WO1998016193A1 - Dispersion of particulate titanium dioxide in silicone - Google Patents

Dispersion of particulate titanium dioxide in silicone Download PDF

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Publication number
WO1998016193A1
WO1998016193A1 PCT/JP1997/002760 JP9702760W WO9816193A1 WO 1998016193 A1 WO1998016193 A1 WO 1998016193A1 JP 9702760 W JP9702760 W JP 9702760W WO 9816193 A1 WO9816193 A1 WO 9816193A1
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WIPO (PCT)
Prior art keywords
titanium dioxide
silicone
dispersion
dispersion according
fine particle
Prior art date
Application number
PCT/JP1997/002760
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French (fr)
Japanese (ja)
Inventor
Hideo Futamata
Hideo Takahashi
Masakazu Hattori
Masanori Iida
Original Assignee
Ishihara Sangyo Kaisha, Ltd.
Priority date (The priority date 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 date listed.)
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Publication date
Priority claimed from JP28913296A external-priority patent/JP3224750B2/en
Application filed by Ishihara Sangyo Kaisha, Ltd. filed Critical Ishihara Sangyo Kaisha, Ltd.
Priority to AU37840/97A priority Critical patent/AU3784097A/en
Publication of WO1998016193A1 publication Critical patent/WO1998016193A1/en

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Classifications

    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • A61K8/894—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone modified by a polyoxyalkylene group, e.g. cetyl dimethicone copolyol
    • 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
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/58—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing atoms other than carbon, hydrogen, halogen, oxygen, nitrogen, sulfur or phosphorus
    • A61K8/585—Organosilicon compounds
    • 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
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89—Polysiloxanes
    • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
    • 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
    • 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

