ethanol, forming a thin film with a thickness of about 15 μm on a glass plate, and drying it. X-ray diffraction was performed using Rigaku Denki (model: RAD-200) using CuKα rays, 40 kV,
(020) and (200) of the crystal
The diffraction peak intensity of the plane was measured and the intensity ratio [(020)
/(200)]. If this strength ratio is less than 1.5, the powder will have poor slipperiness and will not feel good when used in cosmetics, and if it exceeds 100, the structure in the thickness direction will be underdeveloped and mechanical It has the disadvantage that it lacks physical strength, and its plate-like structure collapses when it is blended into cosmetics, paints, etc., or when used.
【０００６】本発明の板状硫酸バリウムは、更に、濃度
２０重量％、厚さ１５μｍの薄膜を形成したときの散乱
強度が５５％以上で、かつ全透過率が７０％以上である
のが好ましい。ここにおいて、散乱強度及び全透過率は
次のようにして測定されたものを意味する。すなわち、
分散媒としてシリコン油を使用し、これに硫酸バリウム
試料を２０重量％加えて均一に混練し、アプリケータに
より、１５μｍの薄膜をガラス板上に形成させ、これを
ヘイズメーター〔村上色彩技術研究所製（形式：ＨＲ−
１００）〕により、平行光線透過率（Ｔｐ）と散乱光透
過率（Ｔｄ）を測定し、Ｔｐ＋Ｔｄを全透過率〔Ｔｄ／
（Ｔｐ＋Ｔｄ）〕×１００を散乱強度とした。[0006] The plate-like barium sulfate of the present invention preferably has a scattering intensity of 55% or more and a total transmittance of 70% or more when a thin film having a concentration of 20% by weight and a thickness of 15 μm is formed. . Here, the scattering intensity and total transmittance mean those measured as follows. That is,
Using silicone oil as a dispersion medium, add 20% by weight of barium sulfate sample, knead it uniformly, form a 15 μm thin film on a glass plate with an applicator, and measure this with a haze meter [Murakami Color Technology Research Institute] Manufactured by (model: HR-
100)] to measure the parallel light transmittance (Tp) and scattered light transmittance (Td), and calculate Tp+Td as the total transmittance [Td/
(Tp+Td)]×100 was defined as the scattering intensity.
【０００７】本発明の上記条件を具備した板状硫酸バリ
ウムは、例えば、所定濃度のバリウム塩溶液と硫酸又は
硫酸塩溶液を５〜１００℃、好ましくは１５〜９５℃の
温度で混合反応せしめることにより製造される。バリウ
ム塩は、塩化バリウム、硝酸バリウム、酢酸バリウム等
の水、アルコール等の溶媒に可溶のものであればよく、
純度は本発明の特徴である透明性を阻害させないために
、バリウム以外の金属イオンが１０００ｐｐｍ 以下で
あることが望ましい。硫酸又は硫酸塩溶液は硫酸、硫酸
ナトリウム等の水、アルコール等の溶媒に可溶で、バリ
ウム塩の場合と同様に透明性の観点から金属イオンを含
有しないものが好ましい。バリウム塩溶液及び、硫酸又
は硫酸塩溶液の濃度は０．００１〜０．５Ｍであること
が望ましい。この範囲外では（０２０）面の発達が阻害
されて、微粉状になり易い。[0007] The plate-shaped barium sulfate having the above conditions of the present invention can be obtained by, for example, mixing and reacting a barium salt solution with a predetermined concentration with a sulfuric acid or sulfate solution at a temperature of 5 to 100°C, preferably 15 to 95°C. Manufactured by. The barium salt may be one that is soluble in a solvent such as water or alcohol, such as barium chloride, barium nitrate, or barium acetate.
The purity is preferably 1000 ppm or less of metal ions other than barium so as not to impede transparency, which is a feature of the present invention. The sulfuric acid or sulfate solution is preferably one that is soluble in a solvent such as water, alcohol, etc., such as sulfuric acid or sodium sulfate, and does not contain metal ions from the viewpoint of transparency, as in the case of barium salt. The concentration of the barium salt solution and the sulfuric acid or sulfate solution is preferably 0.001 to 0.5M. Outside this range, the development of the (020) plane is inhibited and it tends to become fine powder.
