JP4514526B2 - Cosmetics and method for producing the same - Google Patents

Cosmetics and method for producing the same Download PDF

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JP4514526B2
JP4514526B2 JP2004175725A JP2004175725A JP4514526B2 JP 4514526 B2 JP4514526 B2 JP 4514526B2 JP 2004175725 A JP2004175725 A JP 2004175725A JP 2004175725 A JP2004175725 A JP 2004175725A JP 4514526 B2 JP4514526 B2 JP 4514526B2
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porous body
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solid cosmetic
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聡 坂西
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Mitsubishi Pencil Co Ltd
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Description

本発明は、複合多孔質体を含有する化粧料及びその製造方法に関し、更に詳しくは、アイライナー、アイブロウなどの固形化粧料、粉体化粧料などに好適な化粧料及びその製造方法に関する。   The present invention relates to a cosmetic containing a composite porous body and a method for producing the same, and more particularly, to a cosmetic suitable for a solid cosmetic such as an eyeliner and eyebrow, a powder cosmetic, and a method for producing the same.

従来より、吸着剤や固形化粧料の骨格として多孔質体を用いることが知られている。
この多孔質体を固形化粧料などに用いる理由は、化粧料に微細な孔があいた多孔質構造を有する材料を配合することにより、毛穴の汚れや、古くなった角質を吸着、除去することができる上、有効成分を吸着保持でき、また、広い表面積を有するため、有効成分などが効果的に作用するためである。
Conventionally, it is known to use a porous body as a skeleton of an adsorbent or a solid cosmetic.
The reason for using this porous material for solid cosmetics, etc., is to adsorb and remove pore dirt and old keratin by blending a material having a porous structure with fine pores in the cosmetic. This is because the active ingredient can be adsorbed and held and has a large surface area, so that the active ingredient and the like act effectively.

この化粧品用材料として用いられる多孔質体としては、例えば、炭素数10以上のアルキル基及び重合性の炭素―炭素二重結合を一分子内に持つモノマーと架橋剤とを重合して得られる多孔質ポリマーゲルを化粧品用材料として用いることが知られている(例えば、特許文献1参照)。
しかしながら、上記多孔質ポリマーゲルでは、構成材料が有機高分子であるため、粒子は柔軟性に富む代わりに、硬度が低いため、化粧料中に多く配合すると、塗布感がパウダリーで良好な塗布感になり難いという課題がある。
Examples of the porous material used as the cosmetic material include a porous material obtained by polymerizing a monomer having an alkyl group having 10 or more carbon atoms and a polymerizable carbon-carbon double bond in one molecule and a crosslinking agent. It is known to use a porous polymer gel as a cosmetic material (for example, see Patent Document 1).
However, in the porous polymer gel, since the constituent material is an organic polymer, the particles have a low hardness instead of being rich in flexibility. There is a problem that it is difficult to become.

また、化粧品用材料として用いられる多孔質体として、開口の外殻に酸化ケイ素を配し、開口深さが50〜300nmである塊状メソポーラス粉体を用いたもの(例えば、特許文献2参照)や、金属の酸化物及び水酸化物から選ばれる2種以上と無機発泡性固形物及び有機固形物から選ばれる1種以上とを焼結させてなる焼結空隙粉体を用いたもの(例えば、特許文献3参照)が知られているが、これらの材料そのものは無機材料で構成されているため、柔軟性に乏しい結果となっている。   Moreover, as a porous body used as a cosmetic material, silicon oxide is disposed on the outer shell of the opening, and a massive mesoporous powder having an opening depth of 50 to 300 nm is used (see, for example, Patent Document 2) Using a sintered void powder obtained by sintering two or more selected from metal oxides and hydroxides and one or more selected from inorganic foamable solids and organic solids (for example, However, since these materials themselves are composed of inorganic materials, the results are poor in flexibility.

更に、多孔質体を固形化粧料の骨格として応用したものとして、結合剤に粘土を使用し、粘土を焼結させたもの(例えば、特許文献4参照)や、気孔形成材を使用し、より多孔質な焼結体にしたもの(例えば、特許文献5参照)が知られている。   Furthermore, as an application of the porous body as a skeleton of a solid cosmetic, a clay is used as a binder, a clay is sintered (for example, see Patent Document 4), a pore forming material is used, and more A porous sintered body (see, for example, Patent Document 5) is known.

しかしながら、上記特許文献4に開示される発明は、焼結処理を施すことにより多孔質の骨格を形成する粘土の焼結体中に、粉末状に分散含有された無機顔料を含有させた棒状化粧料であり、その多孔質とは、当該文献では、「気孔率は大きいほど使用時のタッチや塗布性が良くなる傾向にあり、また、気孔率が小さく緻密化すればするほど強度が大きくなる傾向にある。」と記載され、結局当該文献が開示するのは気孔率が50〜90%程度の焼結体である。すなわち、粘土の焼結体では、十分な機械的強度は得られるものの硬く、肌に塗布することは困難であるが、多孔質の焼結体にすることにより、十分な機械的強度と良好な塗布感を同時に満たす棒状化粧料が得られるというものである。   However, the invention disclosed in Patent Document 4 discloses a stick-shaped makeup in which an inorganic pigment dispersed and contained in a powder form is contained in a clay sintered body that forms a porous skeleton by performing a sintering treatment. According to the document, “the larger the porosity, the better the touch and applicability during use, and the smaller the porosity, the higher the strength. "It is in a tendency.", And this document eventually discloses a sintered body having a porosity of about 50 to 90%. In other words, a clay sintered body can provide sufficient mechanical strength but is hard and difficult to apply to the skin. However, by making a porous sintered body, sufficient mechanical strength and good strength can be obtained. A bar-shaped cosmetic material that satisfies the feeling of application at the same time is obtained.

しかしながら、良好な塗布感と十分な機械的強度とを同時に満たすためには、気孔率の調整が不可欠であるが、気孔率の調整は、上記特許文献4に記載されるように焼結処理時の温度や粘土と粉末状の顔料の使用割合をかえるだけであり、当該特許文献4に記載される好ましい50〜90%程度の気孔率の焼結体を得ることは非常に困難である。
更に、上記特許文献5に開示される焼結気孔形成材を使用し、より多孔質な焼結体にしたものでは、十分な機械的強度と良好な塗布感を同時に満たす化粧料が得られないものである。
However, in order to satisfy a good coating feeling and sufficient mechanical strength at the same time, the adjustment of the porosity is indispensable. However, the adjustment of the porosity is performed during the sintering process as described in Patent Document 4 above. However, it is very difficult to obtain a sintered body having a preferable porosity of about 50 to 90% described in Patent Document 4 only by changing the temperature and the usage ratio of clay and powdered pigment.
Furthermore, the use of the sintered pore forming material disclosed in the above-mentioned Patent Document 5 makes it possible to obtain a cosmetic material satisfying sufficient mechanical strength and good coating feeling at the same time by using a more porous sintered body. Is.

更にまた、良好な塗布感と十分な機械的強度とを同時に満たす棒状の化粧料等としては、例えば、本願出願人によるベントナイト、スメクタイト、モンモリロナイト、ピーデライト、ノントライト、ヘクトライト及びサポナイトからなる群より選ばれた少なくとも1種を1〜10重量%と無機の体質顔料及び無機の着色顔料を必須成分とし、これらを300〜1000℃の温度範囲で焼結して得た炭化物を全く残さない無機粉体及び水よりなる成形組成物を乾燥後300〜1000℃の熱処理を施してなる棒状化粧料(例えば、特許文献6参照)が知られているが、上記と同様に粘土を焼結させて結合材としているため、軟らかい塗布感となるものに配合した場合には強度が弱くなってしまうという点に若干の課題がある。   Furthermore, the bar-shaped cosmetic material that simultaneously satisfies a good coating feeling and sufficient mechanical strength, for example, is selected from the group consisting of bentonite, smectite, montmorillonite, pedelite, nontrite, hectorite and saponite by the applicant of the present application. 1 to 10% by weight of at least one of these inorganic powders and inorganic color pigments as essential components, and inorganic powders obtained by sintering these in a temperature range of 300 to 1000 ° C. leaving no carbide In addition, a rod-shaped cosmetic (for example, see Patent Document 6) obtained by drying a molding composition comprising water and heat-treating at 300 to 1000 ° C. is known. Therefore, there is a slight problem in that the strength becomes weak when blended into a soft coating feeling.

