JPS63218615A - Anti-suntan skin cosmetic - Google Patents
Anti-suntan skin cosmeticInfo
- Publication number
- JPS63218615A JPS63218615A JP5214487A JP5214487A JPS63218615A JP S63218615 A JPS63218615 A JP S63218615A JP 5214487 A JP5214487 A JP 5214487A JP 5214487 A JP5214487 A JP 5214487A JP S63218615 A JPS63218615 A JP S63218615A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- titanium
- fine particles
- particle size
- weight
- 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
- 239000002537 cosmetic Substances 0.000 title claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 61
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000009826 distribution Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims description 6
- 230000000475 sunscreen effect Effects 0.000 claims description 6
- 239000000516 sunscreening agent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 150000003609 titanium compounds Chemical class 0.000 abstract description 15
- 239000010936 titanium Substances 0.000 abstract description 10
- 229910052719 titanium Inorganic materials 0.000 abstract description 10
- -1 titanium alkoxide Chemical class 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 16
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 14
- 238000000635 electron micrograph Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 239000006071 cream Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 7
- 239000006200 vaporizer Substances 0.000 description 7
- 206010015150 Erythema Diseases 0.000 description 5
- 231100000321 erythema Toxicity 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011491 glass wool Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 2
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 2
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001089 thermophoresis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Cosmetics (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は日焼は止め皮膚化粧料に関し、詳しくは特定の
粒径分布を有する酸化チタン微粒子を皮膚化粧料基材に
配合することにより、２９０〜４００ｎｓの紫外線すべ
てに対して遮蔽効果を持ち、使用性の良好な日焼は止め
化粧料に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to sunscreen skin cosmetics, and more specifically, by blending titanium oxide fine particles having a specific particle size distribution into a skin cosmetic base material, The present invention relates to a sunscreen cosmetic that has a shielding effect against all ultraviolet rays of 290 to 400 ns and is easy to use.
［従来の技術および発明が解決しようとする問題点］
酸化チタンは人体に対する毒性が少なく、特に粒径が１
０〜１００ｒｖの大きさの酸化チタン粒子は紫外線の散
乱効果が大きいため化粧料に広く用いられている。[Problems to be solved by the prior art and the invention] Titanium oxide has low toxicity to the human body, especially when the particle size is 1.
Titanium oxide particles with a size of 0 to 100 rv are widely used in cosmetics because they have a large ultraviolet scattering effect.
例えば特公昭４７−４２５０２号公報には粒径３０〜４
０ｎｍの酸化チタンを配合した日焼は止め化粧料が開示
されている。特開昭５８−４９３０７号公報では粒径ｌ
Ｏ〜４０ｎｍの表面処理酸化チタンを配合した化粧料が
提案されている。また、特開昭５８−６２１０８号公報
では酸化チタンの粒径が紫外線の遮蔽効果に影響するこ
とが指摘されており、平均粒子径１０〜３０ｎｍの疎水
化された微粒子状酸化チタンを０．１〜４０重量％配合
した化粧料は、皮膚に紅斑を惹起する波長２９０〜３２
０ｎｍ （ＵＶ−Ｂ波長領域）の紫外線を反射散乱し皮
膚を紫外線から守るのに有効であるとしている。For example, in Japanese Patent Publication No. 47-42502, particle size 30-4
A sunscreen cosmetic containing 0 nm titanium oxide has been disclosed. In JP-A No. 58-49307, the particle size l
Cosmetics containing surface-treated titanium oxide of 0 to 40 nm have been proposed. Furthermore, in JP-A No. 58-62108, it has been pointed out that the particle size of titanium oxide affects the ultraviolet shielding effect, and 0.1 Cosmetics containing ~40% by weight contain wavelengths of 290 to 32, which cause erythema on the skin.
It is said to be effective in protecting the skin from ultraviolet rays by reflecting and scattering ultraviolet rays of 0 nm (UV-B wavelength range).
しかし、上記した化粧料等に用いられた微粒子酸化チタ
ンは形状がサイコロ状、直方体状、鱗片状、針状なとで
あり、球状のものはなかった。そのため、化粧料製造時
の分散性や保存中の安定性などが充分でなく、使用時に
おいてものび、つき、仕上りなどの点で満足のゆくもの
ではなかった。またこれらの酸化チタンは粒径分布も非
常に狭いために２９０〜３２０ｎｍの紫外線には遮蔽効
果はあるが、３２０〜４００ｎｍ （ＵＶ−へ波長領域
）の皮膚の黒化（サンタン）の原因になるとされている
紫外線の遮蔽は不可能であった。酸化チタンの配合量を
極端に増やせばすべての領域の紫外線を遮蔽することは
可能であるが、従来の酸化チタンを配合したものでは可
視光線の透過性が低減し、皮膚に塗布した際に青白さが
目立ち、厚化粧状となり好ましくないという問題点があ
った。However, the fine particles of titanium oxide used in the above-mentioned cosmetics and the like are dice-shaped, rectangular parallelepiped-shaped, scale-shaped, and needle-shaped, and there are no spherical ones. As a result, the dispersibility during cosmetic production and stability during storage were not sufficient, and the spread, adhesion, and finish during use were unsatisfactory. In addition, these titanium oxides have a very narrow particle size distribution, so although they have a shielding effect against ultraviolet rays in the 290-320 nm range, they can cause skin tanning (santan) in the 320-400 nm (UV-wavelength range). It was impossible to block the ultraviolet rays that were present. It is possible to block UV rays in all regions by extremely increasing the amount of titanium oxide, but conventional products containing titanium oxide reduce the transparency of visible light and cause a bluish-white appearance when applied to the skin. There was a problem in that it became noticeable and resulted in a thick cosmetic appearance, which was undesirable.
