JPS63141912A - Cosmetic - Google Patents
CosmeticInfo
- Publication number
- JPS63141912A JPS63141912A JP28777786A JP28777786A JPS63141912A JP S63141912 A JPS63141912 A JP S63141912A JP 28777786 A JP28777786 A JP 28777786A JP 28777786 A JP28777786 A JP 28777786A JP S63141912 A JPS63141912 A JP S63141912A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- titanium
- fine particles
- cosmetic
- oxide fine
- 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 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000010419 fine particle Substances 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 abstract description 36
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 15
- 239000010936 titanium Substances 0.000 abstract description 15
- 229910052719 titanium Inorganic materials 0.000 abstract description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003609 titanium compounds Chemical class 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000012159 carrier gas Substances 0.000 description 12
- 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 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 238000002835 absorbance Methods 0.000 description 10
- 239000006071 cream Substances 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- -1 titanium alkoxide Chemical class 0.000 description 7
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229960005235 piperonyl butoxide Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000000635 electron micrograph Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 239000006200 vaporizer Substances 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008160 cosmetics carrier oil Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 2
- 206010015150 Erythema Diseases 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 231100000321 erythema Toxicity 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 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 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
- 239000000049 pigment Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- 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 1
- 238000004438 BET method Methods 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- DMHAYBRJLHVFHF-UHFFFAOYSA-N [O-]CC.[O-]CC.[O-]CC.[O-]CC.[Ti+4].[Ti+4] Chemical compound [O-]CC.[O-]CC.[O-]CC.[O-]CC.[Ti+4].[Ti+4] DMHAYBRJLHVFHF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000149 argon plasma sintering Methods 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
- 239000002199 base oil Substances 0.000 description 1
- 238000005282 brightening 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
- 238000001354 calcination Methods 0.000 description 1
- 229960001777 castor oil Drugs 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- KELHQGOVULCJSG-UHFFFAOYSA-N n,n-dimethyl-1-(5-methylfuran-2-yl)ethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=C(C)O1 KELHQGOVULCJSG-UHFFFAOYSA-N 0.000 description 1
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229940032094 squalane Drugs 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 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
- 238000001089 thermophoresis Methods 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 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
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は化粧料に関し、詳しくは実質的に結晶性かつ実
質的に球状の酸化チタン微粒子を化粧料基材に配合する
ことにより、製造時の粒子の分散性、貯蔵安定性が良好
で、可視光透過性および紫外線遮蔽効果が優れており、
使用性の良好な化粧料に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to cosmetics, and more specifically, by blending substantially crystalline and substantially spherical titanium oxide fine particles into a cosmetic base material, The particles have good dispersibility and storage stability, and have excellent visible light transmittance and ultraviolet shielding effect.
This invention relates to cosmetics with good usability.
［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、しかも隠蔽力
が強いために化粧料に広く用いられている。酸化チタン
は通常特定の粒子径をもたず、付着力が強いために塊状
の粒子であり、アナターゼ型およびルチル型のいずれも
可視光線をほとんど吸収しないので白色である。屈折率
はアナターゼ型２．５２．ルチル型２．７２といずれも
白色の粉末中級も高い、また一般顔料用酸化チタンの粒
径は０．２〜０．４鉢層であり、これらが酸化チタンの
最も可視光線の散乱効果の大きい粒径であるとされてい
る。このように酸化チタンは顔料として化耕料に特に好
んで配合されている。さらに粒径が０．１ ｕ、ｒａ以
下の微粒子になると紫外線を散乱させる効果が大きくな
るため化粧料に広く用いられている。[Prior Art and Problems to be Solved by the Invention] Titanium oxide is widely used in cosmetics because it has little toxicity to the human body and has strong hiding power. Titanium oxide usually does not have a specific particle size and is a lumpy particle due to its strong adhesive force, and both anatase type and rutile type are white because they hardly absorb visible light. The refractive index is anatase type 2.52. The rutile type is 2.72 and both white powder intermediate grades are also high, and the particle size of titanium oxide for general pigments is 0.2 to 0.4 pot layer, and these are titanium oxide that has the largest visible light scattering effect. It is said to be the particle size. As described above, titanium oxide is particularly preferably blended as a pigment in agrochemicals. Furthermore, fine particles with a particle size of 0.1 u, ra or less have a greater effect of scattering ultraviolet rays, and are therefore widely used in cosmetics.
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。また、特開昭５８−４９３０７号公報では
粒径ｌＯ〜４０ｎｓ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。さらに特開昭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、乎均粒子径ｌＯ〜３０ｎｍ
の疎水化された微粒子状耐化チタンを配合した化粧料は
、皮膚に紅斑を惹起する２９０〜３２０ｎｍ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. Furthermore, Japanese Patent Application Laid-Open No. 58-49307 proposes a cosmetic containing surface-treated titanium oxide having a particle size of 10 to 40 ns. Furthermore, JP-A-58-62108
In the publication, it is pointed out that the particle size of titanium oxide affects the ultraviolet shielding effect, and the average particle size is lO ~ 30 nm.