また、このように粘土を焼成して結合材とする場合、有機顔料や染料は変色してしまうため、無機顔料等の耐熱性の高い顔料しか使用することができないため、十分な多色化と発色性を得ることは困難であるという課題がある。
特開昭63−243012号公報(特許請求の範囲、実施例等) 特開平10−152317号公報(特許請求の範囲、実施例等) 特開平10−130117号公報(特許請求の範囲、実施例等) 特開昭61−176513号公報(特許請求の範囲、実施例等) 特開昭61−197507号公報(特許請求の範囲、実施例等) 特開平8−188518号公報(特許請求の範囲、実施例等)
In addition, when the clay is baked in this way to form a binder, the organic pigments and dyes change color, so only high heat-resistant pigments such as inorganic pigments can be used. There is a problem that it is difficult to obtain color developability.
Japanese Patent Laid-Open No. 63-243012 (Claims, Examples, etc.) JP-A-10-152317 (Claims, Examples, etc.) Japanese Patent Laid-Open No. 10-130117 (Claims, Examples, etc.) JP 61-176513 (Claims, Examples, etc.) Japanese Patent Laid-Open No. 61-197507 (Claims, Examples, etc.) JP-A-8-188518 (Claims, Examples, etc.)

本発明は、上記従来技術の課題等に鑑み、また、本願出願人らの先行技術を更に改良して多孔質体としての機能及び付加価値を更に拡大させることであり、塗布感がサラサラして良好でありつつ、柔軟性と保湿効果を有し、かつ、鮮やかな発色性と濃度を有する多色化可能な化粧料及びその製造方法を提供することを目的とする。   In view of the above-mentioned problems of the prior art, the present invention further improves the prior art of the applicants of the present application and further expands the function and added value as a porous body, and the coating feeling is smooth. An object of the present invention is to provide a cosmetic capable of being multicolored having good flexibility and moisture retention, vivid color developability and concentration, and a method for producing the same.

本発明者は、上記従来の課題等を解決するために、鋭意研究を行った結果、少なくとも、特定の化合物中に水溶性有機高分子を含有し、連通孔を有することで広い表面積を作り上げた複合多孔質体を化粧料に含有させることによって、上記目的の化粧料及びその製造方法が得られることを見い出し、本発明を完成するに至ったのである。   As a result of intensive studies to solve the above-described conventional problems, the present inventor has created a wide surface area by including a water-soluble organic polymer in a specific compound and having communication holes. The inventors have found that the above-mentioned cosmetics and production methods thereof can be obtained by incorporating the composite porous material into the cosmetics, and have completed the present invention.

すなわち、本発明は、次の(1)〜(14)に存する。
(1) 金属酸化物中に水溶性有機高分子を含有した複合多孔質体を含有することを特徴とする化粧料。
(2) 複合多孔質体は、金属酸化物中に水溶性有機高分子が均一に混合され、少なくとも連通孔を有する上記(1)記載の化粧料。
(3) 複合多孔質体は、金属酸化物中に水溶性有機高分子が包括して混合されている上記(1)又は(2)記載の化粧料。
(4) 水溶性有機高分子の分子鎖中に、ポリオキシメチレン鎖、ポリオキシエチレン鎖、ポリオキシプロピレン鎖の少なくとも一つを含有している上記(1)〜(3)の何れか一つに記載の化粧料。
(5) 水溶性有機高分子が、ポリアクリル酸系高分子である上記(1)〜(4)の何れか一つに記載の化粧料。
(6) 金属酸化物が、酸化珪素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化亜鉛から選ばれる少なくとも1種である上記(1)〜(5)の何れか一つに記載の化粧料。
(7) 複合多孔質体に香料が含有されている上記(1)〜(6)の何れか一つに記載の化粧料。
(8) 複合多孔質体に界面活性剤が含有されている上記(1)〜(7)の何れか一つに記載の化粧料。
(9) 複合多孔質体に潤滑剤が含有されている上記(1)〜(8)の何れか一つに記載の化粧料。
(10) 複合多孔質体に色材が含有されている上記(1)〜(9)の何れか一つに記載の化粧料。
(11) 複合多孔質体中の水溶性有機高分子の含有量が、0.1〜90重量%である上記(1)〜(10)の何れか一つに記載の化粧料。
(12) 化粧料が複合多孔質体を骨格とする固形化粧料からなる上記(1)〜(11)の何れか一つに記載の化粧料。
(13) 化粧料が複合多孔質体を骨格とする化粧鉛筆からなる上記(1)〜(12)の何れか一つに記載の化粧料。
(14) 水溶性有機高分子と金属酸化物前駆体中とを混合し、金属酸化物前駆体と水溶性有機高分子を分相させ、金属酸化物前駆体をセラミック化することによって合成した複合多孔質体を化粧料として配合することを特徴とする化粧料の製造方法。
That is, the present invention resides in the following (1) to (14).
(1) A cosmetic comprising a composite porous body containing a water-soluble organic polymer in a metal oxide.
(2) The composite porous body according to (1), wherein the water-soluble organic polymer is uniformly mixed in the metal oxide and has at least communicating holes.
(3) The composite porous body according to (1) or (2), wherein the metal oxide is comprehensively mixed with a water-soluble organic polymer.
(4) Any one of the above (1) to (3), wherein the molecular chain of the water-soluble organic polymer contains at least one of a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain Cosmetics described in 1.
(5) The cosmetic according to any one of (1) to (4), wherein the water-soluble organic polymer is a polyacrylic acid polymer.
(6) The cosmetic according to any one of (1) to (5), wherein the metal oxide is at least one selected from silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and zinc oxide.
(7) The cosmetic according to any one of (1) to (6), wherein a fragrance is contained in the composite porous body.
(8) The cosmetic according to any one of (1) to (7), wherein a surfactant is contained in the composite porous body.
(9) The cosmetic according to any one of (1) to (8), wherein a lubricant is contained in the composite porous body.
(10) The cosmetic according to any one of (1) to (9), wherein a color material is contained in the composite porous body.
(11) The cosmetic according to any one of (1) to (10), wherein the content of the water-soluble organic polymer in the composite porous body is 0.1 to 90% by weight.
(12) The cosmetic according to any one of (1) to (11), wherein the cosmetic is a solid cosmetic having a composite porous body as a skeleton.
(13) The cosmetic according to any one of the above (1) to (12), wherein the cosmetic comprises a cosmetic pencil having a composite porous body as a skeleton.
(14) A composite synthesized by mixing a water-soluble organic polymer and a metal oxide precursor, separating the phase of the metal oxide precursor and the water-soluble organic polymer, and converting the metal oxide precursor into a ceramic. A method for producing a cosmetic comprising blending a porous material as a cosmetic.

本発明によれば、金属酸化物中に水溶性有機高分子を含有した複合多孔質体を含有せしめることにより、十分な発色性、描線濃度を持ちながら、塗布感を孔の大きさや分布、若しくは材料種によって硬くも軟らくも自由に設定でき、機械的強度(曲げ強度、引張強度、衝撃強度等)にも優れる化粧料及びその製造方法が提供される。
また、セラミック材料を基本骨格として用いているため、パウダリーで良好な塗布感が得られ、更に低温で合成できるため、顔料の選択が自由であると同時に、連通孔を有する広い表面積の骨格内に水溶性高分子を含有することにより、柔軟性と保湿効果を付与することができる化粧料及びその製造方法が提供される。
According to the present invention, by including a composite porous body containing a water-soluble organic polymer in a metal oxide, the coating feeling can be improved in size and distribution of pores while having sufficient color developability and line density, or A cosmetic material that can be freely set to be hard or soft depending on the type of material and that is excellent in mechanical strength (bending strength, tensile strength, impact strength, etc.) and a method for producing the same are provided.
In addition, since ceramic materials are used as the basic skeleton, powdery and good coating feeling can be obtained, and synthesis can be performed at a low temperature, so that the choice of pigment is free, and at the same time, the skeleton has a large surface area with communication holes. By containing a water-soluble polymer, a cosmetic that can impart flexibility and a moisturizing effect and a method for producing the same are provided.