そこで本発明者らは、従来の酸化チタンを配合した化粧
料の諸問題を解決すべく鋭意研究を重ねた結果、特定の
粒径分布を有する球状の酸化チタン微粒子を配合するこ
とにより、該微粒子の化粧料基材への分散性や保存中の
安定性が良好で、皮膚へ塗布した際に青白みが少なく、
透明感を与え、しかもすべての領域の紫外線を遮蔽する
効果のあることを見出し、かかる知見に基いて本発明を
完成するに至った。Therefore, the present inventors have conducted intensive research to solve various problems of conventional cosmetics containing titanium oxide, and as a result, by blending spherical titanium oxide fine particles with a specific particle size distribution, the fine particles It has good dispersibility in cosmetic base materials and stability during storage, and has little paleness when applied to the skin.
They have discovered that it provides transparency and is effective in blocking ultraviolet rays in all regions, and based on this knowledge, they have completed the present invention.
［問題点を解決するための手段］
すなわち本発明は、皮膚化粧料基材に対して、特定の粒
径分布を有する球状の酸化チタン微粒子を０．０１〜５
０重量％の割合で配合したことを特徴とする日焼は止め
皮膚化粧料に関するものである。[Means for Solving the Problems] That is, the present invention provides spherical titanium oxide fine particles having a specific particle size distribution in an amount of 0.01 to 5
The present invention relates to a sunscreen skin cosmetic characterized in that it is blended in a proportion of 0% by weight.
本発明に用いる酸化チタンは球状であれば結晶性（ルチ
ル型、アナターゼ型あるいはこれらの混合形態）であっ
ても、非結晶性であってもよい。The titanium oxide used in the present invention may be crystalline (rutile type, anatase type, or a mixed form thereof) or non-crystalline as long as it is spherical.
ここで球状とは粒子の最小径が最大径の８０％以上のも
ので、好ましくは９０％以上で、表面がなめらかな、い
わゆるピンボン玉のような球をいう。Here, the term spherical refers to a particle whose minimum diameter is 80% or more of the maximum diameter, preferably 90% or more, and whose surface is smooth, such as a so-called pin-bond ball.
本発明でいう特定の粒径分布とは、下記に示す通りであ
る。The specific particle size distribution as used in the present invention is as shown below.
粒子径 含有量
５〜１９０１５〜１０重量％
２０〜４９ｎ＋＊ １０〜７０重量％５０〜７
９ｎｍ １〜８０重量％８０〜１１０９ｎ
１０〜２０重量％１１０〜１５０ｎｏ＋
５〜１０重量％このような球状酸化チタン微粒子
の１例につき、第１図にＸ線回折パターンを、第２図に
電子顕微鏡写真を示す。Particle size Content 5-190 15-10% by weight 20-49n+* 10-70% by weight 50-7
9nm 1-80% by weight 80-1109n
10-20% by weight 110-150no+
FIG. 1 shows an X-ray diffraction pattern, and FIG. 2 shows an electron micrograph of an example of such spherical titanium oxide fine particles containing 5 to 10% by weight.
このような酸化チタン微粒子は種々の方法で製造するこ
とができる０例えば気化したチタン化合物を熱分解また
は加水分解し、必要に応じて焼成することにより得るこ
とができる。Such titanium oxide fine particles can be produced by various methods.For example, they can be obtained by thermally decomposing or hydrolyzing a vaporized titanium compound and, if necessary, calcining it.
ここで用いるチタン化合物としてはチタンアルコキサイ
ドやハロゲン化チタンなど、加熱することにより容易に
気化するチタン化合物を用いる。The titanium compound used here is a titanium compound that is easily vaporized by heating, such as titanium alkoxide or titanium halide.
チタンアルコキサイドとして具体的には例えばチタンテ
トラメトキサイド、チタンテトラエトキサイド、チタン
テトライソプロポキサイド、チタンテトラブトキサイド
、ジェトキシチタンオキサイドなどを挙げることができ
る。またハロゲン化チタンとして具体的には四塩化チタ
ン、四臭化チタンなどのテトラハロゲン化チタンが挙げ
られる。Specific examples of the titanium alkoxide include titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and jetoxytitanium oxide. Specific examples of titanium halides include titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide.