Definitions

  • the present invention relates to a dispersion in which fine particle titanium dioxide is dispersed in silicone and a sunscreen cosmetic using the same.
  • Fine particle titanium dioxide with a single particle size of about 0.15 ⁇ m or less when incorporated into a film or molded product such as a resin, shields ultraviolet rays and protects substances that are altered by ultraviolet rays, while transmitting visible light. It is well known that it exhibits properties different from pigment-grade titanium dioxide having a single particle size of 0.15 to 0.5 ⁇ m, such as high transparency. In addition, since its effect on the human body is extremely low and there is almost no deterioration by ultraviolet light or chemicals, particulate titanium dioxide is a highly safe, stable, and highly transparent ultraviolet shielding agent for paints and cosmetics. It is used for chemical fiber.
  • silicones have come to be widely used in paints and cosmetics as a material having excellent water resistance, water repellency, chemical resistance, and weather resistance.
  • cosmetics have attracted much attention because of their excellent water-resistance, good stretchability when applied to the skin, and a light touch.
  • titanium dioxide is blended with silicone-based cosmetics for the purpose of imparting ultraviolet shielding properties, the surface of titanium dioxide is hydrophilic, while silicone has high hydrophobicity. Titanium dioxide particles were agglomerated without being compatible with silicone, causing a problem that the original transparency and ultraviolet shielding properties were not exhibited.
  • the present invention relates to a fine particle titanium dioxide, which is an ultraviolet ray shielding agent with excellent safety, stability, and transparency, that is formulated into a highly dispersed state by a relatively simple dispersion treatment when blended with silicone-based cosmetics.
  • An object of the present invention is to provide a dispersion capable of imparting an excellent ultraviolet shielding ability.
  • the present inventors have formulated fine particle titanium dioxide into a silicone cosmetic.
  • the dispersant is used and the silicone is used as a solvent and the silicone is used as a medium, the above-mentioned problems can be solved.
  • the feeling of elongation is improved.
  • the present inventors have found that there is an excellent effect not found in the prior art, such as improvement of the conventional technology, and completed the present invention.
  • the fine particle titanium dioxide dispersion of the present invention comprises silicone as a medium, fine particle titanium dioxide, and a dispersant that stably disperses the particles.
  • the dispersion medium is 20 to 70% by weight, preferably 40 to 70% by weight
  • the fine particle titanium dioxide is 30 to 70% by weight
  • the dispersant is 1 to 40% by weight. It is.
  • the shape of the fine particle titanium dioxide in the fine particle titanium dioxide dispersion of the present invention may be any of a spherical shape, a rod shape, a spindle shape, a dendritic shape, and a starfish shape, and the average single particle size is 0.005 to 0.15. ⁇ M, preferably 0.005 to 0.11 ⁇ m.
  • ⁇ M preferably 0.005 to 0.11 ⁇ m.
  • particulate titanium dioxide having a shape other than spherical their volumes were determined and a true sphere equivalent to the volume was assumed, and the diameter was taken as the average single particle diameter of each shape.
  • titanium dioxide having a length of 0.05 to 6 / m and an axial ratio of 3 or more is preferable.
  • the average major axis diameter is 0.
  • the fine particle titanium dioxide used in the present invention can be produced by various methods.
  • the titanium tetrachloride aqueous solution is neutralized and hydrolyzed with an alkali, and the obtained hydrous titanium dioxide is calcined or hydrous titanium dioxide is produced.
  • a hydrous titanium dioxide solution obtained by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride may be peptized with an acid, or may be further baked.
  • the fine particle titanium dioxide is coated with, for example, at least one oxide or hydrated oxide of aluminum, silicon, zirconium, titanium, zinc, and tin in order to improve the affinity with the dispersant and the light resistance.
  • fine particle titanium dioxide is an organic substance such as higher fatty acids such as stearic acid and lauric acid and metal salts thereof; siloxane compounds such as dimethyl polysiloxane and methyl hydrogen polysiloxane; and polyol compounds such as trimethylolethane and trimethylolpropane. It may be coated.
  • the silicone used as a solvent in the present invention may be selected according to the cosmetic to be blended.
  • methylpolysiloxane; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Such as methylcyclopolysiloxane; methylfluoropolysiloxane.
  • the dispersant used in the present invention is preferably a silicone compound, for example, dimethylpolysiloxane-methyl (polyoxyalkylene) siloxane copolymer, trimethylsiloxycyanic acid, carboxy-modified silicone oil, amino And modified silicone oil.
  • a good silicone dispersion in terms of dispersibility, viscosity, stability and the like can be obtained.
  • the greater the specific surface area of titanium dioxide and the greater the amount of surface coating the greater the optimal blending of the dispersant.
  • the optimum amount of the dispersant varies depending on the method of producing ultrafine titanium dioxide and the type of surface coating agent. In some cases, it is better to use a combination of two or more dispersants. This is because the use of only one dispersant can suppress the elongation and the emulsification stability of cosmetics, if they are not sufficient.
  • the dispersion of the present invention is obtained by pre-mixing a specific dispersant, a solvent solution, and particulate titanium dioxide using a blade-type stirrer, disperser, homomixer, or the like, and then using a pulverizer such as a sand mill, a pebble mill, or a disk mill. To obtain fine particles of titanium dioxide.
  • the heat treatment may be performed at a temperature of 50 ° C. or more, preferably 80 ° C. or more, before, after, or after such a dispersion operation.
  • the type of mill, the selection of grinding media, and the setting of optimal grinding conditions are important in adjusting advanced dispersions.
  • a vertical or horizontal sand mill with a 0.5 mm diameter zircon It is desirable to pulverize using. Since the fine particle titanium dioxide dispersion thus obtained contains the fine particle titanium dioxide in an extremely dispersed state, when blended in cosmetics, the fine particle titanium dioxide inherently has excellent ultraviolet shielding ability. In addition to fully exerting the effect, it has the effect of improving the stability of the combined cosmetics and improving the feeling of use such as good elongation.