以下に、本発明の実施形態を詳しく説明する。
本発明の化粧料は、金属酸化物中に水溶性有機高分子を含有した複合多孔質体を含有することを特徴とするものであり、また、本発明の化粧料の製造方法は、水溶性有機高分子と金属酸化物前駆体とを混合し、金属酸化物前駆体と水溶性有機高分子を分相させ、金属酸化物前駆体をセラミック化することによって合成した多孔質体を化粧料として配合することを特徴とするものである。
Hereinafter, embodiments of the present invention will be described in detail.
The cosmetic of the present invention is characterized by containing a composite porous body containing a water-soluble organic polymer in a metal oxide, and the method for producing the cosmetic of the present invention comprises a water-soluble A porous material synthesized by mixing an organic polymer and a metal oxide precursor, phase-separating the metal oxide precursor and the water-soluble organic polymer, and ceramicizing the metal oxide precursor is used as a cosmetic. It is characterized by blending.

本発明に用いる水溶性有機高分子は、成形性の向上(高収率化と高強度化)と同時に金属酸化物(無機高分子)を安定化させるために含有せしめるものである。用いる水溶性有機高分子としては、疎水性、親水性のバランスや、造膜性、成形性の点から、その分子鎖中に、ポリオキシメチレン鎖、ポリオキシエチレン鎖、ポリオキシプロピレン鎖の少なくとも一つを含有しているものが挙げられ、これらであればいずれの平均分子量(以下、単に「分子量」という)においても使用することができる。
具体的には、トリオキサンにエチレンオキサイド等を結合して作られたコポリマーなどが挙げられ、また、分子鎖の端を疎水基で置換した非イオン性界面活性剤、例えば、ポリオキシエチレン(n=23)ラウリルエーテルなども用いることができるが、必ずしもこれに限定されるものではない。
これらは、単独で用いることとなるが、2種類以上を混合して用いることも可能であり、目的とする成形体の形状や成形方法によって適宜選択される。
The water-soluble organic polymer used in the present invention is contained in order to stabilize the metal oxide (inorganic polymer) at the same time as improving moldability (higher yield and higher strength). The water-soluble organic polymer to be used includes at least one of a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain in the molecular chain from the viewpoint of the balance between hydrophobicity and hydrophilicity, film forming property, and moldability. One of them may be used, and any of these may be used at any average molecular weight (hereinafter simply referred to as “molecular weight”).
Specific examples include copolymers formed by combining ethylene oxide and the like with trioxane, and nonionic surfactants in which molecular chain ends are substituted with hydrophobic groups, such as polyoxyethylene (n = 23) Lauryl ether can also be used, but is not necessarily limited thereto.
These can be used alone, but two or more types can be mixed and used, and are appropriately selected depending on the shape of the target molded body and the molding method.

更に、水溶性有機高分子としては、疎水性、親水性のバランスや、造膜性、成形性の点から、ポリアクリル酸系高分子を用いることができ、一般的にポリアクリル酸系高分子に分類されるものであればいずれの分子量においても使用することができ、アルキル基を置換したアクリル酸エステル、例えば、アクリル酸アルキル共重合体、アクリル酸・アクリル酸アシド・アクリル酸エチル共重合体や、アクリル酸ソーダ、例えば、アクリル酸カルシウム、アクリル酸亜鉛等のアクリル酸金属塩などを使用することができるが、必ずしもこれに限定されるものではない。
これらは、単独で用いることとなるが、2種類以上を混合して用いることも可能であり、目的とする成形体の形状や成形方法によって適宜選択される。
Furthermore, as the water-soluble organic polymer, a polyacrylic acid polymer can be used from the viewpoint of the balance between hydrophobicity and hydrophilicity, film forming property, and moldability, and generally a polyacrylic acid polymer. Can be used in any molecular weight as long as it is classified as follows: an acrylate ester substituted with an alkyl group, for example, an alkyl acrylate copolymer, an acrylic acid / acrylic acid acid / ethyl acrylate copolymer Alternatively, sodium acrylate, for example, acrylate metal salts such as calcium acrylate and zinc acrylate can be used, but is not necessarily limited thereto.
These can be used alone, but two or more types can be mixed and used, and are appropriately selected depending on the shape of the target molded body and the molding method.

本発明に用いる金属酸化物前駆体は、酸化珪素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化亜鉛などの金属酸化物の前駆体となる無機高分子であればいずれも用いることができ、例えば、テトラメチルオルソシリケート(TMOS)、テトラエチルオルソシリケート(TEOS)、テトラプロピルオルソシリケート(TPOS)、テトラブチルオルソシリケート(TBOS)、チタンイソプロポキシド、アルミノキサン、ジルコノキサン等の金属アルコキシドの縮合体を用いることができる。
これらは、単独で用いることとなるが、2種類以上を混合して用いることも可能であり、目的とする成形体の形状や成形方法によって適宜選択される。
As the metal oxide precursor used in the present invention, any inorganic polymer can be used as long as it is a precursor of a metal oxide such as silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and zinc oxide. Use of a metal alkoxide condensate such as tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetrabutylorthosilicate (TBOS), titanium isopropoxide, aluminoxane, zircoxane it can.
These can be used alone, but two or more types can be mixed and used, and are appropriately selected depending on the shape of the target molded body and the molding method.

本発明において、複合多孔質体中の水溶性有機高分子の含有量としては、用途によって異なるが、複合多孔質体組成物中に、少なくとも0.1〜90重量%とすることが好ましく、固形化粧料の骨格として用いる場合には、0.1〜50重量%が望ましく、粉末化粧料として用いる場合は、40〜80重量%が望ましい。
この水溶性有機高分子の含有量が0.1重量%未満では、成形時の造形性や均一性等が著しく損なわれ、一定形状の成形体を得ることが難しくなり、また、配合する水溶性高分子の効果を低くなり、好ましくない。一方、水溶性有機高分子の含有量が90重量%を超えると、金属酸化物が骨格をなさなくなってしまい、好ましくない。
In the present invention, the content of the water-soluble organic polymer in the composite porous body varies depending on the application, but is preferably at least 0.1 to 90% by weight in the composite porous body composition, When used as a cosmetic skeleton, 0.1 to 50% by weight is desirable, and when used as a powder cosmetic, 40 to 80% by weight is desirable.
If the content of the water-soluble organic polymer is less than 0.1% by weight, the formability and uniformity during molding are remarkably impaired, and it becomes difficult to obtain a molded product having a fixed shape. The effect of the polymer is lowered, which is not preferable. On the other hand, when the content of the water-soluble organic polymer exceeds 90% by weight, the metal oxide does not form a skeleton, which is not preferable.

本発明において、複合多孔質体中には、更なる十分な発色性、描線濃度、塗布感、機械的強度、趣向性等の向上させる点から、香料、界面活性剤、潤滑剤の少なくとも1種を適宜量更に含有せしめることができる。
本発明で用いられる香料としては、一般的に香料に分類されているものであればいずれも使用することいができ、天然香料であっても合成香料であっても使用することができる。
天然香料としては、例えば、ローズ、ジャスミン、チュベローズ、イランイラン、ラベンダー、アイリス、ブァイオレット、ミモザ等の植物性香料、アンバー、ムスク、シベット、カストリウム、ムスクラット等の動物性香料などが挙げられ、また、合成香料としては、例えば、アルデヒド等をブレンドさせたものや、単離香料が挙げられるが、必ずしもこれに限定されるものではない。
この香料の含有量としては、好ましくは、複合多孔質体組成物中に、1〜15重量%、更に好ましくは、5〜15重量%とすることが望ましい。
In the present invention, the composite porous body contains at least one of a fragrance, a surfactant, and a lubricant from the viewpoint of improving further sufficient color developability, line density, coating feeling, mechanical strength, preference and the like. Can be further added in an appropriate amount.
As the fragrance used in the present invention, any fragrance generally classified as a fragrance can be used. Either a natural fragrance or a synthetic fragrance can be used.
Examples of natural fragrances include plant fragrances such as rose, jasmine, tuberose, ylang ylang, lavender, iris, violet, mimosa, and animal fragrances such as amber, musk, civet, castrium, and muskrat. Examples of synthetic fragrances include blends of aldehydes and the like, and isolated fragrances, but are not necessarily limited thereto.
The content of the fragrance is preferably 1 to 15% by weight, more preferably 5 to 15% by weight in the composite porous body composition.