さらにトリハロゲン化モノアルコキシチタン、モノハロ
ゲン化トリアルコキシチタン、ジハロゲン化ジアルコキ
シチタンなどの揮発性を有するチタン化合物を用いるこ
ともできる。これらチタン化合物は単独で用いてもよく
、あるいは２種類以上を組合せて用いてもよい。これら
の中でもチタンテトラメトキサイド、チタンテトラエト
キサイド、チタンテトライソプロポキサイドなどが好ま
しく、特にチタンテトライソホキサイドが好ましい。Further, volatile titanium compounds such as trihalogenated monoalkoxytitanium, monohalogenated trialkoxytitanium, and dihalogenated dialkoxytitanium can also be used. These titanium compounds may be used alone or in combination of two or more. Among these, titanium tetramethoxide, titanium tetraethoxide, titanium tetraisopropoxide, etc. are preferred, and titanium tetrasophoxide is particularly preferred.
これらチタン化合物を原料として球状チタンを製造する
には、第３図に示されているような反応装置を用い、以
下のごとくして製造することができる。すなわち、原料
のチタン化合物３はケミカルポンプ２などを用いて気化
器６に送り込む。気化器６においてはチタン化合物は加
熱された後、ノズルから噴出させるかまたはグラスウー
ル５など、表面積の大きな充填物上で気化させる。気化
温度は原料チタン化合物の沸点よりも若干低い温度が好
ましい。ここで気化したチタン化合物は窒素、アルゴン
、ヘリウム等の不活性ガスや空気などで希釈してもよい
。これらの気体は気化したチタン化合物を反応器に送り
込むためのキャリアーガスの役割りを果たすものである
。次いで、気化したチタン化合物を反応器７に送り込む
。反応器７は円筒または角筒などの筒状容器であり、外
部または内部から加熱される。反応器７の形状としては
直径と塔の高さの比が１：１から１：１００のものが用
いられ、その上部または下部より、上記の気化したチタ
ン化合物および希釈もしくは分解ガスを送り込む。分解
温度は３００℃以上が好ましい。また、反応器７中での
滞留時間は適宜決定すればよいが、好ましくは０．１〜
１０ｓｅｃとする。また流速は１〜５０ｃｍ／ｓｅｃが
好ましい。さらに原料濃度は２ ｘ １Ｏ−５１ｎｏｉ
）／ｊ！ ”’ ２ ｘ １０−’ｍｏＲ／Ｒが好まし
く、特に４ ｘ １０−’ｍｏｉ’／Ｊ 〜１２ｘ １
０−’ｍｏＩｌ／Ｊが好ましい。Spherical titanium can be produced using these titanium compounds as raw materials using a reaction apparatus as shown in FIG. 3 in the following manner. That is, the raw material titanium compound 3 is sent to the vaporizer 6 using the chemical pump 2 or the like. In the vaporizer 6, the titanium compound is heated and then ejected from a nozzle or vaporized on a filling material with a large surface area, such as glass wool 5. The vaporization temperature is preferably slightly lower than the boiling point of the raw material titanium compound. The titanium compound vaporized here may be diluted with an inert gas such as nitrogen, argon, or helium, or air. These gases serve as carrier gases for feeding the vaporized titanium compound into the reactor. Next, the vaporized titanium compound is sent to the reactor 7. The reactor 7 is a cylindrical container such as a cylinder or a rectangular tube, and is heated from the outside or inside. The shape of the reactor 7 used is such that the ratio of diameter to column height is 1:1 to 1:100, and the vaporized titanium compound and dilution or decomposition gas are fed into the reactor from its upper or lower part. The decomposition temperature is preferably 300°C or higher. In addition, the residence time in the reactor 7 may be determined as appropriate, but is preferably 0.1 to
It is assumed to be 10 seconds. Moreover, the flow rate is preferably 1 to 50 cm/sec. Furthermore, the raw material concentration is 2 x 1O-51noi
)/j! "' 2 x 10-'moR/R is preferred, especially 4 x 10-'moi'/J ~ 12x 1
0-'mol/J is preferred.
このようにして生成した酸化チタン微粒子はそのままフ
ィルターで回収してもよいが、できるだけ早く冷却すれ
ば粒子同志が凝集することなく微粒子状のものが得られ
る。生成した酸化チタンの分離はメンブランフィルタ−
９濾紙などのフィルターで濾過してフィルター表面上に
捕集する。この際捕集器内部に冷却部分を設は熱泳動に
より収集してもよい。また、収集した酸化チタン微粒子
は必要に応じて適宜公知の技術で疎水化、親木化等の表
面処理を行なうことができる。The titanium oxide fine particles thus generated may be collected as they are by a filter, but if they are cooled as quickly as possible, fine particles can be obtained without agglomeration of the particles. The generated titanium oxide is separated using a membrane filter.