Cosmetics containing hydrophobized particulate hardened titanium are said to be effective in protecting the skin from ultraviolet rays by reflecting and scattering ultraviolet rays of 290 to 320 nm that cause erythema on the skin.
しかし、上記した化粧料等に用いられた酸化チタンは形
状がサイコロ状、直方体状９Ｍ片状。However, the titanium oxide used in the above-mentioned cosmetics and the like has a dice-like shape, a rectangular parallelepiped-like 9M piece.
針状をなすものであるため、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、しかも伸び、つき、自
然な仕上りなどの使用性に劣るという欠点があった。ま
た、紫外線を充分に遮蔽するために酸化チタンの配合量
を増やす必要があり。Because they are needle-shaped, they have the drawbacks of insufficient dispersibility during cosmetic production and stability during storage, and poor usability such as spreadability, stickiness, and natural finish. Additionally, it is necessary to increase the amount of titanium oxide in order to sufficiently block UV rays.
この場合従来の酸化チタンを配合した化粧料は可視光線
の透過性が充分でないため微粒子相互の干渉作用により
皮膚に塗布した際に青白さが目立ち、好ましくないとい
う問題点があった。In this case, conventional cosmetics containing titanium oxide do not have sufficient visible light transmittance, so when applied to the skin, the interference between the fine particles makes the skin look pale, which is not desirable.
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、実質的
に結晶性かつ実質的に球状の酸化チタン微粒子を配合し
た化粧料が、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、皮膚へ塗布したときに青白みが少な
く、透明感を与え、しかも紫外線の遮蔽効果のすぐれて
いることを見出し、この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, a cosmetic containing substantially crystalline and substantially spherical titanium oxide fine particles has been developed. discovered that the fine particles have good dispersibility in cosmetic base materials and stability during storage, have little paleness when applied to the skin, give a transparent appearance, and have excellent ultraviolet shielding effects. Based on this knowledge, the present invention was completed.
［問題点を解決するための手段］
すなわち未発明は、実質的に結晶性かつ実質的に球状の
酸化チタン微粒子を０．０１〜５０重量％配合してなる
化粧ネ４である。[Means for Solving the Problems] That is, what has not yet been invented is a makeup paste 4 which contains 0.01 to 50% by weight of substantially crystalline and substantially spherical titanium oxide fine particles.
本発明に使用する酸化チタンは、実Ｔ的に結晶性でしか
も実質的に球状をなす微粒子状のものである。ここで実
質的に結晶性でとは、通常ルチル型またはアナターゼ型
のものであることを意味するが、これら両者の混合形態
であってもよい、また実質的に球状とは粒子の最小径が
最大径の８０％以上のもので、好ましくは粒子の最小径
が最大径の９０％以上の、表面がなめらかなものを相称
する。さらにこの実質的に結晶性かつ実質的に球状の酸
化チタン微粒子の平均粒子径は０．００５〜０．０３μ
鳳（５〜３０ｎ鵬）、粒子径分布は０．００１〜０．０
５鉢層（１〜５０■）であり、比表面積は３０〜１００
ｍ２／ｇ （ＢＥＴ法）と非常に大きい。コノヨラな
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。The titanium oxide used in the present invention is actually crystalline and in the form of fine particles that are substantially spherical. Here, "substantially crystalline" usually means that it is of rutile type or anatase type, but it may also be a mixture of these two forms, and "substantially spherical" means that the minimum diameter of the particles is Particles with a smooth surface having a diameter of 80% or more of the maximum diameter, preferably a minimum diameter of 90% or more of the maximum diameter are commonly referred to as particles. Furthermore, the average particle diameter of the substantially crystalline and substantially spherical titanium oxide fine particles is 0.005 to 0.03μ.
Peng (5-30n Peng), particle size distribution is 0.001-0.0
There are 5 pot layers (1 to 50 cm), and the specific surface area is 30 to 100.
m2/g (BET method), which is extremely large. FIG. 1 shows an X-ray diffraction pattern and FIG. 2 shows an electron micrograph of an example of fine titanium oxide particles.
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、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, by thermally decomposing or hydrolyzing a vaporized titanium compound and, if necessary, calcining the titanium compound.
アナターゼ型の球状酸化チタン微粒子を製造する具体的
な方法としては、例えば第３図に示されているような反
応装置を用い、以下の如くして製造することができる。As a specific method for producing anatase type spherical titanium oxide fine particles, for example, using a reaction apparatus as shown in FIG. 3, they can be produced as follows.