  • the fine particle titanium dioxide silicone dispersion is prepared under conditions that are very suitable for dispersing the fine particle titanium dioxide, it is blended with a desired cosmetic, so that the inherent ultraviolet ray shielding capability inherent in the fine particle titanium dioxide is sufficiently exhibited. You. On the other hand, in general, even if the fine particle titanium dioxide is blended in such a way that the powder is blended into the cosmetic, the fine particle titanium dioxide does not sufficiently exhibit the inherent ultraviolet shielding ability. Problems such as sedimentation and separation from the silicone component often occur.
  • the fine particle titanium dioxide silicone dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component mainly containing silicone, a humectant, a surfactant, a pigment, a fragrance, a preservative, water, alcohols, It can be used in various forms, such as lotions, creams, pastes, sticks, emulsions, etc., by mixing with a viscous agent.
  • a sunscreen cosmetic for example, an oily component mainly containing silicone, a humectant, a surfactant, a pigment, a fragrance, a preservative, water, alcohols, It can be used in various forms, such as lotions, creams, pastes, sticks, emulsions, etc., by mixing with a viscous agent.
  • the slurry 7 0 sodium aluminate with good stirring was heated to ° C was added 5% T i 0 2 weight as A 1 2 0 -3, subsequently Mature form and hydrated oxides of aluminum was precipitated and coated on the titanium dioxide particles.
  • the solid content is filtered and washed, and the washed cake is dried and then powdered with a hammer type mill. This was ground to obtain ultrafine titanium dioxide powder (average single particle diameter: 0.02 urn).
  • the hydrous titanium oxide obtained by hydrolysis of the titanium tetrachloride aqueous solution was used as an aqueous suspension having a concentration of 100 g / 1 in terms of T i 0.
  • To this aqueous suspension 21 was added 1400 g of a 48% aqueous sodium hydroxide solution with stirring, heated at 95 ° C. for 120 minutes, filtered, and sufficiently washed. .
  • the washed cake was Reparupu with water, and T i 0 2 conversion 1 0 0 g / 1 concentration of the aqueous suspension, placed the aqueous suspension 1.5 1 reflux condenser flask, 35% hydrochloric acid 4 After adding 0 g with stirring, the mixture was heated and aged at 95 ° C for 120 minutes, and the major axis of the rutile crystal was 0.20 // m, the axial ratio was 5.0 (average single particle diameter). When expressed, an aqueous suspension of 0.078 ⁇ m) of rod-shaped fine particle titanium oxide was obtained.
  • the hydrous titanium oxide obtained by hydrolysis of titanium tetrachloride aqueous solution was T i 0 2 conversion 1 0 0 g / 1 concentration of the aqueous suspension.
  • To this aqueous suspension 21 was added 1400 g of a 48% aqueous sodium hydroxide solution with stirring, and after heating at 95 ° C for 120 minutes, filtration was performed. And thoroughly washed.
  • the washed cake was Reparupu with water, T i 0 2 and converted 1 0 0 gZ l aqueous suspension with a concentration of, putting the aqueous suspension 1.5 1 reflux condenser flask, 3 5% hydrochloric acid 5 7 0 g was added instantaneously with stirring, and the mixture was aged by heating at 95 ° C for 120 minutes, and the long axis of the rutile crystal was 0.30 ⁇ m and the short axis was 0.055 ⁇ m (average). An aqueous suspension of dendritic particulate titanium oxide having a particle diameter of 0.11 ⁇ m) was obtained.
  • the suspension was added 5% T i 0 2 weight sodium aluminate as A 1 2 0 3 with good stirring after heating to a 7 0 ° C, hydrated oxides of Aruminiu beam subsequently was aged Was precipitated and coated on the titanium dioxide particles.
  • the solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain dendritic fine particles of titanium dioxide powder.
  • the dendritic titanium dioxide powder 40 parts by weight of the dendritic titanium dioxide powder was mixed with a dispersion of 12 parts by weight of a dispersant (trimethylsiloxygayic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane) using a disperser. did. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (C) having a viscosity of 130 cP.
  • a dispersant trimethylsiloxygayic acid
  • a dispersion medium decamethylcyclopentasiloxane
  • Example 4 40 parts by weight of the fine particle titanium dioxide powder of Example 1 was dispersed with a dispersant (6 parts by weight of trimethylsiloxy gay acid and 6 parts by weight of dimethylpolysiloxane 'methyl (polyoxyethylene) siloxane copolymer) in a total of 12 parts by weight.
  • the mixture was mixed with a solvent (octamethylcyclotetrasiloxane) 48 parts by weight using a disper.
  • this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (D) having a viscosity of 90 cP.
  • the fine particle titanium dioxide of Example 1 was used as a powder (E).
  • the rod-shaped fine particle titanium dioxide of Example 2 was used as a powder (F).
  • the dendritic particulate titanium dioxide of Example 3 was used as the powder (G). Test example 1
  • a sunscreen cream (WZO emulsion) is prepared by blending the silicone dispersion (A) to (D) and the powders (E) to (G) of the fine particle titanium dioxide in the following formulation so that the total amount is 100 parts by weight.
  • the components (1) to (5) were mixed and dispersed with a disperser, and the premixed components (6) to (8) were gradually added with stirring to prepare a sunscreen cream.
  • Each of the above creams was applied on a quartz glass plate so as to have a thickness of 25 // m, and the transmittance at 750 to 300 nm was measured with a spectrophotometer.
  • the fine particle titanium dioxide silicone dispersion of the present invention contains finely particulate titanium dioxide, which is an ultraviolet shielding agent excellent in safety, stability, and transparency, in a very well-dispersed state.
  • finely particulate titanium dioxide which is an ultraviolet shielding agent excellent in safety, stability, and transparency, in a very well-dispersed state.

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Abstract

An attempt at blending a silicone-base cosmetic material with particulate titanium dioxide for imparting ultraviolet-screening properties to the material causes the agglomeration of particulate titanium dioxide and thus fails in exhibiting the transparency and ultraviolet-screening properties inherent in the titanium dioxide, because the surface of the particulate titanium dioxide is hydrophilic while silicone is highly hydrophobic, i.e., both components are incompatible with each other. The present invention provides a stable dispersion prepared by dispersing particulate titanium dioxide having a mean single particle diameter of 0.005 to 0.15 νm in a silicone medium by the use of a dispersant.