9 Filter through a filter such as filter paper and collect on the filter surface. At this time, a cooling section may be provided inside the collector to collect the material by thermophoresis. In addition, the collected titanium oxide fine particles can be subjected to surface treatments such as hydrophobicization and wood-philicization using appropriate known techniques, if necessary.
このようにして特定の粒径分布を有し、粒径５〜１５０
ｎｍの球状の酸化チタンを回収することができる。この
球状の酸化チタン微粒子を乳液、クリーム等の化粧料基
材に０．０１〜５０重量％、好ましくは０．０１〜２０
重量％の割合で配合して化粧料とする。この酸化チタン
微粒子の配合割合が０．０１重量％未満では紫外線の遮
蔽効果が十分でなく、また５０重量％を超えると均一分
散が困難となるため、いずれも好ましくない。In this way, it has a specific particle size distribution, with a particle size of 5 to 150
Spherical titanium oxide of nanometer size can be recovered. These spherical titanium oxide fine particles are added to cosmetic base materials such as emulsions and creams in an amount of 0.01 to 50% by weight, preferably 0.01 to 20% by weight.
It is blended in a proportion of % by weight to make a cosmetic. If the blending ratio of the titanium oxide fine particles is less than 0.01% by weight, the ultraviolet ray shielding effect will not be sufficient, and if it exceeds 50% by weight, uniform dispersion will become difficult, so both are not preferred.
［実施例］ 次に実施例により本発明をさらに詳細に説明する。[Example] Next, the present invention will be explained in more detail with reference to Examples.
製造例！
（アモルファス球状酸化チタン微粒子の製造）第３図に
示す装置を用いて球状酸化チタンの製造を行なった。原
料としてチタンテトライソプロポキサイドを０．３ｃｃ
／ｍｉｎ、の割合でケミカルポンプ２により２００℃に
加熱した気化器６に送り込んだ。この気化器は内径１７
ｍｍ、長さ１０ｍｍで、内部にグラスウール５を充填し
たものを用いた。同時に気化したチタンテトライソプロ
ポキサイドを送るためにキャリアーガスとして乾燥空気
を、チタンテトライソプロポキサイドの濃度が５ Ｘ
１０−’ｍａｉｌ／Ｉ！どなるような割合で送り込んだ
。次いで、この混合ガスを３００℃に加熱した反応器７
に送り込んだ。反応器７は内径５５ｍｍ、長さ１１００
ＩＩ１のものを用いた。さらに反応器７には分解促進用
ガスとして水蒸気を、キャリアーガスとともに反応させ
た。全体としてのキャリアーガスの流量は２０，０００
ｍ１ｄ／ｍｉｎ、で滞留一時間は約０．６秒であった。Manufacturing example! (Production of amorphous spherical titanium oxide fine particles) Spherical titanium oxide was produced using the apparatus shown in FIG. 0.3cc of titanium tetraisopropoxide as raw material
/min, into a vaporizer 6 heated to 200° C. by a chemical pump 2. This vaporizer has an inner diameter of 17
mm, length 10 mm, and the inside was filled with glass wool 5. At the same time, dry air was used as a carrier gas to transport the vaporized titanium tetraisopropoxide, and the concentration of titanium tetraisopropoxide was 5X.
10-'mail/I! They were sent in at an alarming rate. Next, this mixed gas was heated to 300°C in reactor 7.
I sent it to. Reactor 7 has an inner diameter of 55 mm and a length of 1100 mm.
II1 was used. Further, in the reactor 7, water vapor was reacted as a gas for promoting decomposition together with a carrier gas. The overall carrier gas flow rate is 20,000
The residence time was approximately 0.6 seconds at m1d/min.
生成した酸化チタンはＸ線回折測定の結果、非晶質であ
った。第４図にＸ線回折パターンを、第５図に電子顕微
鏡写真を示す。また、このものの粒径分布は下記の通り
であった。なお、粒径分布は電子顕微鏡写真から大きさ
と個数分布を求め、比重３．０を用いて重量％を算出し
た。As a result of X-ray diffraction measurement, the produced titanium oxide was found to be amorphous. FIG. 4 shows an X-ray diffraction pattern, and FIG. 5 shows an electron micrograph. Moreover, the particle size distribution of this product was as follows. Incidentally, the particle size distribution was determined by determining the size and number distribution from an electron micrograph, and calculating the weight % using a specific gravity of 3.0.