先ず、原料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。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２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。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、チタンテトライン
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。First, a titanium compound that is easily vaporized by heating, such as titanium alkoxide or titanium halide, is used as a raw material. Specific examples of the titanium alkoxide include titanium tetramethoxide, di-titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, and jetoxytitanium oxide. Specific examples of titanium halides include titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide. 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 tetraline propoxide, etc. are preferred, and titanium tetrasophoxide is particularly preferred. Sides are preferred.
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４など、表面積の大きな充填物上で気化
させる。気化せしめられたチタン化合物は適宜他の気体
で希釈してもよい、この気体は気化せしめられたチタン
化合物を反応器に送り込むためのキャリアーガスとして
の役割を果たすものである。この気体としては窒素、ア
ルゴン、ヘリウム等の不活性ガスや空気などを用いるこ
とができる。The compound is heated and then ejected through a nozzle or vaporized over a large surface area packing such as glass wool 4. The vaporized titanium compound may be optionally diluted with another gas, which serves as a carrier gas for feeding the vaporized titanium compound into the reactor. As this gas, an inert gas such as nitrogen, argon, or helium, or air can be used.
次いで、気化せしめられたチタン化合物を反応器５に送
り込む０反応器５は円筒または角筒などの筒状容器であ
り、内部または外部から加熱される６反応器５としては
直径りと塔の高さＨの比がＤ：Ｈ＝１：１〜１００の範
囲のものが用いられ、その上部または下部より、上記の
気化せしめられたチタン化合物を反応器５内に送り込む
、また、必要に応じて加水分解用の水蒸気を同時に送り
込む、なお、反応器５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１〜５０ｃＩｌ／ｓｅｃ、が好ましい、さらに原
料濃度は２ Ｘ ｌｌ１５ｍｏｊ）／ｉ’〜２ Ｘ １
０−’５ｏｊｉ’／ｊ！が好ましく、特に４ Ｘ １０
−５ｍｏｊ！／ｊｉ！ 〜１２Ｘ １Ｏ−５ｓｏｉｌ／
ｉ’が好ましい、また反応温度は３８０〜８００℃、好
ましくは４００〜５００℃である。なお、図中符号６は
ヒーター、７は冷却管である。Next, the vaporized titanium compound is sent to the reactor 5. The reactor 5 is a cylindrical container such as a cylinder or a rectangular tube, and the reactor 5 is heated from the inside or outside. A reactor with a ratio of D:H in the range of 1:1 to 100 is used, and the vaporized titanium compound is fed into the reactor 5 from the upper or lower part of the reactor. Water vapor for hydrolysis is simultaneously sent in. The residence time in the reactor 5 may be determined as appropriate, but it is preferably 0.1 to 10 seconds, and the flow rate is preferably 1 to 50 cIl/sec. Furthermore, the raw material concentration is 2 X ll15moj)/i' ~ 2 X 1
0-'5oji'/j! is preferable, especially 4×10
-5moj! /ji! ~12X 1O-5soil/
i' is preferred, and the reaction temperature is 380-800°C, preferably 400-500°C. In addition, the code|symbol 6 in the figure is a heater, and 7 is a cooling pipe.
次いで、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。Next, the titanium oxide fine particles thus generated may be collected as they are with 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 by filtration using a filter such as membrane filter 9 filter paper and collected on the surface of the filter. At this time, a cooling section may be provided inside the collector to collect the material by thermophoresis.
このようにして粒子径５〜５０ｎｍの実質的に結晶性か
つ実質的に球状の酸化チタン微粒子を回収することがで
きる０回収した酸化チタン微粒子は目的等を考慮して適
宜公知の技術で疎水化、親油化等の表面処理を行なうこ
とができる。In this way, substantially crystalline and substantially spherical titanium oxide fine particles with a particle size of 5 to 50 nm can be recovered. The recovered titanium oxide fine particles are hydrophobized using known techniques as appropriate in consideration of the purpose etc. , surface treatment such as lipophilization can be performed.
このような実質的に結晶性かつ実質的に球状の酸化チタ
ン微粒子を乳液、クリーム等の化粧料基材に０．０１〜
５０重凝％、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０．０１１℃％以下ではその添加効果が十分でなく
、また、５０重量％を超えると化粧料基材油に対する分
散性が低下するので、いずれも好ましくない。Such substantially crystalline and substantially spherical titanium oxide fine particles are added to cosmetic base materials such as emulsions and creams at a concentration of 0.01 to 100%.
It is blended in a proportion of 50% by weight, preferably 0.01 to 20% by weight to prepare a cosmetic. If the proportion of the titanium oxide fine particles is less than 0.011° C.%, the effect of the addition will not be sufficient, and if it exceeds 50% by weight, the dispersibility in cosmetic base oil will decrease, which is not preferable.