本発明で用いられる界面活性剤としては、一般的に界面活性剤に分類されているものであればいずれも使用することいができ、イオン型界面活性剤であって非イオン型界面活性剤であっても使用することができる。
イオン型界面活性剤としては、例えば、カルボン酸塩、硫酸エステル塩、スルホン酸塩、リン酸エステル塩等のアニオン界面活性剤や、アルキルアミン塩、第4級アンモニウム塩、アルキルピリジウム塩等のカチオン界面活性剤や、アミノ酸方、ベタイン型、スルホン酸塩型、リン酸エステル塩型等の各両性界面活性剤などが挙げられ、非イオン型界面活性剤としては、あっ問えば、ポリエチレングルコール型、多価アルコール型が挙げられるが、必ずしもこれに限定されるものではない、
この界面活性剤の含有量としては、好ましくは、複合多孔質体組成物中に、1〜80重量%、更に好ましくは、1〜30重量%とすることが望ましい。
Any surfactant that is generally classified as a surfactant can be used as the surfactant used in the present invention. It is an ionic surfactant that is a nonionic surfactant. It can be used even if it exists.
Examples of ionic surfactants include anionic surfactants such as carboxylates, sulfate esters, sulfonates, phosphate ester salts, alkylamine salts, quaternary ammonium salts, alkylpyridium salts, and the like. Cationic surfactants and amphoteric surfactants such as amino acid, betaine type, sulfonate type, and phosphate ester type are listed. Nonionic surfactants include polyethylene glycol. Type, polyhydric alcohol type is mentioned, but is not necessarily limited to this,
The content of the surfactant is preferably 1 to 80% by weight, more preferably 1 to 30% by weight in the composite porous material composition.

本発明で用いられる潤滑剤としては、一般的に潤滑剤に分類されているものであればいずれも使用することいができ、潤滑油であってもグリースであっても使用することができる。
潤滑油としては、例えば、エンジンオイル等の鉱物油、シリコーンオイル、エステルオイル等の合成油、ヒマシオイル等の植物油などが挙げられ、グリースとしては、例えば、カルシウム石鹸グリース、リチウム石鹸グリース等の石鹸系、ベントングリース、シリカゲルグリース等の非石鹸系が挙げられるが、必ずしもこれに限定されるものではない、
この潤滑剤の含有量としては、好ましくは、複合多孔質体組成物中に、5〜80重量%、更に好ましくは、10〜30重量%とすることが望ましい。
As the lubricant used in the present invention, any lubricant can be used as long as it is generally classified as a lubricant. Either a lubricating oil or a grease can be used.
Examples of the lubricating oil include mineral oil such as engine oil, synthetic oil such as silicone oil and ester oil, and vegetable oil such as castor oil. Examples of grease include soap such as calcium soap grease and lithium soap grease. Non-soap system such as system, Benton grease, silica gel grease, etc., but is not necessarily limited to this,
The lubricant content is preferably 5 to 80% by weight, more preferably 10 to 30% by weight in the composite porous body composition.

本発明において、複合多孔質体を含有する化粧料は、複合多孔質体、体質材及び顔料等の色材よりなる固形化粧料の骨格として用いることも可能である。容器充填型化粧料、棒状化粧料及び粉体化粧料等、種々の固形化粧料に適用することが可能である。   In the present invention, the cosmetic containing the composite porous body can also be used as a skeleton of a solid cosmetic made of a composite porous body, an extender, and a coloring material such as a pigment. The present invention can be applied to various solid cosmetics such as container-filled cosmetics, stick-shaped cosmetics, and powder cosmetics.

本発明の化粧料に使用される体質材としては、従来の固形化粧料に使用されているものであれば、特に限定されるものではなく、いずれも使用することができる。例えば、窒化ホウ素、カオリン、タルク、マイカ、炭酸カルシウム等の白色系体質材や、固形化粧料の色相によっては、有色系の体質材も使用することができ、当然これら数種類の混合物も使用できる。特に、好ましくは、その物性、形状から窒化ホウ素、カオリン、タルクが挙げられる。更には、前記複合多孔質体も体質材となり得るものである。   The extender used in the cosmetic of the present invention is not particularly limited as long as it is used in conventional solid cosmetics, and any of them can be used. For example, depending on the color of a white body material such as boron nitride, kaolin, talc, mica, calcium carbonate, or the color of a solid cosmetic, naturally a colored body material can also be used. Particularly preferred are boron nitride, kaolin and talc because of their physical properties and shape. Furthermore, the composite porous body can also serve as an extender.

本発明に用いられる色材としては、例えば、酸化チタン、鉄黒、カーボンブラック、紺青、群青、青色1号、弁柄、黄酸化鉄、酸化クロム、水酸化クロム、酸化亜鉛、酸化ジルコニウム、酸化コバルト、魚鱗箔、オキシ塩化ビスマス、雲母チタン、青色2号、青色404号、赤色2号、赤色3号、赤色102号、赤色104号、赤色105号、赤色106号、黄色4号、黄色5号、緑色3号等の顔料等が挙げられ、これらは単独で、又は2種以上混合して用いることができる。
この色材の含有量としては、好ましくは、複合多孔質体組成物中に、0.1〜30重量%、更に好ましくは、5〜15重量%とすることが望ましい。
Examples of the color material used in the present invention include titanium oxide, iron black, carbon black, bitumen, ultramarine blue, blue No. 1, petal, yellow iron oxide, chromium oxide, chromium hydroxide, zinc oxide, zirconium oxide, and oxidation. Cobalt, fish scale foil, bismuth oxychloride, titanium mica, blue No. 2, blue No. 404, red No. 2, red No. 3, red No. 102, red No. 104, red No. 105, red No. 106, yellow No. 4, yellow 5 No., Green No. 3, and the like. These can be used alone or in admixture of two or more.
The content of the coloring material is preferably 0.1 to 30% by weight, more preferably 5 to 15% by weight in the composite porous body composition.

本発明の化粧料における複合多孔質体の含有量としては、化粧料全量に対して、0.1〜50重量%、更に好ましくは、0.1〜20重量%が望ましい。
この複合多孔質体の含有量が0.1重量%未満では、成形時の造形性や均一性等が著しく損なわれ、一定形状の成形体を得ることが難しくなり、また、該成形体の強度も著しく弱いものとなる。一方、複合多孔質体の含有量が50重量%を超えると、強度は高くなるが、硬くて塗布できなかったり、摩耗しずらくなったりするなどの弊害が生じる。
As content of the composite porous body in the cosmetics of this invention, 0.1-50 weight% with respect to cosmetics whole quantity, More preferably, 0.1-20 weight% is desirable.
If the content of the composite porous body is less than 0.1% by weight, the formability and uniformity during molding are remarkably impaired, and it becomes difficult to obtain a molded body having a fixed shape. Is significantly weaker. On the other hand, when the content of the composite porous body exceeds 50% by weight, the strength is increased, but there are problems such as being hard and unable to be applied, and difficult to wear.