粒子径 含有量
５〜１９ｎｍｌＯ重量％
２０〜４９ｎｍｌＯ瓜量％
５０〜７９ｎｍ６０重量％
８０〜１１０９ｎ １０重量％１１０〜１５
０ｎｍ １０重量％製造例２
（アナターゼ型球状酸化チタン微粒子の製造）反応は製
造例１と同じ装置で行なった。原料のチタンテトライソ
プロポキサイドを０．３ｃｃ／ｍｌｎ、の割合でケミカ
ルポンプ２により２００℃に加熱した気化器６に送り込
んだ。同時に気化したチタン化合物を送るためにキャリ
アーガスとして乾燥空気を、チタンテトライソプロポキ
サイドの濃度が５ Ｘ １０−’ｍａｉｌ／４１となる
ような割合で送り込んだ。Particle size Content 5-19nmlO weight% 20-49nmlO weight% 50-79nm 60% by weight 80-1109n 10% by weight 110-15
0 nm 10% by weight Production Example 2 (Production of Anatase Type Spherical Titanium Oxide Fine Particles) The reaction was carried out in the same apparatus as Production Example 1. Titanium tetraisopropoxide as a raw material was fed into a vaporizer 6 heated to 200° C. by a chemical pump 2 at a rate of 0.3 cc/ml. At the same time, in order to transport the vaporized titanium compound, dry air was supplied as a carrier gas at a rate such that the concentration of titanium tetraisopropoxide was 5 x 10-'mail/41.
次いで、この混合ガスを６００℃に加熱した反応器７に
送り込んだ、さらに反応器７にはキャリアーガスととも
に反応促進のため水蒸気を送り込んだ。全体としてのキ
ャリアーガスの流量は２０．０００１１１７／ｌｌｌ１
ｎ、で滞留時間は約０．６秒であった。生成した酸化チ
タンはＸ線回折測定の結果、結晶性でありその形態はア
ナターゼ型であった。第６図にＸ線回折パターンを、第
７図に電子顕微鏡写真を示す、また、このものの粒径分
布は下記の通りであった。なお、粒径分布は製造例１と
同様な方法で求めた。Next, this mixed gas was fed into a reactor 7 heated to 600° C., and water vapor was further fed into the reactor 7 together with a carrier gas to promote the reaction. The overall carrier gas flow rate is 20.0001117/lll1
n, the residence time was about 0.6 seconds. As a result of X-ray diffraction measurement, the produced titanium oxide was found to be crystalline and in the form of anatase. The X-ray diffraction pattern is shown in FIG. 6, and the electron micrograph is shown in FIG. 7.The particle size distribution of this product was as follows. Incidentally, the particle size distribution was determined in the same manner as in Production Example 1.
粒子径 含有量
５〜１９ｎｍｌＯ重量％
２０〜４９ｎｍ１５重量％
５（１〜７９ｎｍ ５０重量％８０〜１１０
９ｎ １５瓜量％１１０〜１５０ｒ＋＋ｓ
１０重量％製造例３
（ルチル型球状酸化チタン微粒子の製造）製造例１で得
られた試料を電気炉にて８５０℃で２時間焼成した。焼
成後の生成物はＸ線回折測定の結果、結晶性であり、そ
の形態はルチル型の二酸化チタンであった。第８図にこ
のもののＸ線回折パターンを、第９図に電子顕微鏡写真
を示す。Particle size Content: 5-19 nm 15 wt% 20-49 nm 5 (1-79 nm 50 wt% 80-110
9n 15 Melon amount% 110-150r++s
10% by weight Production Example 3 (Production of rutile-type spherical titanium oxide fine particles) The sample obtained in Production Example 1 was fired at 850° C. for 2 hours in an electric furnace. As a result of X-ray diffraction measurement, the product after firing was found to be crystalline, and its form was rutile-type titanium dioxide. FIG. 8 shows an X-ray diffraction pattern of this product, and FIG. 9 shows an electron micrograph.
実施例１〜３および比較例１，２
酸化チタンとして、前記製造例１〜３で得られた特定の
粒径分布を有する球状酸化チタン微粒子３種（実施例１
〜３）、または比較のために特開昭８１−２０１６０４
号明細書記載の実施例に準じて製造した粒径分布の狭い
非晶質の球状酸化チタン微粒子（比較例１）または立方
体状の酸化チタン微粒子（***デグッサ社製、商品名：
Ｐ−２５） （比較例２）を用いて、下記の処方に
よりファンデーションクリームを調製した。Examples 1 to 3 and Comparative Examples 1 and 2 As titanium oxide, three kinds of spherical titanium oxide fine particles having a specific particle size distribution obtained in Production Examples 1 to 3 (Example 1) were used as titanium oxide.
~3), or for comparison, JP-A-81-201604
Amorphous spherical titanium oxide fine particles with a narrow particle size distribution (Comparative Example 1) or cubic titanium oxide fine particles (manufactured by Degussa AG, West Germany, product name:
P-25) (Comparative Example 2), a foundation cream was prepared according to the following formulation.