Description

明 細 書 微粒子二酸化チタンシリコ一ン分散体 技術分野  Description Fine particle titanium dioxide silicone dispersion Technical field
本発明は、 微粒子二酸化チタンをシリコーンに分散させた分散体及びこれを用 いた日焼け止め化粧料に関するものである。  TECHNICAL FIELD The present invention relates to a dispersion in which fine particle titanium dioxide is dispersed in silicone and a sunscreen cosmetic using the same.
背景技術 Background art
単一粒子径約 0 . 1 5〃m以下の微粒子二酸化チタンは、 樹脂などの膜或いは 成形物に配合すると、 紫外線を遮蔽して紫外線により変質する物質を保護する一 方、 可視光線を透過して透明性を有するといったように、 単一粒子径 0 . 1 5〜 0 . 5〃mの顔料級二酸化チタンとは異なった性質を示すことは良く知られてい る。 更に、 人体への作用が極めて低く、 またそれ自体紫外線や薬品などによる変 質がほとんどないことから、 微粒子二酸化チタンは、 安全性、 安定性、 透明性の 高い紫外線遮蔽剤として、 塗料、 化粧料、 化学繊維に利用されている。  Fine particle titanium dioxide with a single particle size of about 0.15 μm or less, when incorporated into a film or molded product such as a resin, shields ultraviolet rays and protects substances that are altered by ultraviolet rays, while transmitting visible light. It is well known that it exhibits properties different from pigment-grade titanium dioxide having a single particle size of 0.15 to 0.5 μm, such as high transparency. In addition, since its effect on the human body is extremely low and there is almost no deterioration by ultraviolet light or chemicals, particulate titanium dioxide is a highly safe, stable, and highly transparent ultraviolet shielding agent for paints and cosmetics. It is used for chemical fiber.
ところで近年、 塗料、 化粧品には、 耐水性、 撥水性、 耐薬品性、 耐候性に優れ た材料として、 シリコーンが多く利用されるようになってきた。 とくに、 化粧料 用には、 耐水性などに加えて、 肌に塗ったときの伸びのよさ、 さらつとした感触 力'、 極めて優れていることから、 非常に注目されている。 しかしながら、 紫外線 遮蔽性を付与する目的で、 シリコーン系の化粧料に二酸化チタンを配合しようと すると、 二酸化チタン表面が親水性であるのに対し、 シリコーンが高い疎水性を 有していることから、 二酸化チタン粒子がシリコーンになじまずに凝集してしま い、 本来の透明性、 紫外線遮蔽性が発揮されないという問題が生じた。  In recent years, silicones have come to be widely used in paints and cosmetics as a material having excellent water resistance, water repellency, chemical resistance, and weather resistance. In particular, cosmetics have attracted much attention because of their excellent water-resistance, good stretchability when applied to the skin, and a light touch. However, if titanium dioxide is blended with silicone-based cosmetics for the purpose of imparting ultraviolet shielding properties, the surface of titanium dioxide is hydrophilic, while silicone has high hydrophobicity. Titanium dioxide particles were agglomerated without being compatible with silicone, causing a problem that the original transparency and ultraviolet shielding properties were not exhibited.
発明の開示 Disclosure of the invention
本発明は、 安全性、 安定性、 透明性に優れた紫外線遮蔽剤である微粒子二酸化 チタンについて、 シリコーン系の化粧料に配合したときに、 比較的簡単な分散処 理操作で高分散状態に配合し得、 非常に優れた紫外線遮蔽能を付与し得る分散体 を提供することにある。  The present invention relates to a fine particle titanium dioxide, which is an ultraviolet ray shielding agent with excellent safety, stability, and transparency, that is formulated into a highly dispersed state by a relatively simple dispersion treatment when blended with silicone-based cosmetics. An object of the present invention is to provide a dispersion capable of imparting an excellent ultraviolet shielding ability.
本発明者等は、 微粒子二酸化チタンについて、 シリコーン系の化粧料に配合し たときに、 本来有する紫外線遮蔽能を完全に発揮するような形態を種々検討した。 その結果、 分散剤を用い、 シリコーンを媒液として、 予め良く分散させた形態で あれば、 前記問題点を解決し得るのに加え、 配合した化粧料の安定性向上、 伸び のよさなど使用感の向上など、 従来技術にない優れた効果があるとの知見を得、 本発明を完成した。 The present inventors have formulated fine particle titanium dioxide into a silicone cosmetic. In this study, we examined various forms that fully exhibit the inherent ultraviolet shielding ability. As a result, if the dispersant is used and the silicone is used as a solvent and the silicone is used as a medium, the above-mentioned problems can be solved. In addition to improving the stability of the blended cosmetics, the feeling of elongation is improved. The present inventors have found that there is an excellent effect not found in the prior art, such as improvement of the conventional technology, and completed the present invention.
本発明の微粒子二酸化チタン分散体は、 媒液としてのシリコーン、 微粒子二酸 化チタン、 およびこの粒子を安定的に分散せしめる分散剤で構成されている。 分散体の配合としては、 分散媒が 2 0〜 7 0重量％、 望ましくは 4 0〜 7 0重 量％、 微粒子二酸化チタンが 3 0〜 7 0重量％及び分散剤が 1〜 4 0重量％であ る。  The fine particle titanium dioxide dispersion of the present invention comprises silicone as a medium, fine particle titanium dioxide, and a dispersant that stably disperses the particles. As for the composition of the dispersion, the dispersion medium is 20 to 70% by weight, preferably 40 to 70% by weight, the fine particle titanium dioxide is 30 to 70% by weight and the dispersant is 1 to 40% by weight. It is.
本発明の微粒子二酸化チタン分散体における微粒子二酸化チタンの形状は、 球 状、 棒状、 紡錘状、 樹枝状、 ヒトデ状のいずれでも良く、 平均単一粒子径が 0 . 0 0 5〜0 . 1 5〃m、 好ましくは 0 . 0 0 5〜0 . 1 1〃mである。 球状以外 の形状を有する微粒子二酸化チタンの場合には、 それらの体積を求めてその体積 と等価の真球状を想定し、 その径を各形状の平均単一粒子径とした。 なお、 形状 が棒状である場合は、 その長さが 0 . 0 5〜 6 / m、 軸比が 3以上の二酸化 チタンが好ましく、 樹枝状或いはヒトデ状である場合は、 平均長軸径が 0 . 2〜 0 . 5 m、 平均短軸径が 0 . 0 4〜 0 . 1 m、 軸比が 3以上の二酸化チ夕ン が好ましい。  The shape of the fine particle titanium dioxide in the fine particle titanium dioxide dispersion of the present invention may be any of a spherical shape, a rod shape, a spindle shape, a dendritic shape, and a starfish shape, and the average single particle size is 0.005 to 0.15. 〃M, preferably 0.005 to 0.11〃m. In the case of particulate titanium dioxide having a shape other than spherical, their volumes were determined and a true sphere equivalent to the volume was assumed, and the diameter was taken as the average single particle diameter of each shape. When the shape is rod-shaped, titanium dioxide having a length of 0.05 to 6 / m and an axial ratio of 3 or more is preferable.When the shape is dendritic or starfish-shaped, the average major axis diameter is 0. Preference is given to titanium dioxide having an average minor axis diameter of 0.04 to 0.1 m and an axial ratio of 3 or more.