【０００８】[0008]
【発明の効果】本発明の板状硫酸バリウムは、従来のも
のに比較し、Ｘ線回折による（０２０）面がよく発達し
ていて隠蔽力に優れ、粉体の摩擦係数は格段に低く、伸
び付き等の使用感がよく、高い光散乱性及び透明性を有
するので、化粧品顔料、塗料用顔料、樹脂充填剤、γ線
吸収剤等の広い分野に使用することができる。Effects of the Invention: Compared to conventional barium sulfate, the (020) plane determined by X-ray diffraction is well developed and has excellent hiding power, and the friction coefficient of the powder is much lower. Since it spreads well and has a good feel when used, and has high light scattering properties and transparency, it can be used in a wide range of fields such as cosmetic pigments, paint pigments, resin fillers, and gamma ray absorbers.
【０００９】[0009]
【実施例】次に実施例を挙げて説明する。[Example] Next, an example will be given and explained.
【００１０】実施例１
特級塩化バリウム１．９７４ｇと特級硫酸０．５０５ｇ
をイオン交換水１０００ｇにそれぞれ溶解し、０．００
８Ｍのバリウム溶液、０．００５Ｍの硫酸溶液とした。
次に各溶液を７０℃に加温し、Ｕ字型撹拌バネを用い、
回転数１０００ｒｐｍ で撹拌した硫酸溶液にバリウム
溶液を１０分間で滴下し、その後３分間撹拌を続け反応
を終了させた。次に、常温まで冷却した後、５Ｃの濾紙
で濾過し、粉末１．１２ｇを得た。得られた粉末は、平
均径が５．３μｍで、Ｘ線回折において、硫酸バリウム
結晶の（０２０）と（２００）面の回折ピーク強度比（
ピーク面積比）が１５．３で、よく発達した板状構造を
呈し、滑り易い粉体であった。そのＸ線回折パターンを
図１に示す。また粉体濃度２０％で、厚さ１５μｍの薄
膜を形成したときの散乱強度及び全透過率は、それぞれ
７３％、９３％で、透明性、光散乱性に優れていた。こ
れを化粧料のファンデーションに配合したところ、従来
のマイカ、タルク等の体質顔料を配合したものに較べて
、使用感が良く、化粧膜の透明性は高く色むらを抑制す
る効果があった。Example 1 1.974g of special grade barium chloride and 0.505g of special grade sulfuric acid
Dissolve each in 1000 g of ion-exchanged water, and add 0.00
An 8M barium solution and a 0.005M sulfuric acid solution were used. Next, each solution was heated to 70°C, and using a U-shaped stirring spring,
The barium solution was added dropwise over 10 minutes to the sulfuric acid solution stirred at 1000 rpm, and stirring was continued for 3 minutes to complete the reaction. Next, after cooling to room temperature, it was filtered through a 5C filter paper to obtain 1.12 g of powder. The obtained powder has an average diameter of 5.3 μm, and in X-ray diffraction, the diffraction peak intensity ratio of the (020) and (200) planes of barium sulfate crystal (
The powder had a peak area ratio of 15.3, had a well-developed plate-like structure, and was slippery. The X-ray diffraction pattern is shown in FIG. Furthermore, when a thin film with a thickness of 15 μm was formed at a powder concentration of 20%, the scattering intensity and total transmittance were 73% and 93%, respectively, indicating excellent transparency and light scattering properties. When this was blended into a cosmetic foundation, it felt better to use and the cosmetic film had a higher transparency than those containing conventional extender pigments such as mica and talc, and was effective in suppressing color unevenness.