タ ル り
１５．０ ％カ オ リ
ン ４．０ ％
の酸化チタン微粒子（比較例２） ２
０．０ ％酸化鉄（赤）０．３％
酸化鉄（黄）０．７％
酸化鉄（黒） ０．０３％固形パラフ
ィン ３．０％ラ ノ リ
ン
１０００％流動パラフィン ２７．０
％グリセリルモノオレイン酸エステル
５８０％精 製 水
１５．０％香 料
適 量タルク、カオリン、球状酸化チタン
または立方体状酸化チタン、酸化鉄（赤、黄、黒）を混
合し、ボールミルで処理して粉体部を得た。この粉体部
に流動パラフィンの一部とグリセリルモノオレイン酸エ
ステルを加え、ホモミキサーで均一に分散し、精製水を
除く他の成分を加熱融解してこれに加え、７０℃に保っ
て油相とした。次に精製水を７０℃に加熱したのち油相
に加え、ホモミキサーで均一に乳化分散し、攪拌しなが
ら４０℃に保ち、ファンデーションクリームを調製した
。Tarri
15.0% Kaori
4.0%
Titanium oxide fine particles (Comparative Example 2) 2
0.0% iron oxide (red) 0.3% iron oxide (yellow) 0.7% iron oxide (black) 0.03% solid paraffin 3.0% lanoli
hmm
1000% liquid paraffin 27.0
%glyceryl monooleate
580% purified water
15.0% fragrance
Appropriate amounts of talc, kaolin, spherical titanium oxide or cubic titanium oxide, and iron oxide (red, yellow, black) were mixed and processed in a ball mill to obtain a powder part. Add a part of liquid paraffin and glyceryl monooleate to this powder, disperse uniformly with a homomixer, heat and melt the other components except for purified water, add to this, and keep at 70°C to phase out the oil phase. And so. Next, purified water was heated to 70°C, added to the oil phase, uniformly emulsified and dispersed using a homomixer, and maintained at 40°C while stirring to prepare a foundation cream.
このファンデーションクリームについて以下の如き試験
を行なった。The following tests were conducted on this foundation cream.
（１）紫外線（ＵＶ）遮蔽性
前記の処方により調製されたファンデーションクリーム
を透明石英板上に厚さ５ｐｍの薄膜を作り、日立２２８
型ダブルビ一ム分光光度計を用いて２００〜４００ｒｖ
の波長領域の吸光度を測定し、ＵＶＪ蔽効果を調べた。(1) Ultraviolet (UV) shielding property A thin film with a thickness of 5 pm was made on a transparent quartz plate with the foundation cream prepared according to the above formulation, and Hitachi 228
200-400rv using a type double beam spectrophotometer
The absorbance in the wavelength region was measured to investigate the UVJ shielding effect.
この結果を第１表に示す。The results are shown in Table 1.
（２）実使用時の紫外線防御効果および使用感衣に、上
記５種のファンデーションクリーム（試料）を皮膚１
ｃｍ２当り０．１ｇの割合でパネラ−１０人の皮膚に塗
布して実使用時の紫外線防御効果および使用感を調べた
。実使用時の紫外線防御効果の調査は昭和６１年７月２
７日（快晴）、千葉県富津市富津海岸において行ない、
午前１１時から午後１時までの２時間、試料塗布皮膚面
に日光を照射したのち試料を落とし、日焼は状態（紅斑
の強弱）を１時間後および１日後の２回にわたり肉眼で
判定した。(2) Apply the above five types of foundation creams (samples) to the skin 1 to 1 to determine the UV protection effect during actual use and to the affected skin.
It was applied to the skin of 10 panelists at a rate of 0.1 g per cm 2 to examine the UV protection effect and feeling of use during actual use. A survey of the UV protection effect during actual use was conducted on July 2, 1986.
The event was held on the 7th (sunny day) at Futtsu Beach, Futtsu City, Chiba Prefecture.
After irradiating the sample-applied skin with sunlight for 2 hours from 11:00 a.m. to 1:00 p.m., the sample was dropped, and the condition of sunburn (strength or weakness of erythema) was determined visually twice, once one hour later and one day later. .
また実使用時の使用感については、このファンデーショ
ンクリームについて「のび」、ｒつき」、「さっばり感
」および「総合評価」の４項目で評価した。結果は各項
目についてパネラ−が最も良いと回答した人数で示した
。これらの結果を第１表に示す。第１表から明らかなよ
うに、特定の粒径分布を有する球状酸化チタン微粒子を
用いた本発明のファンデーションクリームは、従来のも
のよりも紫外線防御効果においても、実使用性能におい
てもすぐれていることが判る。Regarding the feeling of use during actual use, this foundation cream was evaluated in four categories: ``spreadability'', ``stickiness'', ``light feeling'', and ``overall evaluation''. The results are shown as the number of panelists who answered that each item was the best. These results are shown in Table 1. As is clear from Table 1, the foundation cream of the present invention, which uses spherical titanium oxide fine particles with a specific particle size distribution, is superior to conventional products in terms of UV protection effect and performance in actual use. I understand.