本発明の化粧料は、上述の水溶性有機高分子と金属酸化物前駆体とを混合し、金属酸化物前駆体と水溶性有機高分子を分相させ、金属酸化物前駆体を低温度(100℃以下)でセラミック化することによって合成した多孔質体を化粧料として配合することにより、更に具体的には、分子鎖中に、ポリオキシメチレン鎖、ポリオキシエチレン鎖、ポリオキシプロピレン鎖の少なくとも一つを含有する水溶性有機高分子と、テトラメチルオルソシリケート(TMOS)、テトラエチルオルソシリケート(TEOS)、テトラプロピルオルソシリケート(TPOS)、テトラブチルオルソシリケート(TBOS)、チタンイソプロポキシド、アルミノキサン、ジルコノキサン等の金属アルコキシドの縮合体などの金属酸化物前駆体とを混合し、50〜100℃で金属酸化物前駆体を硬化させ、水溶性高分子と分相させた後、必要に応じて、超音波振動による水溶性高分子の溶出を行った後、マイクロ波加熱などの加熱等によって低温セラミック化することにより合成した多孔質体を化粧料として配合することにより目的の化粧料が製造されることとなる。
得られる複合多孔質体は、水溶性高分子と金属酸化物が化学的に結合しているので、金属酸化物中に水溶性有機高分子が均一に混合分散され、少なくとも連通孔を有するものとなり、また、複合多孔質体は、分相、溶媒除去の過程で分子レベルで複合されているため、金属酸化物中に水溶性有機高分子が包括して混合分散された状態も作られる。
本発明において、含有される複合多孔質体は水溶性有機高分子の種類、分子量、含有量によって連通孔の含有率(気孔率)が自由に設定できるため、強度、摩耗量、塗布感を自由に設定できるものとなる。なお、複合多孔質体の気孔率は、化粧料の用途、形状等により変動するが、複合多孔質体中に50〜98%とすることが望ましい。
The cosmetic of the present invention is a mixture of the water-soluble organic polymer and the metal oxide precursor, phase-separating the metal oxide precursor and the water-soluble organic polymer, and reducing the metal oxide precursor at a low temperature ( By blending a porous material synthesized by ceramicizing at 100 ° C. or lower) as a cosmetic, more specifically, a polyoxymethylene chain, a polyoxyethylene chain, a polyoxypropylene chain is included in the molecular chain. Water-soluble organic polymer containing at least one, tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), tetrapropylorthosilicate (TPOS), tetrabutylorthosilicate (TBOS), titanium isopropoxide, aluminoxane And a metal oxide precursor such as a condensate of a metal alkoxide such as zirconia. After the metal oxide precursor is cured at 100 ° C. and phase-separated with the water-soluble polymer, if necessary, the water-soluble polymer is eluted by ultrasonic vibration, followed by heating such as microwave heating. The target cosmetic is produced by blending the porous material synthesized by low-temperature ceramicization as a cosmetic.
In the obtained composite porous body, since the water-soluble polymer and the metal oxide are chemically bonded, the water-soluble organic polymer is uniformly mixed and dispersed in the metal oxide, and has at least communication holes. In addition, since the composite porous body is composited at the molecular level in the process of phase separation and solvent removal, a state in which the water-soluble organic polymer is comprehensively mixed and dispersed in the metal oxide is also created.
In the present invention, the composite porous body contained can freely set the content of pores (porosity) according to the type, molecular weight, and content of the water-soluble organic polymer, so that the strength, wear amount, and coating feeling can be freely set. It can be set to. In addition, although the porosity of a composite porous body changes with uses, shapes, etc. of cosmetics, it is desirable to set it as 50 to 98% in a composite porous body.

本発明では、上述の如く、水溶性有機高分子と金属酸化物前駆体中とを混合し、金属酸化物前駆体と水溶性有機高分子を分相させ、金属酸化物前駆体を低温下でセラミック化することによって合成した多孔質体、すなわち、金属酸化物中に水溶性有機高分子が均一に混合分散され、少なくとも連通孔を有する複合多孔質体を化粧料として配合することにより製造することができるため、耐熱性の低い顔料を含む様々な顔料を熱処理による劣化を発生させずに、使用することができ、発色が損なわれることも少ない十分な多色化と鮮やかな発色性を有する化粧料が製造されることとなる。
得られる化粧料は、粉体化粧料の他、繰り出し容器用棒状化粧料、木軸用棒状化粧料、紙巻棒状化粧料等の固形化粧料に好適に適用することができ、特に化粧鉛筆として好適に適用することができる。
In the present invention, as described above, the water-soluble organic polymer and the metal oxide precursor are mixed, the metal oxide precursor and the water-soluble organic polymer are phase-separated, and the metal oxide precursor is cooled at a low temperature. A porous material synthesized by ceramicization, that is, a composite porous material in which a water-soluble organic polymer is uniformly mixed and dispersed in a metal oxide and has at least communicating pores is prepared as a cosmetic. Therefore, it is possible to use various pigments, including pigments with low heat resistance, without causing deterioration due to heat treatment. The fee will be manufactured.
The obtained cosmetic can be suitably applied to solid cosmetics such as powder cosmetics, stick cosmetics for feeding containers, stick cosmetics for wooden shafts, and cigarette sticks, and particularly suitable as a cosmetic pencil. Can be applied to.

このように構成される本発明では、金属酸化物中に水溶性有機高分子を含有した複合多孔質体が含有されることとなるので、十分な発色性、描線濃度を持ちながら、塗布感を金属酸化物の大きさや分布、若しくは材料種によって硬くも軟らくも自由に設定でき、機械的強度(曲げ強度、引張強度、衝撃強度等)にも優れると共に、多色化を可能とした化粧料及びその製造方法が得られるものとなる。   In the present invention configured as described above, a composite porous body containing a water-soluble organic polymer is contained in the metal oxide, so that the coating feeling can be obtained while having sufficient color development and line density. Cosmetics that can be freely set to be hard or soft depending on the size and distribution of the metal oxide, or the material type, have excellent mechanical strength (bending strength, tensile strength, impact strength, etc.), and can be multicolored And a method for producing the same.

次に、実施例及び比較例により本発明を更に説明するが、本発明は下記実施例に限定されるものではない。   Next, the present invention will be further described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(実施例1)
イオン交換水300g、ポリオキシエチレン(分子量600、ポリエチレングルコール600、和光純薬社製)300g、0.1mol/lのHClを25g入れ、30℃で、30分間撹拌を行った(溶液1)。次いで、Si源としてのテトラエチルオルソシリケート(TEOS)50gと、Ti源としてのチタンイソプロポキシド50gとの混合液を上記溶液1に加え、30℃で2時間撹拌し、溶液Aを調製した。この溶液Aを用いて下記配合組成物及び下記製法により化粧料を得た。
Example 1
300 g of ion-exchanged water, 300 g of polyoxyethylene (molecular weight 600, polyethylene glycol 600, manufactured by Wako Pure Chemical Industries, Ltd.), 25 g of 0.1 mol / l HCl were added and stirred at 30 ° C. for 30 minutes (Solution 1) . Next, a mixed liquid of 50 g of tetraethylorthosilicate (TEOS) as a Si source and 50 g of titanium isopropoxide as a Ti source was added to the solution 1 and stirred at 30 ° C. for 2 hours to prepare a solution A. Using this solution A, a cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液A 30.0重量%
チタン被覆マイカ 34.0重量%
紺青 16.0重量%
タルク 10.0重量%
窒化ホウ素 10.0重量%
上記配合組成物を混練し、この混練物を薄皿状の容器に充填し、50℃まで昇温して24時間乾燥し、容器充填方固形化粧料を得た。
Formulation composition:
Solution A 30.0% by weight
Titanium-coated mica 34.0% by weight
Bitumen 16.0% by weight
Talc 10.0% by weight
Boron nitride 10.0% by weight
The above blended composition was kneaded, and the kneaded product was filled into a thin dish-shaped container, heated to 50 ° C. and dried for 24 hours to obtain a container filling solid cosmetic.

(実施例2)
実施例1の溶液Aを用いて下記配合組成物及び下記製法により化粧料を得た。
配合組成物:
溶液A 30.0重量%
紺青 24.0重量%
酸化チタン 6.0重量%
カオリン 30.0重量%
窒化ホウ素 20.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中50℃で24時間乾燥し、直径4.0mmの水色棒状化粧料を得た。
(Example 2)
A cosmetic was obtained using the solution A of Example 1 by the following composition and the following production method.
Formulation composition:
Solution A 30.0% by weight
Bitumen 24.0% by weight
Titanium oxide 6.0% by weight
Kaolin 30.0% by weight
Boron nitride 20.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 50 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 4.0 mm.