本発明において使用する微粒子二酸化チタンは、 種々の方法によって製造し得 るが、 例えば四塩化チタン水溶液をアルカリで中和加水分解し、 得られた含水二 酸化チタンを焼成するか、 あるいは含水二酸化チタンを水酸化ナトリウムで加熱 処理し、 得られた反応生成物を酸で加熱熟成して得ることができる。 このものは、 さらに必要に応じて焼成して粒子径ゃ粒子形状の調整、 更に耐候性の向上をはか つてもよい。 また、 硫酸チタン水溶液や四塩化チタン水溶液を加熱加水分解して 得られた含水二酸化チタンを酸で解こう処理したものや、 このものをさらに焼成 したものであってもよい。 さらに微粒子二酸化チタンは、 分散剤との親和性ゃ耐 光性の向上をはかるべく、 例えばアルミニウム、 珪素、 ジルコニウム、 チタン、 亜鉛およびスズの少なくとも 1種の酸化物または含水酸化物で被覆されている方 が好ましい。 さらに、 微粒子二酸化チタンはステアリン酸、 ラウリン酸などの高 級脂肪酸およびその金属塩； ジメチルポリシロキサン、 メチル水素ポリシロキサ ンなどのシロキサン化合物； トリメチロールェタン、 トリメチロールプロパンな どのポリオール化合物などの有機物で被覆されていてもよい。 The fine particle titanium dioxide used in the present invention can be produced by various methods. For example, the titanium tetrachloride aqueous solution is neutralized and hydrolyzed with an alkali, and the obtained hydrous titanium dioxide is calcined or hydrous titanium dioxide is produced. Can be heat-treated with sodium hydroxide, and the resulting reaction product can be obtained by heating and aging with an acid. This may be further baked, if necessary, to adjust the particle diameter / particle shape, and to further improve the weather resistance. Further, a hydrous titanium dioxide solution obtained by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride may be peptized with an acid, or may be further baked. Furthermore, the fine particle titanium dioxide is coated with, for example, at least one oxide or hydrated oxide of aluminum, silicon, zirconium, titanium, zinc, and tin in order to improve the affinity with the dispersant and the light resistance. One Is preferred. In addition, fine particle titanium dioxide is an organic substance such as higher fatty acids such as stearic acid and lauric acid and metal salts thereof; siloxane compounds such as dimethyl polysiloxane and methyl hydrogen polysiloxane; and polyol compounds such as trimethylolethane and trimethylolpropane. It may be coated.
本発明において使用する媒液としてのシリコーンとしては、 配合しょうとする 化粧料に合わせて選択すればよく、 例えば、 メチルポリシロキサン；ォクタメチ ルシクロテトラシロキサン、 デカメチルシクロペンタシロキサン、 ドデカメチル シクロへキサシロキサンなどのメチルシクロポリシロキサン；メチルフ 二ルポ リシロキサンなどが挙げられる。  The silicone used as a solvent in the present invention may be selected according to the cosmetic to be blended. For example, methylpolysiloxane; octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane Such as methylcyclopolysiloxane; methylfluoropolysiloxane.
本発明において使用する分散剤は、 シリコーン系の化合物であることが好まし く、 例えば、 ジメチルポリシロキサン ·メチル （ポリオキシアルキレン） シロキ サン共重合体、 トリメチルシロキシケィ酸、 カルボキシ変性シリコーンオイル、 ァミノ変性シリコーンオイルなどが挙げられる。 シリコーン系分散剤は、 重量基 準で 1〜4 0 %、 好ましくは、 5〜3 0 %配合することによって、 分散性、 粘度、 安定性等の点で良好なシリコーン分散体が得られる。 概ね、 二酸チタンの比表面 積が大きいほど、 また、 表面被覆剤の量が多いほど、 分散剤の最適配合は多くな る。 また、 超微粒子二酸化チタンの製法、 表面被覆剤の種類によっても分散剤の 最適配合量は異なってくる。 分散剤は、 2種以上のものを組み合わせて使用した 方がよい場合がある。 1種だけの分散剤の使用では、 化粧品の伸びや乳化安定性 力〈十分でない場合に、 それらを抑えることができるからである。  The dispersant used in the present invention is preferably a silicone compound, for example, dimethylpolysiloxane-methyl (polyoxyalkylene) siloxane copolymer, trimethylsiloxycyanic acid, carboxy-modified silicone oil, amino And modified silicone oil. By blending the silicone-based dispersant in an amount of 1 to 40%, preferably 5 to 30% on a weight basis, a good silicone dispersion in terms of dispersibility, viscosity, stability and the like can be obtained. In general, the greater the specific surface area of titanium dioxide and the greater the amount of surface coating, the greater the optimal blending of the dispersant. The optimum amount of the dispersant varies depending on the method of producing ultrafine titanium dioxide and the type of surface coating agent. In some cases, it is better to use a combination of two or more dispersants. This is because the use of only one dispersant can suppress the elongation and the emulsification stability of cosmetics, if they are not sufficient.
次に、 本発明の微粒子二酸化チタンシリコーン分散体の製造方法について述べ る。 本発明の分散体は、 特定の分散剤、 媒液及び微粒子二酸化チタンを、 羽根型 攪拌機、 デイスパー、 ホモミキサー等を用いて予備混合したのち、 サンドミル、 ぺブルミル、 ディスクミル等の粉砕機を用いて、 微粒子二酸化チタンを分散せし めることにより得られる。 なお、 また、 この様な分散操作の前および Zまたは後 に 5 0 °C以上、 望ましくは 8 0 °C以上の温度で加熱処理を行ってもよい。 粉碎機 の種類、 粉砕メディアの選定、 最適粉砕条件の設定は、 高度な分散体を調整する 上で重要であるが、 例えば縦型、 横型のサンドミルで直径 0 . 5 mmのジルコ二 アビ一ズを用いて粉砕するのが望ましい。 このようにして得られた微粒子二酸化チタンシリコーン分散体は、 微粒子二酸 化チタンを非常に良く分散した状態で含有するため、 化粧料に配合すると、 微粒 子二酸化チタンが本来有する優れた紫外線遮蔽能を十分に発揮するのに加え、 配 合した化粧料の安定性向上、 伸びのよさなどの使用感の向上の効果を発現する。 微粒子二酸化チタンシリコーン分散体は、 微粒子二酸化チタンの分散に非常に 適した条件で作製されたのち、 所望の化粧料に配合されるため、 微粒子二酸化チ タンが本来有する紫外線遮蔽能が十分に発揮される。 これに対し、 通常、 化粧料 に粉末を配合するような方法で微粒子二酸化チタンを配合しても、 微粒子二酸化 チタンが本来有する紫外線遮蔽能が十分発揮されないばかり力、、 経時的に微粒子 二酸化チタンがシリコーン成分から分離して沈降するなどの問題が生ずることが 多い。 本発明の微粒子二酸化チタンシリコーン分散体を日焼け止め化粧料として 利用する場合には、 例えばシリコーンを主とする油性成分、 保湿剤、 界面活性剤、 顔料、 香料、 防腐剤、 水、 アルコール類、 增粘剤等と配合し、 ローション状、 ク リーム状、 ペースト状、 スティック状、 乳液状など、 各種の形態で用いることが できる。 Next, a method for producing the fine particle titanium dioxide silicone dispersion of the present invention will be described. The dispersion of the present invention is obtained by pre-mixing a specific dispersant, a solvent solution, and particulate titanium dioxide using a blade-type stirrer, disperser, homomixer, or the like, and then using a pulverizer such as a sand mill, a pebble mill, or a disk mill. To obtain fine particles of titanium dioxide. The heat treatment may be performed at a temperature of 50 ° C. or more, preferably 80 ° C. or more, before, after, or after such a dispersion operation. The type of mill, the selection of grinding media, and the setting of optimal grinding conditions are important in adjusting advanced dispersions.For example, a vertical or horizontal sand mill with a 0.5 mm diameter zircon It is desirable to pulverize using. Since the fine particle titanium dioxide dispersion thus obtained contains the fine particle titanium dioxide in an extremely dispersed state, when blended in cosmetics, the fine particle titanium dioxide inherently has excellent ultraviolet shielding ability. In addition to fully exerting the effect, it has the effect of improving the stability of the combined cosmetics and improving the feeling of use such as good elongation. Since the fine particle titanium dioxide silicone dispersion is prepared under conditions that are very suitable for dispersing the fine particle titanium dioxide, it is blended with a desired cosmetic, so that the inherent ultraviolet ray shielding capability inherent in the fine particle titanium dioxide is sufficiently exhibited. You. On the other hand, in general, even if the fine particle titanium dioxide is blended in such a way that the powder is blended into the cosmetic, the fine particle titanium dioxide does not sufficiently exhibit the inherent ultraviolet shielding ability. Problems such as sedimentation and separation from the silicone component often occur. When the fine particle titanium dioxide silicone dispersion of the present invention is used as a sunscreen cosmetic, for example, an oily component mainly containing silicone, a humectant, a surfactant, a pigment, a fragrance, a preservative, water, alcohols, It can be used in various forms, such as lotions, creams, pastes, sticks, emulsions, etc., by mixing with a viscous agent.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