◆１：３００ｒ＋ｍの吸光度が 中２：３６０ｎｍの
吸光度が２．８以上 ・・・◎ １．８以上 ・
・・◎２．７〜２．５ ・Ｏ１，７〜１．５−０２．４
〜２．０・・・△ １．４〜１，０・・・△１．
９以下 ・・・×０．９以下 ・・・Ｘとして表わした
。 とじて表わした。◆1: Absorbance at 300r+m Medium 2: Absorbance at 360nm is 2.8 or more ・・・◎ 1.8 or more ・
・・◎2.7~2.5 ・O1,7~1.5-02.4
~2.0...△ 1.4~1,0...△1.
9 or less ... x 0.9 or less ... Expressed as X. It is expressed in a closed form.
中３：相対比較結果 ○：全く紅斑が認められない。Middle 3: Relative comparison results ○: No erythema observed at all.
△：弱い紅斑が認められる。△: Weak erythema is observed.
×：やや強い紅斑が認められる。×: Slightly strong erythema is observed.
中４＝パネラー１Ｏ人について最もよいと答えた人数
［発明の効果］
本発明の化粧料は、波長２９０〜４０Ｑｎｍの紫外線す
べてに対してすぐれた遮蔽効果を有し、使用感も良好で
青白さもない。また本発明の化粧料は製造時の粒子の分
散性、安定性が良好である。Medium 4 = Number of panelists who answered that it was the best among 10 people [Effects of the invention] The cosmetic of the present invention has an excellent shielding effect against all ultraviolet rays with a wavelength of 290 to 40 Qnm, has a good feeling of use, and does not cause paleness. do not have. Furthermore, the cosmetic composition of the present invention has good particle dispersibility and stability during production.
第１図は本発明で用いる酸化チタン微粒子の１例につい
てのＸ線回折パターンであり、第２図はその電子顕微鏡
写真である。第３図は本発明の製造例で用いた装置を示
す説明図である。第４図は本発明の製造例１で得られた
アモルファス球状酸化チタン微粒子のＸ線回折パターン
であり、第５図はその電子顕微鏡写真である。第６図は
本発明の製造例２で得られたアナターゼ型球状酸化チタ
ン微粒子のＸ線回折パターンであり、第７図はその電子
顕微鏡写真である。第８図は製造例３で得られたルチル
型球状酸化チタン微粒子のＸ線回折パターンであり、第
９図はその電子顕微鏡写真である。
１・・・モーター、 ２・・・ケミカルポンプ
。
３・・・原料、 ４・・・ヒーター。
５・・・グラスウール、 ６・・・気化器。
７・・・反応器、 ８・・・温度計。
９・・・マントルヒーター、１０・・・受槽。
１１・・・フィルター
００ｎｍ
００ｎｍ
第３図
手続主甫正書（方式） ６
昭和６２年６月２５日
特許庁長官 小川 邦人 殿 ７１
、事件の表示
特願昭６２−５２１４４ ８２、発
明の名称
日焼は止め皮膚化粧料 を３、補
正をする者
東京都中央区京橋１丁目１番１０号
補正の対象
明細書の図面の簡単な説明の欄
補正の内容
別紙のとおり
、添付書類の目録
明細書の図面の簡単な説明の欄
正確に記載した書面 １通（以上）
４、図面の簡単な説明
第１図は本発明で用いる酸化チタン微粒子の１例につい
てのＸ線回折パターンであり、第２図は本発明で用いる
酸化チタン微粒子の１例についての粒子構造を示す電子
顕微鏡写真である。第３図は本発明の製造例で用いた装
置を示す説明図である。第４図は本発明の製造例１で得
られたアモルファス球状酸化チタン微粒子のＸ線回折パ
ターンであり、第５図は本発明の製造例１で得られたア
モルファス球状酸化チタン微粒子の粒子構造を示す電子
顕微鏡写真である。第６図は本発明の製造例２で得られ
たアナターゼ型球状酸化チタン微粒子のＸ線回折パター
ンであり、第７図は本発明の製造例２で得られたアナタ
ーゼ型球状酸化チタン微粒子の粒子構造を示す電子顕微
鏡写真である。第８図は製造例３で得られたルチル型球
状酸化チタン微粒子のＸ線回折パターンであり、第９図
は製造例３で得られたルチル型球状酸化チタン微粒子の
粒子構造を示す電子顕微鏡写真である。
１・・・モーター、 ２・・・ケミカルポンプ
。
３・・・原料、 ４・・・ヒーター。
５・・・グラスウール、 ６・・・気化器。
７・・・反応器、 ８・・・温度計。
９・・・マントルヒーター、 １０・・・受槽。
１１・・・フィルターFIG. 1 is an X-ray diffraction pattern of an example of titanium oxide fine particles used in the present invention, and FIG. 2 is an electron micrograph thereof. FIG. 3 is an explanatory diagram showing an apparatus used in a manufacturing example of the present invention. FIG. 4 is an X-ray diffraction pattern of amorphous spherical titanium oxide fine particles obtained in Production Example 1 of the present invention, and FIG. 5 is an electron micrograph thereof. FIG. 6 is an X-ray diffraction pattern of anatase type spherical titanium oxide fine particles obtained in Production Example 2 of the present invention, and FIG. 7 is an electron micrograph thereof. FIG. 8 is an X-ray diffraction pattern of the rutile type spherical titanium oxide fine particles obtained in Production Example 3, and FIG. 9 is an electron micrograph thereof. 1...Motor, 2...Chemical pump. 3...Raw material, 4...Heater. 5... Glass wool, 6... Vaporizer. 7...Reactor, 8...Thermometer. 9... Mantle heater, 10... Receiving tank. 11...Filter 00nm 00nm Figure 3 Procedural Master's Manual (Method) 6 June 25, 1988 Mr. Kunito Ogawa, Commissioner of the Patent Office 71