【００１１】実施例２
特級酢酸バリウム１１０．４３ｇをイオン交換水２００
０ｇに溶解し、０．２Ｍのバリウム溶液と特級硫酸ナト
リウム２９．２６ｇをイオン交換水２０００ｇに溶解し
、０．２Ｍの硫酸溶液とし、８５℃に加温した後、実施
例１と同様の条件で硫酸バリウムを合成した。得られた
粉末は６５．３ｇで、平均径が７．２μｍで、Ｘ線回折
において、硫酸バリウム結晶の（０２０）と（２００）
面の回折ピーク強度比が５．３で、（０２０）面のよく
発達したものであった。また、粉体濃度２０％で、厚さ
１５μｍの薄膜を形成したときの散乱強度、全透過率は
それぞれ、６２％、９１％で、透明性、光散乱性に優れ
ていた。化粧料のファンデーションに配合したところ、
使用感が良く、化粧膜の透明性は高く色むらを抑制する
効果があった。Example 2 110.43 g of special grade barium acetate was added to 200 g of ion-exchanged water.
A 0.2M barium solution and 29.26g of special grade sodium sulfate were dissolved in 2000g of ion-exchanged water to make a 0.2M sulfuric acid solution, heated to 85°C, and then subjected to the same conditions as in Example 1. barium sulfate was synthesized. The obtained powder weighed 65.3 g and had an average diameter of 7.2 μm, and X-ray diffraction revealed that the (020) and (200)
The diffraction peak intensity ratio of the plane was 5.3, indicating that the (020) plane was well developed. Further, when a thin film with a thickness of 15 μm was formed at a powder concentration of 20%, the scattering intensity and total transmittance were 62% and 91%, respectively, indicating excellent transparency and light scattering properties. When added to cosmetic foundation,
It was easy to use, had a highly transparent cosmetic film, and was effective in suppressing color unevenness.
【００１２】比較例１
特級塩化バリウム２４６．７５ｇと特級硫酸１０１．０
０ｇをイオン交換水１０００ｇにそれぞれ溶解し、０．
１Ｍのバリウム溶液、０．１Ｍの硫酸溶液とした。次に
各溶液を３０℃で、実施例１と同様の方法で粉末を合成
した。得られた粉末は１９５ｇで、平均径が０．３μｍ
で、Ｘ線回折において、硫酸バリウム結晶の（０２０）
と（２００）面の回折ピーク強度比が１．０で、板状構
造の発達は悪く、滑り難い粉末であった。そのＸ線回折
パターンを図２に示す。また粉体濃度２０％で、厚さ１
５μｍの薄膜を形成したときの散乱強度、全透過率は、
それぞれ３９％、６１％で、透明性、光散乱性に劣って
いた。Comparative Example 1 246.75g of special grade barium chloride and 101.0g of special grade sulfuric acid
0g of each was dissolved in 1000g of ion-exchanged water.
A 1M barium solution and a 0.1M sulfuric acid solution were used. Next, powders were synthesized using each solution at 30° C. in the same manner as in Example 1. The obtained powder weighed 195 g and had an average diameter of 0.3 μm.
So, in X-ray diffraction, (020) of barium sulfate crystal
The diffraction peak intensity ratio of the (200) and (200) planes was 1.0, the plate-like structure was poorly developed, and the powder was difficult to slip. The X-ray diffraction pattern is shown in FIG. Also, at a powder concentration of 20%, the thickness is 1
The scattering intensity and total transmittance when forming a 5 μm thin film are:
The transparency and light scattering properties were 39% and 61%, respectively.
【００１３】実施例３〜１３、比較例２〜５表１に示す
濃度のバリウム溶液と硫酸溶液を、所定の混合比（バリ
ウム溶液／硫酸溶液）及び反応温度で実施例１と同様に
して反応させ、表１に示す摩擦係数、全透過率、Ｘ線ピ
ーク強度比（％）〔（０２０）／（２００）〕及び結晶
形の硫酸バリウムを得た。Examples 3 to 13, Comparative Examples 2 to 5 Barium solutions and sulfuric acid solutions having the concentrations shown in Table 1 were reacted in the same manner as in Example 1 at a predetermined mixing ratio (barium solution/sulfuric acid solution) and reaction temperature. Then, the friction coefficient, total transmittance, X-ray peak intensity ratio (%) [(020)/(200)] and crystalline barium sulfate shown in Table 1 were obtained.