［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が、本
発明の範囲を超えない限り、これに限定されるものでは
ない。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto unless it exceeds the scope of the present invention.
製造例１
（アナターゼ型球状酸化チタン微粒子の製造）第３図に
示す装置を用いてアナターゼ型球状酸化チタン微粒子の
製造を行なった。すなわち原料としてのチタンテトライ
ソプロポキサイドを０．０５ｃｃ／ｗｉｎ、の割合でケ
ミカルポンプ２により２３０℃に加熱した気化器３に送
り込んだ、この気化器は内径７ｍｍ、長さｉｏａｍで、
内部にグラスウール４を充填したものを用いた。同時に
気化せしめられ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ヘリウムをチタンテトラ
イソプロポキサイドの濃度が８ Ｘ １（１５ｍｏｆ’
＃となるような割合で送り込んだ０次いで、この混合ガ
スを５００℃に加熱した反応器５に送り込んだ。Production Example 1 (Production of anatase type spherical titanium oxide fine particles) Anatase type spherical titanium oxide fine particles were manufactured using the apparatus shown in FIG. That is, titanium tetraisopropoxide as a raw material was fed at a rate of 0.05 cc/win into a vaporizer 3 heated to 230° C. by a chemical pump 2. This vaporizer had an inner diameter of 7 mm and a length of ioam.
The inside was filled with glass wool 4. At the same time, in order to transport the vaporized titanium tetraisopropoxide, helium was used as a carrier gas so that the concentration of titanium tetraisopropoxide was 8
Then, this mixed gas was fed into a reactor 5 heated to 500°C.
反応器５は内径２６■、長さ１００ ｍｍのものを用い
た。さらに反応器５にはキャリアーガスとしてヘリウム
を送り込み、また反応を促進するために水蒸気を送り込
んだ、全体としてのキャリアーガスの流量は］０００ｍ
ρ／ｗｉｎ、で滞留時間は約１秒とした。さらに反応器
出口は冷却ガスによりクエンチングし、生成粒子の合体
、凝集を防いだ。生成した粒子はＸ線回折測定の結果、
アナターゼ型球状酸化チタン微粒子であった。第４図に
このもののＸ線回折パターン（Ｃｕ−に、線使用）を、
第５図に電子顕微鏡写真を示す、また、このものは５〜
３０ｎｍの粒子径分布を有し、その数乎均粒子径は２０
ｎｍであった。The reactor 5 used had an inner diameter of 26 mm and a length of 100 mm. Furthermore, helium was fed into the reactor 5 as a carrier gas, and water vapor was fed into the reactor 5 to promote the reaction.The overall flow rate of the carrier gas was ]000 m
ρ/win, and the residence time was about 1 second. Furthermore, the outlet of the reactor was quenched with cooling gas to prevent coalescence and aggregation of the produced particles. As a result of X-ray diffraction measurement, the generated particles were
They were anatase-type spherical titanium oxide fine particles. Figure 4 shows the X-ray diffraction pattern of this material (Cu- line used).
Figure 5 shows an electron micrograph.
It has a particle size distribution of 30 nm, and its average particle size is 20 nm.
It was nm.
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０．０５ｃｃ／ｓｉｎ。Production Example 2 (Production of Anatase Type Spherical Titanium Oxide Fine Particles) The reaction was carried out using the same apparatus as Production Example 1. The raw material titanium tetraisopropoxide is 0.05cc/sin.
の割合でケミカルポンプ２により２３０℃に加熱した気
化器３に送り込んだ、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ヘリ
ウムを原料のチタンテトライソプロポキサイドの濃度が
１．４ Ｘ １０＝ｍａｉｌ／ｊ）となるような割合で
送り込んだ０次いで、この混合ガスを４５０℃に加熱し
た反応器５に送り込んだ。さらに反応器５にはキャリア
ーガスとしてヘリウムを送り込み、また反応を促進する
ために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２０００ｍｊ）／ｗｉｎ、で滞留時間は約１
．５秒とした。この場合にも製造例１と同様にして反応
後は冷却した。生成した粒子はｘ＆ｌａ回折測定の結果
、アナターゼ型球状酸化チタン微粒子であった。このも
のは２０〜３０ｎｍの粒子径分布を有し、その数平均粒
子径は２５ｎｍであった拳
製造例３
（ルチル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ノルマル
ブトキサイドを０．０５ｃｃ／ｒａｉｎ、の割合でケミ
カルポンプ２により２８０℃に加熱した気化器３に送り
込んだ、同時に気化したチタンテトラノルマルブトキサ
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
ンテトラノルマルブトキサイドの濃度が８ Ｘ １０−
５１１０１！／Ｒとなるような割合で送り込んだ０次い
で、この混合ガスを３５０°Ｃにｆｔｎ熱した反応器５
に送り込んだ。The concentration of titanium tetraisopropoxide used as a raw material was 1.4 10=mail/j) Next, this mixed gas was fed into the reactor 5 heated to 450°C. Further, helium was fed into the reactor 5 as a carrier gas, and water vapor was fed into the reactor 5 to promote the reaction.The overall flow rate of the carrier gas was 2000 mj)/win, and the residence time was about 1.