(実施例3)
TEOS50gをエタノール50gで希釈し、ポリオキシエチレン(分子量400、ポリエチレングルコール400、和光純薬社製)を50g徐々に滴下し、1時間混合後、0.1N−HCL水溶液を100g滴下して6時間混合し、溶液Bを調製した。この溶液Bを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
(Example 3)
50 g of TEOS was diluted with 50 g of ethanol, and 50 g of polyoxyethylene (molecular weight 400, polyethylene glycol 400, manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise. After mixing for 1 hour, 100 g of 0.1N-HCL aqueous solution was added dropwise. Mix for hours to prepare Solution B. Using this solution B, a stick-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液B 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution B 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 80 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

(実施例4)
TEOS50gをエタノール50gで希釈し、ポリオキシエチレン(分子量400、ポリエチレングルコール400、和光純薬社製)を100g徐々に滴下し、1時間混合後、0.1N−HCL水溶液を100g滴下して6時間混合し、溶液Cを調製した。この溶液Cを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
Example 4
50 g of TEOS was diluted with 50 g of ethanol, 100 g of polyoxyethylene (molecular weight 400, polyethylene glycol 400, manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise, and after mixing for 1 hour, 100 g of 0.1N-HCL aqueous solution was added dropwise. Mix for hours to prepare Solution C. Using this solution C, a rod-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液C 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution C 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 80 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

(実施例5)
TEOS50gをエタノール50gで希釈し、ポリオキシエチレン(分子量600、ポリエチレングルコール600、和光純薬社製)を100g徐々に滴下し、1時間混合後、0.1N−HCL水溶液を100g滴下して6時間混合し、溶液Dを調製した。この溶液Dを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
(Example 5)
50 g of TEOS was diluted with 50 g of ethanol, 100 g of polyoxyethylene (molecular weight 600, polyethylene glycol 600, manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise, and after mixing for 1 hour, 100 g of 0.1N-HCL aqueous solution was added dropwise. Mix for hours to prepare solution D. Using this solution D, a bar-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液D 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution D 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 80 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

(実施例6)
TEOS50gをエタノール50gで希釈し、ポリオキシエチレン(分子量1000、ポリエチレングルコール1000、和光純薬社製)を100g徐々に滴下し、1時間混合後、0.1N−HCL水溶液を100g滴下して6時間混合し、溶液Eを調製した。この溶液Eを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
(Example 6)
50 g of TEOS was diluted with 50 g of ethanol, 100 g of polyoxyethylene (molecular weight 1000, polyethylene glycol 1000, manufactured by Wako Pure Chemical Industries, Ltd.) was gradually added dropwise, mixed for 1 hour, and then 100 g of 0.1N-HCL aqueous solution was added dropwise. Mix for hours to prepare Solution E. Using this solution E, a bar-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液E 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution E 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 80 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

(実施例7)
TEOS50gをエタノール50gで希釈し、ポリオキシエチレン(n=23)ラウリルエーテルを100gを徐々に滴下し、1時間混合後、0.1N−HCL水溶液を100g滴下して6時間混合し、溶液Fを調製した。この溶液Fを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
(Example 7)
50 g of TEOS was diluted with 50 g of ethanol, 100 g of polyoxyethylene (n = 23) lauryl ether was gradually added dropwise and mixed for 1 hour, then 100 g of 0.1N-HCL aqueous solution was added dropwise and mixed for 6 hours. Prepared. Using this solution F, a bar-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液F 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution F 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition was kneaded, and the kneaded product was extruded into a thin line with an extruder and dried in air at 80 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

(実施例8)
実施例7の溶液Fを用いて下記配合組成物及び下記製法により化粧料を得た。
配合組成物:
溶液F 30.0重量%
青色一号 5.0重量%
紺青 10.5重量%
酸化チタン 8.0重量%
カオリン 26.5重量%
窒化ホウ素 20.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、更にマイクロ波加熱(2,45GHz,700W)を3分間行い、直径2.0mmの水色棒状化粧料を得た。
(Example 8)
A cosmetic was obtained using the solution F of Example 7 by the following composition and the following production method.
Formulation composition:
Solution F 30.0% by weight
Blue No.1 5.0 wt%
Bitumen 10.5% by weight
Titanium oxide 8.0% by weight
Kaolin 26.5% by weight
Boron nitride 20.0% by weight
The above blended composition is kneaded, this kneaded product is extruded into a thin line with an extruder, and further subjected to microwave heating (2,45 GHz, 700 W) for 3 minutes to obtain a light blue stick-shaped cosmetic with a diameter of 2.0 mm. It was.

(実施例9)
配合組成物:
TEOS 10.0重量%
0.1mol%−NaOH水溶液 1.0重量%
ポリオキシエチレン(n=23)ラウリルエーテル 30.0重量%
マイカ 30.0重量%
紺青 10.0重量%
カオリン 19.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中で80℃まで昇温して72時間乾燥し、直径2.0mmの水色パール棒状化粧料を得た。
Example 9
Formulation composition:
TEOS 10.0% by weight
0.1 mol% -NaOH aqueous solution 1.0 wt%
Polyoxyethylene (n = 23) lauryl ether 30.0% by weight
Mica 30.0% by weight
Bitumen 10.0% by weight
Kaolin 19.0% by weight
The above blended composition is kneaded, and the kneaded product is extruded into a thin line with an extruder, heated to 80 ° C. in air and dried for 72 hours to obtain a light blue pearl bar cosmetic with a diameter of 2.0 mm. It was.

(実施例10)
配合組成物:
チタンイソプロポキシド 10.0重量%
0.1mol%−NaOH水溶液 1.0重量%
ポリオキシエチレン(n=23)ラウリルエーテル 30.0重量%
チタン被覆マイカ 30.0重量%
紺青 10.0重量%
カオリン 19.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中で50℃まで昇温して100時間乾燥し、直径2.0mmの水色パール棒状化粧料を得た。
(Example 10)
Formulation composition:
Titanium isopropoxide 10.0% by weight
0.1 mol% -NaOH aqueous solution 1.0 wt%
Polyoxyethylene (n = 23) lauryl ether 30.0% by weight
Titanium-coated mica 30.0% by weight
Bitumen 10.0% by weight
Kaolin 19.0% by weight
The above blended composition is kneaded, this kneaded product is extruded into a thin line with an extruder, heated to 50 ° C. in air and dried for 100 hours to obtain a light blue pearl bar cosmetic with a diameter of 2.0 mm. It was.

(実施例11)
ポリアクリル酸(分子量5000、アクロース オーガニクス社製)50gを0.1N−HCL水溶液50gとエタノール50gで溶解し、テトラエトキシシラン50gを徐々に滴下し、6時間混合し、溶液Gを調製した。この溶液Gを用いて下記配合組成物及び下記製法により棒状化粧料を得た。
(Example 11)
50 g of polyacrylic acid (molecular weight 5000, manufactured by Akrose Organics) was dissolved in 50 g of 0.1N-HCL aqueous solution and 50 g of ethanol, and 50 g of tetraethoxysilane was gradually added dropwise and mixed for 6 hours to prepare Solution G. Using this solution G, a bar-shaped cosmetic was obtained by the following composition and the following production method.

配合組成物:
溶液G 30.0重量%
紺青 20.0重量%
酸化チタン 5.0重量%
カオリン 15.0重量%
窒化ホウ素 30.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、空気中80℃で24時間乾燥後、更に蒸留水で超音波洗浄を1時間、マイクロ波加熱(2.45GMz、700W)を3分間行い、直径2.0mmの水色棒状化粧料を得た。
Formulation composition:
Solution G 30.0% by weight
Bitumen 20.0% by weight
Titanium oxide 5.0% by weight
Kaolin 15.0% by weight
Boron nitride 30.0% by weight
The above blended composition is kneaded, the kneaded product is extruded into a thin line with an extruder, dried in air at 80 ° C. for 24 hours, and further subjected to ultrasonic cleaning with distilled water for 1 hour by microwave heating (2. 45 GMz, 700 W) for 3 minutes to obtain a light blue stick-shaped cosmetic with a diameter of 2.0 mm.

(実施例12)
実施例11の溶液Gを用いて下記配合組成物及び下記製法により化粧料を得た。
配合組成物:
溶液G 30.0重量%
天然香料(ジャスミン) 5.0重量%
紺青 10.5重量%
酸化チタン 8.0重量%
カオリン 26.5重量%
窒化ホウ素 20.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、更にマイクロ波加熱(2.45GHz、700W)を3分間行い、直径2.0mmの水色棒状化粧料を得た。
(Example 12)
Cosmetics were obtained by using the solution G of Example 11 and the following composition and the following production method.
Formulation composition:
Solution G 30.0% by weight
Natural fragrance (jasmine) 5.0% by weight
Bitumen 10.5% by weight
Titanium oxide 8.0% by weight
Kaolin 26.5% by weight
Boron nitride 20.0% by weight
The above blended composition is kneaded, the kneaded product is extruded into a thin line with an extruder, and further subjected to microwave heating (2.45 GHz, 700 W) for 3 minutes to obtain a light blue stick-shaped cosmetic with a diameter of 2.0 mm. It was.