【００１４】[0014]
【表１】[Table 1]
【００１５】＊摩擦係数：試料の硫酸バリウム粉体１ｇ
を人工皮を張り付けた直径５０ｍｍφ、厚み１０ｍｍの
２枚の円盤の間に保持し、５０ｇｆの垂直荷重を印加し
たまま片方の円盤を３００ｒｐｍ で回転させ、もう一
方の円盤でトルク（Ｆ）を検出し、粉体の摩擦係数（＝
Ｆ／５０）を算出した。*Friction coefficient: 1g of sample barium sulfate powder
is held between two disks with a diameter of 50 mmφ and a thickness of 10 mm covered with artificial skin, one disk is rotated at 300 rpm while applying a vertical load of 50 gf, and the torque (F) is detected with the other disk. The coefficient of friction of the powder (=
F/50) was calculated.
【図１】実施例１で得た本発明板状硫酸バリウムのＸ線
回折パターンである。FIG. 1 is an X-ray diffraction pattern of plate-like barium sulfate of the present invention obtained in Example 1.
【図２】比較例１で得た硫酸バリウムのＸ線回折パター
ンである。FIG. 2 is an X-ray diffraction pattern of barium sulfate obtained in Comparative Example 1.
Claims (2)
（０２０）と（２００）面の回折ピーク強度比が１．５
〜１００であることを特徴とする板状硫酸バリウム。Claim 1: In X-ray diffraction of an oriented sample, the diffraction peak intensity ratio of the (020) and (200) planes of the crystal is 1.5.
100-100.
を形成したときの散乱強度が５５％以上で、かつ全透過
率が７０％以上である請求項１記載の板状硫酸バリウム
。2. The plate-shaped barium sulfate according to claim 1, which has a scattering intensity of 55% or more and a total transmittance of 70% or more when a thin film having a concentration of 20% by weight and a thickness of 15 μm is formed.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2414786A JP2987645B2 (en) | 1990-12-27 | 1990-12-27 | Plate-shaped barium sulfate |
| US07/665,583 US5171572A (en) | 1990-03-07 | 1991-03-06 | Barium sulfate and cosmetic compositions comprising same |
| DE69111852T DE69111852D1 (en) | 1990-03-07 | 1991-03-06 | Platelet-shaped barium sulfate and cosmetic composition. |
| EP91103430A EP0445785B1 (en) | 1990-03-07 | 1991-03-06 | Plate-like barium sulfate and cosmetic composition |
| US07/936,202 US5262148A (en) | 1990-03-07 | 1992-08-27 | Process for preparing barium sulfate |
| US08/098,819 US5340582A (en) | 1990-03-07 | 1993-07-29 | Barium sulfate cosmetic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2414786A JP2987645B2 (en) | 1990-12-27 | 1990-12-27 | Plate-shaped barium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04231324A true JPH04231324A (en) | 1992-08-20 |
| JP2987645B2 JP2987645B2 (en) | 1999-12-06 |
Family
ID=18523230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2414786A Expired - Lifetime JP2987645B2 (en) | 1990-03-07 | 1990-12-27 | Plate-shaped barium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2987645B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009114038A (en) * | 2007-11-08 | 2009-05-28 | Denso Corp | Method of manufacturing crystal oriented ceramic |
| JP2010133189A (en) * | 2008-12-08 | 2010-06-17 | Alpha Kogyo Kk | Filler, and method for confirming filling |
-
1990
- 1990-12-27 JP JP2414786A patent/JP2987645B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009114038A (en) * | 2007-11-08 | 2009-05-28 | Denso Corp | Method of manufacturing crystal oriented ceramic |
| JP2010133189A (en) * | 2008-12-08 | 2010-06-17 | Alpha Kogyo Kk | Filler, and method for confirming filling |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2987645B2 (en) | 1999-12-06 |
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