．． It was set to 5 seconds. In this case as well, the mixture was cooled after the reaction in the same manner as in Production Example 1. As a result of x&la diffraction measurement, the generated particles were found to be anatase type spherical titanium oxide fine particles. This product had a particle size distribution of 20 to 30 nm, and its number average particle size was 25 nm. Fist Production Example 3 (Production of Rutile-type Spherical Titanium Oxide Fine Particles) The reaction was carried out in the same apparatus as Production Example 1. Titanium tetra-normal butoxide as a raw material was fed into a vaporizer 3 heated to 280°C by a chemical pump 2 at a rate of 0.05 cc/rain, and at the same time a carrier gas was used to feed the vaporized titanium tetra-normal butoxide. The concentration of titanium tetranormal butoxide is 8 x 10-
51101! Then, this mixed gas was heated to 350°C in reactor 5.
I sent it to.
さらに反応器５にはキャリアーガスとして空気を送り込
んだ、全体としてのキャリアーガスの流量は１００・Ｏ
ｍｊ）／ｗｉｎ、で滞留時間は約３秒とした。得られた
生成物はｘ＆ａ回折の結果、アモルファスであった。こ
の生成物を空気中にて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、ルチル型球状酸化チ
タン微粒子であった。第６図にこのもののＸ線回折パタ
ーン（ＣＩ−にヶ線使用）を、第７図に電子顕微鏡写真
を示す、また、このものは１０〜４Ｏｎ嘗の粒子径分布
を有し、その数平均粒子径は３０ｎｍであった。Furthermore, air was fed into the reactor 5 as a carrier gas, and the overall flow rate of the carrier gas was 100 O.
mj)/win, and the residence time was about 3 seconds. The obtained product was amorphous as a result of x&a diffraction. This product was calcined in air at 850°C for 2 hours. As a result of X-ray diffraction measurement, the product after firing was found to be rutile-type spherical titanium oxide fine particles. Figure 6 shows the X-ray diffraction pattern (CI- is used), and Figure 7 shows the electron micrograph. The particle size was 30 nm.
製造例４
（ルチル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ノルマル
ブトキサイドを０．０５ｃｃ／ｗｉｎ、の割合でケミカ
ルポンプ２により２８０℃に加熱した気化器３に送り込
んだ、同時に気化したチタンテトラノルマルブトキサイ
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
テトラノルマルブトキサイドの濃度が２ Ｘ １０−’
ｍｏｊ？／ｊ’となるような割合で送り込んだ０次いで
、この混合ガスを３７０°Ｃに加熱した反応器５に送り
込んだ。Production Example 4 (Production of rutile-type spherical titanium oxide fine particles) The reaction was carried out using the same apparatus as Production Example 1. Titanium tetra-normal butoxide as a raw material was fed into a vaporizer 3 heated to 280°C by a chemical pump 2 at a rate of 0.05 cc/win, and at the same time as a carrier gas to send the vaporized titanium tetra-normal butoxide. The concentration of titanium tetranormal butoxide is 2 x 10-'.
moj? Then, this mixed gas was fed into the reactor 5 heated to 370°C.
さらに反応器５にはキャリアーガスとして空気を送り込
んだ、全体としてのキャリアーガスの流量は５００＋ａ
β／ｌｌｌ１ｒ＋、で滞留時間は約６秒とした。得られ
た生成物はＸ線回折の結果、アモルファスであった。こ
の生成物を空気中にて昇温速度１０℃／■ｉｎ。Furthermore, air was fed into the reactor 5 as a carrier gas, and the overall flow rate of the carrier gas was 500+a.
β/llll1r+, and the residence time was about 6 seconds. The obtained product was amorphous as a result of X-ray diffraction. This product was heated in air at a heating rate of 10°C/inch.