本発明を下記実施例により例示しながら更に詳しく説明する。 実施例は本発明 の特定の態様であり、 限定的なものではない。  The present invention will be described in more detail with reference to the following examples. The examples are specific embodiments of the present invention and are not limiting.
実施例 1  Example 1
四塩化チタン水溶液 （T i 02 2 0 0 g/ 1 ) を室温に保持しながら、 水酸化 ナトリウム水溶液で中和してコロイド状の非晶質水酸化チタンを析出させ、 その 後熟成してルチル型の微小チタニアゾルを得た。 このゾルを濾過、 洗浄したのち 6 0 0 °Cで 3時間焼成し、 流体エネルギーミルで粉碎して平均粒子径 2 0 n mの 超微粒子二酸化チタン粉末を得た。 この超微粒子二酸化チタン粉末を水中に分散 させてサンドミルで湿式粉碎して超微粒子二酸化チタンスラリ一 （T i 02 2 0 0 g/ 1 ) とした。 このスラリーを 7 0 °Cに加熱した後よく攪拌しながらアルミ ン酸ナトリウムを A 1 2 0 -3 として T i 02 重量基準で 5 %添加し、 引き続き熟 成してアルミニウムの水和酸化物を該ニ酸化チタン粒子上に沈殿、 被覆させた。 その固形分を濾過、 洗浄し、 洗浄ケーキを乾燥したのちハンマータイプミルで粉 砕して超微粒子二酸化チタン粉末 （平均単一粒子径 0. 0 2 urn) を得た。 この微粒子二酸化チタン粉末 4 0重量部を分散剤 （トリメチルシロキシケィ 酸） 1 2重量部と分散媒 （ォクタメチルシクロテトラシロキサン） 4 8重量部と の混合液中にディスパーを用いて混合した。 次に、 これをジルコンビーズをメデ ィァとして用い、 サンドミルで粉砕したところ、 粘度 1 5 0 c Pのシリコ一ンォ ィル分散体 （A) を得た。 While retaining the aqueous titanium tetrachloride solution (T i 0 2 2 0 0 g / 1) to room temperature, neutralized with aqueous sodium hydroxide solution to precipitate colloidal amorphous titanium hydroxide, and aged after the A rutile-type fine titania sol was obtained. This sol was filtered, washed, calcined at 600 ° C. for 3 hours, and pulverized with a fluid energy mill to obtain ultrafine titanium dioxide powder having an average particle diameter of 20 nm. This was ultrafine titanium dioxide powder is dispersed in water and wet Kona碎with sand mill for ultrafine titanium dioxide slurry one (T i 0 2 2 0 0 g / 1). The slurry 7 0 sodium aluminate with good stirring was heated to ° C was added 5% T i 0 2 weight as A 1 2 0 -3, subsequently Mature form and hydrated oxides of aluminum Was precipitated and coated on the titanium dioxide particles. The solid content is filtered and washed, and the washed cake is dried and then powdered with a hammer type mill. This was ground to obtain ultrafine titanium dioxide powder (average single particle diameter: 0.02 urn). 40 parts by weight of the fine particle titanium dioxide powder was mixed with a dispersion of 12 parts by weight of a dispersant (trimethylsiloxycyanic acid) and 48 parts by weight of a dispersion medium (octamethylcyclotetrasiloxane) using a disper. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone foam dispersion (A) having a viscosity of 150 cP.
実施例 2  Example 2
四塩化チタン水溶液の加水分解により得られた含水酸化チタンを T i 0, 換算 1 0 0 g/1の濃度の水性懸濁液とした。 この水性懸濁液 2 1に 4 8 %水酸化ナ トリゥム水溶液 1 4 0 0 gを攪拌しながら添加し、 9 5 °Cで 1 2 0分加熱後、 ろ 過し、 十分に洗浄を行った。 洗浄ケーキを水でレパルプし、 T i 02 換算 1 0 0 g / 1の濃度の水性懸濁液とし、 この水性懸濁液 1. 5 1を還流器付きフラスコ に入れ、 3 5%塩酸 4 0 0 gを攪拌しながら添加したのち、 9 5°Cで 1 2 0分間 加熱熟成し、 ルチル型結晶の長軸 0. 2 0 //m、 軸比 5. 0 (平均単一粒子径で 表すと、 0. 0 7 8〃m) の棒状微粒子酸化チタンの水性懸濁液を得た。 The hydrous titanium oxide obtained by hydrolysis of the titanium tetrachloride aqueous solution was used as an aqueous suspension having a concentration of 100 g / 1 in terms of T i 0. To this aqueous suspension 21 was added 1400 g of a 48% aqueous sodium hydroxide solution with stirring, heated at 95 ° C. for 120 minutes, filtered, and sufficiently washed. . The washed cake was Reparupu with water, and T i 0 2 conversion 1 0 0 g / 1 concentration of the aqueous suspension, placed the aqueous suspension 1.5 1 reflux condenser flask, 35% hydrochloric acid 4 After adding 0 g with stirring, the mixture was heated and aged at 95 ° C for 120 minutes, and the major axis of the rutile crystal was 0.20 // m, the axial ratio was 5.0 (average single particle diameter). When expressed, an aqueous suspension of 0.078 μm) of rod-shaped fine particle titanium oxide was obtained.
この懸濁液を 7 0°Cに加熱した後よく攪拌しながらアルミン酸ナトリウムを A 1 03 として T i 02 重量基準で 5%添加し、 引き続き熟成してアルミニゥ ムの水和酸化物を該ニ酸化チタン粒子上に沈殿、 被覆させた。 その固形分を濾過、 洗浄し、 洗浄ケーキを乾燥したのちハンマ一タイプミルで粉砕して棒状微粒子二 酸化チタン粉末を得た。 Sodium aluminate was added 5% T i 0 2 weight as A 1 0 3 with good stirring After heating this suspension to 7 0 ° C, the hydrated oxide of Aruminiu beam subsequently was aged Precipitated and coated on the titanium dioxide particles. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer-type mill to obtain rod-shaped fine particle titanium dioxide powder.
この棒状微粒子二酸化チタン粉末 4 0重量部を分散剤 （トリメチルシロキシケ ィ酸） 1 2重量部と分散媒 （デカメチルシクロペンタシロキサン） 4 8重量部と の混合液中にディスパ一を用いて混合した。 次に、 これをジルコンビ一ズをメデ ィァとして用い、 サンドミルで粉砕したところ、 粘度 1 0 0 c Pのシリコーンォ ィル分散体 (B) を得た。  40 parts by weight of the rod-shaped fine particles of titanium dioxide were mixed with a dispersion of 12 parts by weight of a dispersant (trimethylsiloxycholic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane) using a disperser. did. Next, this was pulverized with a sand mill using zircon beads as a media to obtain a silicone roll dispersion (B) having a viscosity of 100 cP.
実施例 3  Example 3
四塩化チタン水溶液の加水分解により得られた含水酸化チタンを T i 02 換算 1 0 0 g/ 1の濃度の水性懸濁液とした。 この水性懸濁液 2 1に 4 8 %水酸化ナ トリウム水溶液 1 4 0 0 gを攪拌しながら添加し、 9 5°Cで 1 2 0分加熱後、 ろ 過し、 十分に洗浄を行った。 洗浄ケーキを水でレパルプし、 T i 02 換算 1 0 0 gZ lの濃度の水性懸濁液とし、 この水性懸濁液 1 . 5 1を還流器付きフラスコ に入れ、 3 5 %塩酸 5 7 0 gを攪拌しながら瞬時に添加したのち、 9 5 °Cで 1 2 0分間加熱熟成し、 ルチル型結晶の長軸 0 . 3 0〃m、 短軸 0 . 0 5 5〃m (平 均単一粒子径で表すと、 0 . 1 1 ^ m) の樹枝状微粒子酸化チタンの水性懸濁液 を得た。 The hydrous titanium oxide obtained by hydrolysis of titanium tetrachloride aqueous solution was T i 0 2 conversion 1 0 0 g / 1 concentration of the aqueous suspension. To this aqueous suspension 21 was added 1400 g of a 48% aqueous sodium hydroxide solution with stirring, and after heating at 95 ° C for 120 minutes, filtration was performed. And thoroughly washed. The washed cake was Reparupu with water, T i 0 2 and converted 1 0 0 gZ l aqueous suspension with a concentration of, putting the aqueous suspension 1.5 1 reflux condenser flask, 3 5% hydrochloric acid 5 7 0 g was added instantaneously with stirring, and the mixture was aged by heating at 95 ° C for 120 minutes, and the long axis of the rutile crystal was 0.30〃m and the short axis was 0.055〃m (average). An aqueous suspension of dendritic particulate titanium oxide having a particle diameter of 0.11 ^ m) was obtained.