(実施例13)
実施例11の溶液Gを用いて下記配合組成物及び下記製法により化粧料を得た。
配合組成物:
溶液G 30.0重量%
シリコーンオイル(KF995、信越シリコーン社製) 10.0重量%
紺青 10.5重量%
酸化チタン 8.0重量%
カオリン 26.5重量%
窒化ホウ素 15.0重量%
上記配合組成物を混練し、この混練物を押出機にて細線状に押出成形し、更にマイクロ波加熱(2.45GHz、700W)を3分間行い、直径2.0mmの水色棒状化粧料を得た。
(Example 13)
Cosmetics were obtained by using the solution G of Example 11 and the following composition and the following production method.
Formulation composition:
Solution G 30.0% by weight
Silicone oil (KF995, manufactured by Shin-Etsu Silicone) 10.0% by weight
Bitumen 10.5% by weight
Titanium oxide 8.0% by weight
Kaolin 26.5% by weight
Boron nitride 15.0% by weight
The above blended composition is kneaded, the kneaded product is extruded into a thin line with an extruder, and further subjected to microwave heating (2.45 GHz, 700 W) for 3 minutes to obtain a light blue stick-shaped cosmetic with a diameter of 2.0 mm. It was.

(比較例1)
配合組成物:
TEOS縮合体 50.0重量%
窒化ホウ素 30.0重量%
塩化ビニル 20.0重量%
上記配合組成物を2本ロールで混練し、更に3本ロールで分散した後、この混練物をスクリュー型押出機にて細線状に押出成形し、窒素雰囲気中で700℃まで昇温して5時間焼成し、炭素残さ物を含む黒色焼成芯体を得た。更に、空気雰囲気中で700℃まで昇温して5時間焼成し、更に窒素雰囲気中で1000℃まで昇温して5時間焼成し、白色芯体を得た。次に、水色インキを含浸させて、直径2.0mmの水色棒状化粧料を得た。
(Comparative Example 1)
Formulation composition:
TEOS condensate 50.0% by weight
Boron nitride 30.0% by weight
Vinyl chloride 20.0% by weight
The above blended composition was kneaded with two rolls and further dispersed with three rolls, and then the kneaded product was extruded into a thin line with a screw type extruder, heated to 700 ° C. in a nitrogen atmosphere and heated to 5 ° C. A black fired core containing carbon residue was obtained by firing for a period of time. Furthermore, the temperature was raised to 700 ° C. in an air atmosphere and baked for 5 hours, and further heated to 1000 ° C. in a nitrogen atmosphere and baked for 5 hours to obtain a white core. Next, it was impregnated with light blue ink to obtain a light blue stick-shaped cosmetic material having a diameter of 2.0 mm.

(比較例2)
配合組成物:
TEOS縮合体 20.0重量%
0.1mol%−NaOH水溶液 1.0重量%
窒化ホウ素 39.0重量%
群青 28.0重量%
酸化チタン 12.0重量%
上記配合組成物を混練し、押出機にて細線状に押出成形し、空気中で80℃で24時間乾燥後、窒素中で700℃まで昇温して5時間焼成し、直径2.0mmの水色棒状化粧料を得た。
(Comparative Example 2)
Formulation composition:
TEOS condensate 20.0% by weight
0.1 mol% -NaOH aqueous solution 1.0 wt%
Boron nitride 39.0% by weight
Ultramarine 28.0% by weight
Titanium oxide 12.0% by weight
The above blended composition was kneaded, extruded into a thin line with an extruder, dried in air at 80 ° C. for 24 hours, heated to 700 ° C. in nitrogen and baked for 5 hours, and had a diameter of 2.0 mm. A light blue stick-shaped cosmetic was obtained.

(比較例3)
配合組成物:
チタンイソプロポキシド縮合体 20.0重量%
0.1mol%−NaOH水溶液 1.0重量%
窒化ホウ素 39.0重量%
群青 28.0重量%
酸化チタン 12.0重量%
上記配合組成物を混練し、押出機にて細線状に押出成形し、空気中で80℃で24時間乾燥後、窒素中で700℃まで昇温して5時間焼成し、直径2.0mmの水色棒状化粧料を得た。
(Comparative Example 3)
Formulation composition:
Titanium isopropoxide condensate 20.0% by weight
0.1 mol% -NaOH aqueous solution 1.0 wt%
Boron nitride 39.0% by weight
Ultramarine 28.0% by weight
Titanium oxide 12.0% by weight
The above blended composition was kneaded, extruded into a thin line with an extruder, dried in air at 80 ° C. for 24 hours, heated to 700 ° C. in nitrogen and baked for 5 hours, and had a diameter of 2.0 mm. A light blue stick-shaped cosmetic was obtained.

(比較例4)
配合組成物:
チタン被覆マイカ 20.0重量%
窒化ホウ素 40.0重量%
カオリン 9.0重量%
マイクロクリスタリンワックス 1.0重量%
流動パラフィン 10.0重量%
パーフルオロポリエーテル 10.0重量%
紺青 10.0重量%
上記配合組成物を混合、分散し、押出機にて細線状に押出成形し、空気中で50℃で24時間乾燥し、直径2.0mmの水色棒状化粧料を得た。
(Comparative Example 4)
Formulation composition:
Titanium-coated mica 20.0% by weight
Boron nitride 40.0% by weight
Kaolin 9.0% by weight
Microcrystalline wax 1.0% by weight
Liquid paraffin 10.0% by weight
Perfluoropolyether 10.0% by weight
Bitumen 10.0% by weight
The above blended composition was mixed and dispersed, extruded into a thin line with an extruder, and dried in air at 50 ° C. for 24 hours to obtain a light blue stick-shaped cosmetic having a diameter of 2.0 mm.

上記実施例1〜13及び比較例1〜4で得られた各棒状化粧料(芯体)の成形性、機械的強度、官能評価による保湿効果(肌に塗布して暫く乾燥しないか)、発色性、塗布感の各評価を行った。
なお、気孔率は、ユアサアイオニックス社製・水銀ポロシメーターで測定し、機械的強度は、支点間20mm、速度5mm/minの条件で三点曲げ強度試験を各芯20本で行い、比較例1の折損荷重(7N)を100とした比率で表し、平均数値が高いほど機械的強度に優れていることを示す。また、保湿効果、発色性と塗布感の評価は木軸に組み込んだ鉛筆の形状で10名のモニターに、1〜5の5段階(5が最も良い評価)で官能評価を行ってもらい、平均値で示した。なお、気孔率において、比較例1〜4の結合剤はほぼ緻密体となっているため棒状化粧料全体の気孔率で示した。
これらの結果を下記表1に示す。
Formability, mechanical strength, moisturizing effect by sensory evaluation of each bar-shaped cosmetic (core) obtained in Examples 1 to 13 and Comparative Examples 1 to 4 (whether it is applied to the skin and does not dry for a while), coloring Each evaluation of a property and a coating feeling was performed.
The porosity was measured with a mercury porosimeter manufactured by Yuasa Ionix Co., Ltd., and the mechanical strength was a 20 point between fulcrums and a speed of 5 mm / min. The breakage load (7N) is expressed as a ratio of 100, and the higher the average value, the better the mechanical strength. In addition, the evaluation of the moisturizing effect, color developability and feeling of application was carried out by having 10 monitors in the shape of a pencil built in a wooden shaft and performing sensory evaluation in 5 stages (5 is the best evaluation). Indicated by value. In addition, in terms of porosity, since the binders of Comparative Examples 1 to 4 are almost dense bodies, they are indicated by the porosity of the entire bar-shaped cosmetic.
These results are shown in Table 1 below.