で９００℃まで昇温した後、電気炉から取り出した。焼
成後の生成物はＸ線回折測定の結果、ルチル型球状酸化
チタン微粒子であった。このものは３０〜５０ｎｍの粒
子径分布を有し、その数平均粒子径は４０ｎｍであった
９
実施例１〜４および比較例１
酸化チタンとして、前記製造例１〜４で得られた結晶性
球状耐化チタン微粒子（実施例１〜４）または***デグ
ッサ社製の結晶性で、かつその形態が主としてサイコロ
状の酸化チタン微粒子（アナターゼ・ルチル型の混合物
９粒子径分布１５〜５０ｎｍ 、数平均粒子径３０ｎｍ
、商品名Ｐ−２５） （比較例１）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。After raising the temperature to 900°C, it was taken out from the electric furnace. As a result of X-ray diffraction measurement, the product after firing was found to be rutile-type spherical titanium oxide fine particles. This material had a particle size distribution of 30 to 50 nm, and the number average particle size was 40 nm.9 Examples 1 to 4 and Comparative Example 1 The crystalline titanium oxide obtained in Production Examples 1 to 4 above Spherical hardened titanium fine particles (Examples 1 to 4) or crystalline titanium oxide fine particles manufactured by West German Degussa and mainly dice-shaped (anatase-rutile type mixture 9 particle size distribution 15-50 nm, number average) Particle size 30nm
, trade name P-25) (Comparative Example 1), a foundation cream was prepared according to the following formulation.
タ ル り
１５．０ 重 量％カ オ リ ン
４．０ 重陽％の１化チタン
微粒子（ｌｌｔＩＩ！１２ｆ１１）２０．０ 重量％
酸化鉄（赤’） ０．２７重量％酸化鉄（黄
）０．７重量％
酸化鉄（黒） ０．０３重量％固形パラフィ
ン ３．０重量％ラ ノ リ
ン １０−０ｍ
ｍ ％流動パラフィン ２７．０重量％グリ
セリルモノオレイ漕エステル ５．０ｆｆｉ１
％精 製 水 １５．０重
量％香 料 適
量タルク、カオリン、結晶性球状酸化チタン微粒子
、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、精製氷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０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 wt% kaolin
Titanium monoxide fine particles (lltII!12f11) with 4.0% deuterium (lltII!12f11) 20.0% by weight
Iron oxide (red') 0.27% by weight Iron oxide (yellow) 0.7% by weight Iron oxide (black) 0.03% by weight Solid paraffin 3.0% by weight La Nori
10-0m
m% liquid paraffin 27.0% by weight glyceryl monooleic ester 5.0ffi1
% purified water 15.0% by weight fragrance Appropriate amounts of talc, kaolin, crystalline spherical titanium oxide fine particles, 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 ingredients except for refined ice, add to this, and keep at 70°C to phase out the oil phase. Next, purified water was heated to 70°C, added to the oil phase, uniformly emulsified and dispersed with a homomixer, and kept at 40°C with stirring to prepare a foundation cream.
このファンデーションクリームまたは酸化チタン微粒子
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 or titanium oxide fine particles.
（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５涛層の膜厚を作り１日立２２８
型ダブルビーム分光光度計を用いて２００〜４００ ｎ
ｍの波長領域の吸光度を測定し、ＵＶ遮蔽効果を調べた
。 ＵＶ遮蔽性の評価は３００ｎｍ （ＵＶ−８と略
す）の吸光度が２．８以上を■印で、２．７〜２．５の
吸光度をＯ印で、２．４〜２．０の吸光度をΔ印で、１
．９以下の吸光度をＸ印でそれぞれ示した。また３ｅＯ
ｎｍ （ＵＶ−Ａと略す）の吸光度が１．８以上を■
印で、１．７〜１．５の吸光度を０印で、１．４・〜１
．０の吸光度をΔ印で、０．９以下の吸光度をｘ印でそ
れぞれ示した。評価結果を第１表に示す、第１表から明
らかなように、結晶性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、従来の酸化チタン
微粒子よりＵＶ−ＡおよびＵＶ−Ｂ共に遮蔽効果がすぐ
れていることが判る。(1) Ultraviolet rays (UV) shielding property A foundation cream prepared according to the above formulation was made into a film with a thickness of 5 layers on a transparent quartz plate and 1 Hitachi 228
200-400 n using a type double beam spectrophotometer
The absorbance in the m wavelength region was measured to examine the UV shielding effect. For the evaluation of UV shielding properties, absorbance at 300 nm (abbreviated as UV-8) is 2.8 or higher with a ■ mark, absorbance between 2.7 and 2.5 is marked O, and absorbance between 2.4 and 2.0 is marked with a ■ symbol. With Δ mark, 1
．． Absorbance of 9 or less was indicated by an X mark. Also 3eO
If the absorbance of nm (abbreviated as UV-A) is 1.8 or more,
The mark indicates an absorbance of 1.7 to 1.5, and the mark indicates an absorbance of 1.4 to 1.
．． An absorbance of 0 is indicated by a Δ symbol, and an absorbance of 0.9 or less is indicated by an x symbol. The evaluation results are shown in Table 1. As is clear from Table 1, the foundation cream of the present invention using crystalline spherical titanium oxide fine particles has a higher UV-A and UV-B shielding effect than conventional titanium oxide fine particles. It turns out that it is excellent.