この懸濁液を 7 0 °Cに加熱した後よく攪拌しながらアルミン酸ナトリウムを A 1 2 03 として T i 02 重量基準で 5 %添加し、 引き続き熟成してアルミニゥ ムの水和酸化物を該ニ酸化チタン粒子上に沈殿、 被覆させた。 その固形分を濾過、 洗浄し、 洗浄ケーキを乾燥したのちハンマータイプミルで粉砕して樹枝状微粒子 二酸化チタン粉末を得た。 The suspension was added 5% T i 0 2 weight sodium aluminate as A 1 2 0 3 with good stirring after heating to a 7 0 ° C, hydrated oxides of Aruminiu beam subsequently was aged Was precipitated and coated on the titanium dioxide particles. The solid content was filtered and washed, and the washed cake was dried and then pulverized with a hammer type mill to obtain dendritic fine particles of titanium dioxide powder.
この樹枝状微粒子二酸化チタン粉末 4 0重量部を分散剤 （トリメチルシロキシ ゲイ酸） 1 2重量部と分散媒 （デカメチルシクロペンタシロキサン） 4 8重量部 との混合液中にディスパ一を用いて混合した。 次に、 これをジルコンビ一ズをメ ディアとして用い、 サンドミルで粉砕したところ、 粘度 1 3 0 c Pのシリコーン オイル分散体 ( C ) を得た。  40 parts by weight of the dendritic titanium dioxide powder was mixed with a dispersion of 12 parts by weight of a dispersant (trimethylsiloxygayic acid) and 48 parts by weight of a dispersion medium (decamethylcyclopentasiloxane) using a disperser. did. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (C) having a viscosity of 130 cP.
実施例 4  Example 4
実施例 1の微粒子二酸化チタン粉末 4 0重量部を分散剤 （トリメチルシロキシ ゲイ酸 6重量部とジメチルポリシロキサン 'メチル （ポリオキシエチレン） シロ キサン共重合体 6重量部） 計 1 2重量部と分散媒 （ォクタメチルシクロテトラシ ロキサン） 4 8重量部との混合液中にディスパーを用いて混合した。 次に、 これ をジルコンビーズをメディアとして用い、 サンドミルで粉碎したところ、 粘度 9 0 c Pのシリコーンオイル分散体 （D) を得た。  40 parts by weight of the fine particle titanium dioxide powder of Example 1 was dispersed with a dispersant (6 parts by weight of trimethylsiloxy gay acid and 6 parts by weight of dimethylpolysiloxane 'methyl (polyoxyethylene) siloxane copolymer) in a total of 12 parts by weight. The mixture was mixed with a solvent (octamethylcyclotetrasiloxane) 48 parts by weight using a disper. Next, this was pulverized with a sand mill using zircon beads as a medium to obtain a silicone oil dispersion (D) having a viscosity of 90 cP.
比較例 1  Comparative Example 1
実施例 1の微粒子二酸化チタンを粉末 （E) として用いた。  The fine particle titanium dioxide of Example 1 was used as a powder (E).
比較例 2  Comparative Example 2
実施例 2の棒状微粒子二酸化チタンを粉末 （F ) として用いた。  The rod-shaped fine particle titanium dioxide of Example 2 was used as a powder (F).
比較例 3  Comparative Example 3
実施例 3の樹枝状微粒子二酸化チタンを粉末 （G) として用いた。 試験例 1 The dendritic particulate titanium dioxide of Example 3 was used as the powder (G). Test example 1
微粒子二酸化チタンのシリコーン分散体 （A) 〜 （D) 及び粉末 （E) 〜 （G) をそれぞれ下記の処方で合計量が 1 0 0重量部になるように配合して日焼け止め クリーム （WZOェマルジヨン） （a) (b) (c) (d) (e) (f ) (g) を得た。  A sunscreen cream (WZO emulsion) is prepared by blending the silicone dispersion (A) to (D) and the powders (E) to (G) of the fine particle titanium dioxide in the following formulation so that the total amount is 100 parts by weight. (A) (b) (c) (d) (e) (f) (g) were obtained.
(1) ォクタメチルシク トテトラシロキサン 20  (1) Octamethylcytotetrasiloxane 20
(2) ジメチルポリシロキサン 1 5  (2) Dimethylpolysiloxane 15
(3) ジメチルポリシロキサン ·  (3) Dimethylpolysiloxane
メチル （ポリオキンエチレン） シロキサン共重合体 0  Methyl (polyquinethylene) siloxane copolymer 0
(4) 微粒子二酸化チタンシリコーン分散体 (A) 〜 （D) 7  (4) Fine particle titanium dioxide silicone dispersion (A) to (D) 7
又は微粒子二酸化チタン粉末 （E) 〜 （G) 3  Or fine particle titanium dioxide powder (E) to (G) 3
(5) ナイロンパウダー （粒子径 5 zm) 1 2  (5) Nylon powder (particle size 5 zm) 1 2
(6) エタノール 1 0 0重量部 (6) 100 parts by weight of ethanol
(7) グリセリン 2 (7) Glycerin 2
(8) 精製水 27  (8) Purified water 27
成分 （1) 〜 （5) を混合してデイスパーで分散したものに、 予め混合した成 分 （6) 〜 （8) の混合物を攪拌しながら徐々に添加して日焼け止めクリームを 調整した。  The components (1) to (5) were mixed and dispersed with a disperser, and the premixed components (6) to (8) were gradually added with stirring to prepare a sunscreen cream.
評価方法 1  Evaluation method 1
上記各クリームを石英ガラス板上に 25 //mの膜厚となるように塗布し、 分光 光度計にて 750〜300 nmの透過率を測定した。  Each of the above creams was applied on a quartz glass plate so as to have a thickness of 25 // m, and the transmittance at 750 to 300 nm was measured with a spectrophotometer.
評価方法 2  Evaluation method 2
上記各クリームを 20〜52歳の女性 1 0名に通常に使用してもらい、 肌の上 での伸びのよさの使用感を相互に評価してもらつた。  Each of the above creams was used by 10 women aged 20 to 52 years ordinarily, and each was evaluated on the feeling of good stretch on the skin.
以上の試験 ·評価結果を表 1に示した。 P 7 7 Table 1 shows the above test and evaluation results. P 7 7
8 表 1  8 Table 1
試料を配合した日焼け止めクリームの透過率 （％) 可視光領域 紫外線 A領域 紫外線 B領域 1史用 (5 5 0 nm) (3 6 0 nm) (3 0 8 nm) 実删 1 (a) ， 0 乙 4. 0 u . o  Permeability of sunscreen cream containing the sample (%) Visible light region UV A region UV B region 1 use (550 nm) (366 nm) (308 nm) Experiment 1 (a), 0 u 4.o u
0 7 瞧 (d) 9 2. 8 2 4. 8 0. 9 9 比赚 (e) 8 0. 3 5 8. 6 4 7. 4 3 鑭 2 (b) 9 0. 1 2 0. 8 1. 2 9 mm (f ) 8 2. 8 5 3. 4 3 8. 4 4 鑭3 (c) 8 4. 7 1 1. 1 3. 9 8 mm (g) 7 7. 8 4 9. 6 5 0. 8 5  0 7 瞧 (d) 9 2.8 2 4.8 0.9.9 Ratio 赚 (e) 8 0.3 5 8.6 4 7.4.3 3 鑭 2 (b) 9 0.1 2 0.8 0.8 1 2 9 mm (f) 8 2.85 5 3.4 3 8.44 4 鑭 3 (c) 8 4.71 1 1.13.98 mm (g) 7 7.8 4 9.6 5 0.85
(注） 使用感は 1 0段階で評価。 数値が大きい程、 伸びが良いことを示す。 産業上の利用可能性 (Note) The usability was evaluated on a 10-point scale. The higher the value, the better the elongation. Industrial applicability
本発明の微粒子二酸化チタンシリコーン分散体は、 安全性、 安定性、 透明性に 優れた紫外線遮蔽剤である微粒子二酸化チ夕ンを非常に良く分散した状態で含有 するため、 化粧料に配合すると、 微粒子二酸化チタンが本来有する優れた紫外線 遮蔽能を十分に発揮するのに加え、 配合した化粧料の安定性向上、 伸びのよさな どの使用感の向上の効果を発現する化粧料を提供する。  The fine particle titanium dioxide silicone dispersion of the present invention contains finely particulate titanium dioxide, which is an ultraviolet shielding agent excellent in safety, stability, and transparency, in a very well-dispersed state. To provide a cosmetic that, in addition to fully exhibiting the excellent ultraviolet shielding ability inherent in fine-grained titanium dioxide, also has the effect of improving the stability of the compounded cosmetic and improving the usability such as good elongation.