, Indication of the case, Patent Application No. 62-52144 82, Title of the invention: Sunscreen and skin cosmetics 3. Person making the amendment: No. 1-10, Kyobashi, Chuo-ku, Tokyo Simple drawing of the specification to be amended Contents of the amendment in the explanation column As shown in the attached document, the brief explanation column of the drawings in the catalog specification of the attached documents must be accurately described in one copy (or more) 4. Brief explanation of the drawings Figure 1 shows the oxidation used in the present invention. This is an X-ray diffraction pattern of one example of titanium fine particles, and FIG. 2 is an electron micrograph showing the particle structure of one example of titanium oxide fine particles used in the present invention. FIG. 3 is an explanatory diagram showing an apparatus used in a manufacturing example of the present invention. Figure 4 shows the X-ray diffraction pattern of the amorphous spherical titanium oxide fine particles obtained in Production Example 1 of the present invention, and Figure 5 shows the particle structure of the amorphous spherical titanium oxide fine particles obtained in Production Example 1 of the present invention. It is an electron micrograph shown. FIG. 6 is an X-ray diffraction pattern of anatase-type spherical titanium oxide fine particles obtained in Production Example 2 of the present invention, and FIG. 7 is an X-ray diffraction pattern of anatase-type spherical titanium oxide fine particles obtained in Production Example 2 of the present invention. It is an electron micrograph showing the structure. Figure 8 is an X-ray diffraction pattern of the rutile type spherical titanium oxide fine particles obtained in Production Example 3, and Figure 9 is an electron micrograph showing the particle structure of the rutile type spherical titanium oxide fine particles obtained in Production Example 3. It is. 1...Motor, 2...Chemical pump. 3...Raw material, 4...Heater. 5... Glass wool, 6... Vaporizer. 7...Reactor, 8...Thermometer. 9... Mantle heater, 10... Receiving tank. 11...filter
Claims (1)
の酸化チタン微粒子を０．０１〜５０重量％の割合で配
合したことを特徴とする日焼け止め皮膚化粧料。 粒子径 含有量 ５〜１９ｎｍ ５〜１０重量％ ２０〜４９ｎｍ １０〜７０重量％ ５０〜７９ｎｍ １〜８０重量％ ８０〜１０９ｎｍ １０〜２０重量％ １１０〜１５０ｎｍ ５〜１０重量％[Scope of Claims] A sunscreen skin cosmetic product characterized by blending spherical titanium oxide fine particles having the following particle size distribution into a skin cosmetic base material at a ratio of 0.01 to 50% by weight. . Particle size Content 5-19nm 5-10% by weight 20-49nm 10-70% by weight 50-79nm 1-80% by weight 80-109nm 10-20% by weight 110-150nm 5-10% by weight
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5214487A JPS63218615A (en) | 1987-03-09 | 1987-03-09 | Anti-suntan skin cosmetic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5214487A JPS63218615A (en) | 1987-03-09 | 1987-03-09 | Anti-suntan skin cosmetic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63218615A true JPS63218615A (en) | 1988-09-12 |
Family
ID=12906681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5214487A Pending JPS63218615A (en) | 1987-03-09 | 1987-03-09 | Anti-suntan skin cosmetic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63218615A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01180819A (en) * | 1988-01-11 | 1989-07-18 | Pola Chem Ind Inc | Cosmetic |
| WO1996037560A1 (en) * | 1995-05-24 | 1996-11-28 | The Procter & Gamble Company | Titanium dioxide hydrogel and sunscreen composition containing it |
| JP2018521060A (en) * | 2015-06-30 | 2018-08-02 | アモーレパシフィック コーポレーション | Sunscreen cosmetic composition |
-
1987
- 1987-03-09 JP JP5214487A patent/JPS63218615A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01180819A (en) * | 1988-01-11 | 1989-07-18 | Pola Chem Ind Inc | Cosmetic |
| WO1996037560A1 (en) * | 1995-05-24 | 1996-11-28 | The Procter & Gamble Company | Titanium dioxide hydrogel and sunscreen composition containing it |
| JP2018521060A (en) * | 2015-06-30 | 2018-08-02 | アモーレパシフィック コーポレーション | Sunscreen cosmetic composition |
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