Figure 0004514526
Figure 0004514526

上記表1の結果から下記のことが明らかなとなった。すなわち、本発明範囲の実施例1は、ファンデーションやアイシャドウ等の容器充填型固形化粧料であり、通常ワックス等の油脂成分で固められているため、使用感にはべとつきがあるが、本発明ではパウダリーな塗布感が得られることが判った。
また、実施例2〜13の化粧料は、摩耗し易くサラサラした塗布感が得られていると同時に極めて発色性が良く機械的強度も強く、また、多孔質体が連通孔を有しているために、水分を吸着しやすく、水溶性高分子に起因する保湿効果と柔軟性も得られることが判った。
更に、チタン被覆マイカを配合した実施例9及び10もパール感を失うことはなく、成形性、発色の良いパール棒状化粧料が得られることが判った。
また、実施例3〜6の棒状化粧料を比較考察すると、ポリオキシエチレンの配合量や分子量を変化させることによって、強度、摩耗量、塗布感を自由に設定でき、容易に目的とする棒状化粧料に合わせた特性を発揮することが可能となることが判った。
これに対して、本発明範囲外となる比較例1〜3は、無機高分子を結合材・成形助剤として用いているため、成形性を良くするため無機高分子を重縮合して粘度を高めたり配合を多くしたりすると、摩耗量、濃度が減少し、また、摩耗量、濃度を多くするため、無機高分子の粘度を下げたり配合量を減らしたりすると、成形性が悪くなってしまった。更に、無機の骨格であるため、保湿効果は小さいものであった。
また、比較例4に示したように、無機高分子の代わりにワックスを用いると、ワックスのぬるっとした塗布感が発現し、結果としてサラサラした塗布感は失われてしまった。

From the results in Table 1 above, the following became clear. That is, Example 1 within the scope of the present invention is a container-filled solid cosmetic such as a foundation or eye shadow, and is usually hardened with an oil and fat component such as wax, but the feeling of use is sticky. Then, it turned out that a powdery coating feeling is obtained.
In addition, the cosmetics of Examples 2 to 13 are easy to wear and have a smooth coating feeling, and at the same time have very good color development and high mechanical strength, and the porous body has communication holes. For this reason, it has been found that moisture is easily adsorbed and a moisturizing effect and flexibility due to the water-soluble polymer can be obtained.
Furthermore, it was found that Examples 9 and 10 containing titanium-coated mica also did not lose the pearl feeling, and a pearl bar-shaped cosmetic material with good moldability and color development was obtained.
Moreover, when the rod-shaped cosmetics of Examples 3 to 6 are compared and considered, the strength, wear amount, and feeling of application can be freely set by changing the blending amount and molecular weight of polyoxyethylene, and the intended rod-shaped makeup can be easily achieved. It has been found that it is possible to exhibit characteristics tailored to the material.
On the other hand, Comparative Examples 1 to 3, which are outside the scope of the present invention, use an inorganic polymer as a binder / molding aid, so that the viscosity is increased by polycondensation of the inorganic polymer to improve moldability. If the amount is increased or the amount is increased, the amount of wear and concentration will decrease, and the amount of wear and concentration will increase, so if the viscosity of the inorganic polymer is decreased or the amount is decreased, the moldability will deteriorate. It was. Furthermore, since it is an inorganic skeleton, the moisturizing effect was small.
Further, as shown in Comparative Example 4, when wax was used instead of the inorganic polymer, a waxy coating feeling was developed, and as a result, the smooth coating feeling was lost.

Claims (14)

金属酸化物中に水溶性有機高分子を含有した複合多孔質体を骨格とすることを特徴とする固形化粧料。 A solid cosmetic comprising a composite porous body containing a water-soluble organic polymer in a metal oxide as a skeleton . 複合多孔質体は、金属酸化物中に水溶性有機高分子が均一に混合され、少なくとも連通孔を有する請求項1記載の固形化粧料。 2. The solid cosmetic according to claim 1, wherein the composite porous body has a water-soluble organic polymer uniformly mixed in a metal oxide and has at least communicating holes. 複合多孔質体は、金属酸化物中に水溶性有機高分子が包括して混合されている請求項1又は2記載の固形化粧料。 3. The solid cosmetic according to claim 1, wherein the composite porous body includes a water-soluble organic polymer mixed in a metal oxide. 水溶性有機高分子の分子鎖中に、ポリオキシメチレン鎖、ポリオキシエチレン鎖、ポリオキシプロピレン鎖の少なくとも一つを含有している請求項1〜3の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 3, wherein the molecular chain of the water-soluble organic polymer contains at least one of a polyoxymethylene chain, a polyoxyethylene chain, and a polyoxypropylene chain. . 水溶性有機高分子が、ポリアクリル酸系高分子である請求項1〜4の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 4, wherein the water-soluble organic polymer is a polyacrylic acid polymer. 金属酸化物が、酸化珪素、酸化アルミニウム、酸化チタン、酸化ジルコニウム、酸化亜鉛から選ばれる少なくとも1種である請求項1〜5の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 5, wherein the metal oxide is at least one selected from silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, and zinc oxide. 複合多孔質体に香料が含有されている請求項1〜6の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 6, wherein a fragrance is contained in the composite porous body. 複合多孔質体に界面活性剤が含有されている請求項1〜7の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 7, wherein a surfactant is contained in the composite porous body. 複合多孔質体に潤滑剤が含有されている請求項1〜8の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 8, wherein a lubricant is contained in the composite porous body. 複合多孔質体に色材が含有されている請求項1〜9の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 9, wherein a color material is contained in the composite porous body. 複合多孔質体中の水溶性有機高分子の含有量が、0.1〜90重量%である請求項1〜10の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 10, wherein the content of the water-soluble organic polymer in the composite porous body is 0.1 to 90% by weight. 固形化粧料が複合多孔質体を骨格とする化粧鉛筆からなる請求項1〜11の何れか一つに記載の固形化粧料。 The solid cosmetic according to any one of claims 1 to 11 , wherein the solid cosmetic comprises a cosmetic pencil having a composite porous body as a skeleton. 固形化粧料が繰り出し容器用棒状化粧料、木軸用棒状化粧料、紙巻棒状化粧料の何れかである請求項1〜12の何れか一つに記載の固形化粧料。The solid cosmetic according to any one of claims 1 to 12, wherein the solid cosmetic is any one of a stick-shaped cosmetic for a feeding container, a stick-shaped cosmetic for a wooden shaft, and a cigarette-shaped cosmetic. 水溶性有機高分子と金属酸化物前駆体とを混合し、金属酸化物前駆体と水溶性有機高分子を分相させ、金属酸化物前駆体をセラミック化することによって合成した複合多孔質体を化粧料として配合することを特徴とする固形化粧料の製造方法。 A composite porous body synthesized by mixing a water-soluble organic polymer and a metal oxide precursor, phase-separating the metal oxide precursor and the water-soluble organic polymer, and ceramicizing the metal oxide precursor. A method for producing a solid cosmetic, comprising blending as a cosmetic.
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JP2001089348A (en) * 1999-09-24 2001-04-03 Noevir Co Ltd Porous titanium oxide retaining water or water soluble substance, method for producing the same titanium oxide and cosmetic containing the same titanium oxide
JP2001130912A (en) * 1999-11-01 2001-05-15 Noevir Co Ltd Porous titanium oxide, method for producing the same, and cosmetic containing the same
JP2001288030A (en) * 2000-03-31 2001-10-16 Shiseido Co Ltd Moisture-holding agent-adsorbing powder and powdered cosmetic obtained by blending the same
JP2003119416A (en) * 2001-10-17 2003-04-23 Mitsubishi Pencil Co Ltd Baked color pencil lead and method for producing the same

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Publication number Priority date Publication date Assignee Title
JP2001089348A (en) * 1999-09-24 2001-04-03 Noevir Co Ltd Porous titanium oxide retaining water or water soluble substance, method for producing the same titanium oxide and cosmetic containing the same titanium oxide
JP2001130912A (en) * 1999-11-01 2001-05-15 Noevir Co Ltd Porous titanium oxide, method for producing the same, and cosmetic containing the same
JP2001288030A (en) * 2000-03-31 2001-10-16 Shiseido Co Ltd Moisture-holding agent-adsorbing powder and powdered cosmetic obtained by blending the same
JP2003119416A (en) * 2001-10-17 2003-04-23 Mitsubishi Pencil Co Ltd Baked color pencil lead and method for producing the same

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