（２）化腓品基材油への分散性
化粧品基材に汎用されている油に対する酸化チタンの分
散性を検δ＝ｆ した。(2) Dispersibility in cosmetic base oils The dispersibility of titanium oxide in oils commonly used as cosmetic base materials was examined (δ=f).
試験は５０ｍ１’目盛付沈降管（ウケナ管）に酸化チタ
ンＩｇを秤取し、汎用の基材油であるスクワラン、流動
パラフィンまたはヒマシ油をそれぞれ５ＯｒｓＲずつ加
えて分散機を用い攪拌９分散させて静置後、１分、５分
、３０分、６０分、１日、３日および７日の７回にわた
り分散状態を観察し、沈降した粒子が認められないもの
を５点、すべて沈降または凝集状態にて沈降しているも
のを１点と評価することにより各観察時の評価点をつけ
、これを合計し、分散性が非常に良いものを１０点、悪
いものを１点とする１０段階法により評価することによ
り行なった。結果を第１表に示す。For the test, titanium oxide Ig was weighed into a 50 m 1' graduated settling tube (Ukena tube), 5 OrsR of each of squalane, liquid paraffin, or castor oil, which are general-purpose base oils, were added and dispersed by stirring using a dispersion machine. After standing still, the dispersion state was observed 7 times for 1 minute, 5 minutes, 30 minutes, 60 minutes, 1 day, 3 days, and 7 days, and 5 points where no settled particles were observed were all settled or aggregated. An evaluation score is given for each observation by evaluating the condition of sedimentation as 1 point, and these are totaled to give a 10-point scale with 10 points for very good dispersibility and 1 point for poor dispersibility. This was done by evaluating according to the law. The results are shown in Table 1.
第１表から明らかなように、本発明で用いる結晶性球状
酸化チタン微粒子は、汎用されている化粧品基材油に良
好に分散することが判る。この理由は従来の酸化チタン
が、その粒子形状が一定していないのに対し、本発明で
用いる酸化チタンはその粒子の形状がビンポン玉のよう
なきれいな一定の球状をなしており、各々の粒子が凝集
しにくいことに起因するものと思われる。As is clear from Table 1, the crystalline spherical titanium oxide fine particles used in the present invention are well dispersed in commonly used cosmetic base oils. The reason for this is that while conventional titanium oxide does not have a uniform particle shape, the titanium oxide used in the present invention has a uniform spherical particle shape similar to a bottle pong ball. This is thought to be due to the fact that it is difficult to aggregate.
（３）可視光透過性
従来の酸化チタン微粒子は干渉光による青白い発色がみ
られ肌を明るくみせる効果がほとんどなかった。そこで
製造例１と製造例３で得られた結晶性球状酸化チタン微
粒子および従来の重版の酸化チタン微粒子（***デグッ
サ社製Ｐ−２５）を用いて可視光透過性を調べた。方法
は各々の酸化チタン４ｇをヒマシ油６ｇ中に懸濁させた
後、３木ローラーを用いて充分に混練した。練ったスラ
リー０．２５ ｇを採り、ざらにヒマシ油０．７５ｇを
加えて軟膏箆で充分に分散させた。該分散液をアプリケ
−ターヲ用いてカラーマツチングパネルの黒地上へ０．
０７８ｍｍの厚さに塗布し、塗布１１ｆｆを日立社製カ
ラーアナライザー６０７型で反射率を測定した。(3) Visible light transmittance Conventional titanium oxide fine particles exhibit a bluish color due to interference light and have little effect on brightening the skin. Therefore, visible light transmittance was investigated using the crystalline spherical titanium oxide fine particles obtained in Production Examples 1 and 3 and the conventional reprinted titanium oxide fine particles (P-25, manufactured by Degussa, Germany). In the method, 4 g of each titanium oxide was suspended in 6 g of castor oil, and then thoroughly kneaded using a Miki roller. 0.25 g of the kneaded slurry was taken, and 0.75 g of castor oil was added to a colander and thoroughly dispersed with an ointment spatula. Using an applicator, apply the dispersion to the black surface of the color matching panel.
The coating was applied to a thickness of 0.078 mm, and the reflectance of the coated 11 ff was measured using a Color Analyzer Model 607 manufactured by Hitachi.
ａｌ一定結果を第８図に示した０図から明らかなように
、本発明で用いる結晶性球状酸化チタン微粒子は可視光
線の透過性が従来品よりも高く、しかも４００〜５００
ｎｍの青味の反射率も低いことが判る。As is clear from Figure 8, which shows the al constant results, the crystalline spherical titanium oxide fine particles used in the present invention have higher visible light transmittance than conventional products, and have a transmittance of 400 to 500.