Claims

請求の範囲 The scope of the claims
I. 分散媒としてのシリコーン、 微粒子二酸化チタン粒子及び分散剤を含むシ リコ一ン分散体で、 該微粒子二酸化チタンが平均単一粒子径 0 . 0 0 5〜 0 . 1 5 mをもつ二酸化チタン分散体。 I. A silicone dispersion containing silicone as a dispersion medium, fine titanium dioxide particles and a dispersant, wherein the fine titanium dioxide has an average single particle diameter of 0.05 to 0.15 m. Dispersion.
2 . 微粒子二酸化チ夕ンの平均単一粒子径 0 . 0 0 5〜 0 . 1 1 mである 請求項 1に記載の二酸化チタン分散体。  2. The titanium dioxide dispersion according to claim 1, wherein the average single particle diameter of the fine particle carbon dioxide is 0.005 to 0.11 m.
3 . 分散媒としてのシリコーンがメチルポリシロキサンである請求項 1に記 載の二酸化チタン分散体。  3. The titanium dioxide dispersion according to claim 1, wherein the silicone as the dispersion medium is methylpolysiloxane.
4 . 分散媒としてのシリコーンがメチルフヱニルポリシロキサンである請求 項 1に記載の二酸化チタン分散体。  4. The titanium dioxide dispersion according to claim 1, wherein the silicone as a dispersion medium is methylphenylpolysiloxane.
5 . 分散媒としてのシリコーンがメチルシクロポリシロキサンである請求項 1に記載の二酸化チタン分散体。  5. The titanium dioxide dispersion according to claim 1, wherein the silicone as a dispersion medium is methylcyclopolysiloxane.
6 . 分散剤がトリメチルシロキシゲイ酸である請求項 1に記載の二酸化チタ ン分散体。  6. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethylsiloxygeic acid.
7 . 分散剤がジメチルポリシロキサン 'メチル （ポリオキシアルキレン） シ ロキサン共重合体である請求項 1に記載の二酸化チタン分散体。  7. The titanium dioxide dispersion according to claim 1, wherein the dispersant is a dimethylpolysiloxane 'methyl (polyoxyalkylene) siloxane copolymer.
8 . 分散剤がトリメチルシロキシゲイ酸及びジメチルポリシロキサン ·メチ ノレ （ポリオキシアルキレン） シロキサン共重合体である請求項 1に記載の二酸化 チタン分散体。  8. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethylsiloxygeic acid and a dimethylpolysiloxane-methylene (polyoxyalkylene) siloxane copolymer.
9 . 微粒子二酸化チタンが、 長さが 0 . 0 5〜 0 . 6 m、 軸比が 3以上の 棒状微粒子二酸化チタンである請求項 1に記載の二酸化チタン分散体。  9. The titanium dioxide dispersion according to claim 1, wherein the fine particle titanium dioxide is a rod-shaped fine particle titanium dioxide having a length of 0.05 to 0.6 m and an axial ratio of 3 or more.
10. 微粒子二酸化チタンの形状が樹枝状或いはヒトデ状であり、 平均長軸径 が 0 . 2〜 0 . 5 m、 平均短軸径が 0 . 0 4〜 0 . 1 / m、 軸比が 3以上であ る請求項 1に記載の二酸化チタン分散体。  10. The fine particle titanium dioxide is dendritic or starfish-shaped, average long axis diameter is 0.2 to 0.5 m, average short axis diameter is 0.04 to 0.1 / m, axis ratio is 3 2. The titanium dioxide dispersion according to claim 1, which is as described above.
II. 請求項 1の微粒子二酸化チタン分散体を含有する日焼け止め化粧料。 補正書の請求の範囲 II. A sunscreen cosmetic comprising the fine particle titanium dioxide dispersion of claim 1. Claims of amendment
[1 998年 1月 29日 （29. 01. 98 ) 国際事務局受理：出願当初の請求の 範囲 1—1 1は捕正された請求の範囲 1—15に置き換えられた。 （2頁） ]  [1 January 29, 1998 (29.01.98) Accepted by the International Bureau: Claims 1–1 1 at the time of filing were replaced with claims 1–15 as captured. (2 pages)]
I. (補正後） 分散媒としてのシリコーンを 2 0〜 7 0重量％、 微粒子二酸化 チタンを 3 0〜 7 0重量％及び分散剤を 1〜 4 0重量％含むシリコーン分散体で、 該微粒子二酸化チタンが平均単一粒子径 0. 0 0 5〜0. 1 5 mをもつ二酸化 チタン分散体。  I. (After correction) A silicone dispersion containing 20 to 70% by weight of silicone as a dispersion medium, 30 to 70% by weight of titanium dioxide and 1 to 40% by weight of a dispersant, A titanium dioxide dispersion in which titanium has an average single particle size of 0.005 to 0.15 m.
2. 微粒子二酸化チタンが平均単一粒子径が 0. 0 0 5〜 0. 1 1 ILL mであ る請求項 1に記載の二酸化チタン分散体。  2. The titanium dioxide dispersion according to claim 1, wherein the fine particle titanium dioxide has an average single particle size of 0.05 to 0.11 ILLm.
3. (追加） 分散媒としてのシリコーンを 4 0〜 7 0重量％含む請求項 1に記 載の二酸化チタン分散体。  3. (Addition) The titanium dioxide dispersion according to claim 1, comprising 40 to 70% by weight of silicone as a dispersion medium.
4. 分散媒としてのシリコーンがメチルポリシロキサンである請求項 1に記 載の二酸化チタン分散体。  4. The titanium dioxide dispersion according to claim 1, wherein the silicone as a dispersion medium is methylpolysiloxane.
5. 分散媒としてのシリコーンがメチルフヱニルポリシロキサンである請求 項 1に記載の二酸化チタン分散体。  5. The titanium dioxide dispersion according to claim 1, wherein the silicone as a dispersion medium is methylphenylpolysiloxane.
6. 分散媒としてのシリコーンがメチルシクロポリシロキサンである請求項 1に記載の二酸化チタン分散体。  6. The titanium dioxide dispersion according to claim 1, wherein the silicone as a dispersion medium is methylcyclopolysiloxane.
7. 分散剤がトリメチルシ口キケィ酸である請求項 1に記載の二酸化チタン 分散体。  7. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethyl citrate.
8. 分散剤がジメチルポリシロキサン 'メチル （ポリオキシアルキレン） シ ロキサン共重合体である請求項 1に記載の二酸化チタン分散体。  8. The titanium dioxide dispersion according to claim 1, wherein the dispersant is a dimethylpolysiloxane 'methyl (polyoxyalkylene) siloxane copolymer.
9. 分散剤がトリメチルシ口キケィ酸及びジメチルポリシロキサン ·メチル (ポリオキシアルキレン） シロキサン共重合体である請求項 1に記載の二酸化チ タン分散体。  9. The titanium dioxide dispersion according to claim 1, wherein the dispersant is trimethyl citrate and dimethylpolysiloxane-methyl (polyoxyalkylene) siloxane copolymer.
10. 微粒子二酸化チタンが、 長さ 0. 0 5〜0. 6 zm、 軸比が 3以上の棒 状微粒子二酸化チタンである請求項 1に記載の二酸化チタン分散体。  10. The titanium dioxide dispersion according to claim 1, wherein the fine particle titanium dioxide is a rod-shaped fine particle titanium dioxide having a length of 0.05 to 0.6 zm and an axial ratio of 3 or more.
II. 微粒子二酸化チタンの形状が、 樹枝状或いはヒ トデ状であり、 平均長軸 径が 0. 2〜 0. 5 m、 平均短軸径が 0. 0 4〜 1 m、 軸比が 3以上で ある請求項 1に記載の二酸化チタン分散体。  II. Particulate titanium dioxide has a dendritic or bird-like shape, average major axis diameter of 0.2 to 0.5 m, average minor axis diameter of 0.04 to 1 m, axial ratio of 3 or more The titanium dioxide dispersion according to claim 1, wherein the titanium dioxide dispersion is:
12. 請求項 1の微粒子二酸化チタン分散体を含有する日焼け止め化粧料。  12. A sunscreen cosmetic comprising the fine particle titanium dioxide dispersion of claim 1.
.補正された用紙 （条約第 19条） Amended paper (Article 19 of the Convention)
13. (追加） 平均単一粒子径が 0 . 0 0 5〜 1 5； mの微粒子二酸化チタ ンを分散剤の存在下にシリコーン分散媒と混合した後、 湿式粉砕してなる二酸化 チタン分散体の製造方法。 13. (Addition) Titanium dioxide dispersion obtained by mixing fine particle titanium dioxide having an average single particle diameter of 0.005 to 15; m with a silicone dispersion medium in the presence of a dispersant, and then wet-milling. Manufacturing method.
14. (追加） 湿式粉砕操作の前および/または後で 5 0 °C以上の加熱処理を行 う請求項 1 3記載の二酸化チタン分散体の製造方法。  14. The process for producing a titanium dioxide dispersion according to claim 13, wherein a heat treatment at 50 ° C or more is performed before and / or after the wet pulverization operation.
15. (追加） 加熱処理の温度が 8 0 °C以上である請求項 1 3記載の二酸化チ夕 ン分散体の製造方法。  15. (Addition) The method for producing a titanium dioxide dispersion according to claim 13, wherein the temperature of the heat treatment is 80 ° C or more.
補正された用紙 （条約第 19条） Amended paper (Article 19 of the Convention)
PCT/JP1997/002760 1996-10-11 1997-08-07 Dispersion of particulate titanium dioxide in silicone WO1998016193A1 (en)

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JP28913296A JP3224750B2 (en) 1995-11-28 1996-10-11 Fine particle titanium dioxide silicone dispersion

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001037795A1 (en) * 1999-11-25 2001-05-31 Shiseido Co., Ltd. Method for producing cosmetics
KR100376089B1 (en) * 2001-03-14 2003-03-15 주식회사 태평양 A base composition for blocking ultraviolet rays and cosmetics containing the same

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115211A (en) * 1990-08-22 1991-05-16 Kao Corp Cosmetic
JPH08127514A (en) * 1994-10-27 1996-05-21 Kanebo Ltd Make-up cosmetic

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03115211A (en) * 1990-08-22 1991-05-16 Kao Corp Cosmetic
JPH08127514A (en) * 1994-10-27 1996-05-21 Kanebo Ltd Make-up cosmetic

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001037795A1 (en) * 1999-11-25 2001-05-31 Shiseido Co., Ltd. Method for producing cosmetics
US6972129B1 (en) 1999-11-25 2005-12-06 Shiseido Co., Ltd. Method for producing cosmetics
KR100376089B1 (en) * 2001-03-14 2003-03-15 주식회사 태평양 A base composition for blocking ultraviolet rays and cosmetics containing the same

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TW409127B (en) 2000-10-21

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