It can be seen that the blue-tinged reflectance of nm is also low.
このことは従来の酸化チタンが青白く見えるのに対し、
本発明で用いる結晶性球状酸化チタン微粒子は青白く見
えないことを意味しよう。This means that while conventional titanium oxide looks pale,
This means that the crystalline spherical titanium oxide fine particles used in the present invention do not look pale.
（４）実使用時の紫外線防御効果および使用感（実使用
性）
次に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（試料）を皮膚１ ｃｔａ？ 当り０．１ｇの割合
で女性パネラ−１０人の上腕部および顔面部に塗布して
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２７日（
快晴）、千葉県富津市富律海岸において行ない、午前１
１時から午後１時までの２時間、試料塗布皮１１ｖ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。(4) Ultraviolet protection effect and feeling of use during actual use (practical usability) Next, the foundation cream (sample) prepared according to the above formulation was applied to the skin 1 cta? The product was applied to the upper arms and faces of 10 female panelists at a rate of 0.1 g per sample 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 27, 1986 (
Clear skies), held at Tomitsu Beach, Futtsu City, Chiba Prefecture, 1:00 AM.
After irradiating the surface of the sample-applied skin 11v with sunlight for 2 hours from 1:00 to 1:00 p.m., the sample was dropped, and the condition of sunburn (strength or weakness of erythema) was visually determined twice, 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」、「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
目につき女性パネラ−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表に示した。これらの結果から
結晶性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、従来品より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 by the number of people who answered that female panelists were the best for each item. These results are shown in Table 1. These results show that the foundation cream of the present invention using crystalline spherical titanium oxide fine particles has better performance in actual use than conventional products.
［発明の効果］
本発明の化粧料は製造時の粒子の分散性、貯蔵安定性が
良好である。[Effects of the Invention] The cosmetic of the present invention has good particle dispersibility and storage stability during production.
また本発明の化粧料は紫外線遮蔽効果がすぐれており、
使用性も良好である。In addition, the cosmetics of the present invention have excellent ultraviolet shielding effects,
It is also easy to use.
さらに本発明の化粧料は、可視光線の透過性の良好な酸
化チタン微粒子を用いているため、青白さがない。Furthermore, since the cosmetic of the present invention uses titanium oxide fine particles that have good visible light transmittance, there is no pale appearance.
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
、第４図は本発明の製造例１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５図
はその電子顕微鏡写真、第６図は本発明の製造例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７図はその電子！１１微鏡写真。
第８図は本発明の実施例１．実施例３および比較例１の
酸化チタン微粒子の可視光透過性を示すグラフである。
ｌ・・・チタン化合物（原料）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 of an example of titanium oxide fine particles used in the present invention. FIG. 3 is an explanatory diagram showing the apparatus used in the production example of the present invention, FIG. 4 is an X-ray diffraction pattern of anatase type spherical titanium oxide fine particles obtained in production example 1 of the present invention, and FIG. The electron micrograph, FIG. 6, is the X-ray diffraction pattern of the rutile-type spherical titanium oxide fine particles obtained in Production Example 3 of the present invention, and FIG. 7 shows the electron! 11 Microscopic photo. FIG. 8 shows Example 1 of the present invention. 3 is a graph showing the visible light transmittance of titanium oxide fine particles of Example 3 and Comparative Example 1. l...Titanium compound (raw material)
Claims (1)
粒子を０．０１〜５０重量％配合してなる化粧料。(1) A cosmetic containing 0.01 to 50% by weight of substantially crystalline and substantially spherical titanium oxide fine particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28777786A JPS63141912A (en) | 1986-12-04 | 1986-12-04 | Cosmetic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28777786A JPS63141912A (en) | 1986-12-04 | 1986-12-04 | Cosmetic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63141912A true JPS63141912A (en) | 1988-06-14 |
Family
ID=17721613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28777786A Pending JPS63141912A (en) | 1986-12-04 | 1986-12-04 | Cosmetic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63141912A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037560A1 (en) * | 1995-05-24 | 1996-11-28 | The Procter & Gamble Company | Titanium dioxide hydrogel and sunscreen composition containing it |
| JP2008033128A (en) * | 2006-07-31 | 2008-02-14 | Kyocera Corp | Optical receptacle and optical module using the same |
-
1986
- 1986-12-04 JP JP28777786A patent/JPS63141912A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996037560A1 (en) * | 1995-05-24 | 1996-11-28 | The Procter & Gamble Company | Titanium dioxide hydrogel and sunscreen composition containing it |
| JP2008033128A (en) * | 2006-07-31 | 2008-02-14 | Kyocera Corp | Optical receptacle and optical module using the same |
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