JP2008031187A - Disintegrative particle - Google Patents
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本発明は洗浄やすすぎの過程で粒子が崩壊する崩壊性粒子、及び洗浄性や洗い流し性の極めて良好な化粧料組成物に関する。 The present invention relates to disintegrating particles in which particles disintegrate in the course of washing and rinsing, and a cosmetic composition having very good washing and washing properties.
粒子（スクラブ剤）を配合した皮膚洗浄剤は、物理的洗浄において通常の洗浄剤組成物では落とし難い余分な角質（垢）や皮溝、毛穴に入り込んだ汚れ等が落とせるという特徴を有する。また、皮膚の炎症の問題を考慮して、スクラブ剤の粒径の大きさ及び硬度を制御した高洗浄性で低刺激性の洗浄剤もある（特許文献１）。一方、飽和溶解度以上の塩化ナトリウム粒子を洗浄剤組成物に配合し、塩化ナトリウムを粒子として存在させ、洗浄力や、皮膚を滑らかに仕上げる等の洗浄剤（特許文献２）もある。
しかしながら、粒径の大きさ及び硬度を制御したスクラブ剤を配合した洗浄剤は、マッサージ時に異物感がある、洗浄後洗い流し難い等の使用上の課題が残されていた。 However, a cleaning agent containing a scrub agent in which the size and hardness of the particle size are controlled has problems in use such as a foreign body feeling at the time of massage and difficult to wash off after cleaning.
また、飽和溶解度以上の塩化ナトリウム粒子を配合した洗浄剤組成物は、スクラブ剤が凝集、沈降等を起こしやすいため、分散性に問題があった。また塩化ナトリウムを飽和溶解度以上に含有するため、洗浄時の起泡性や、洗浄性や使用感の低下といった問題があった。 In addition, the detergent composition containing sodium chloride particles having a saturation solubility or higher has a problem in dispersibility because the scrubbing agent tends to aggregate and settle. Further, since sodium chloride is contained at a saturation solubility or higher, there are problems such as foaming at the time of cleaning, deterioration of cleaning properties and feeling of use.
本発明者らは、少なくとも一部が水不溶性である一次粒子が凝集してなり、水溶性塩類含有水溶液中で水溶性塩類濃度の低下により崩壊する粒子の嵩比重と真比重の比を一定範囲にすれば、使用感、マッサージ感及び崩壊性が良好な崩壊性粒子が得られることを見出した。 The present inventors have a certain range of the ratio between the bulk specific gravity and the true specific gravity of particles in which primary particles that are at least partially insoluble in water aggregate and disintegrate in a water-soluble salt-containing aqueous solution due to a decrease in the concentration of water-soluble salts. In this way, it was found that disintegrating particles having good usability, massage feeling and disintegrating property can be obtained.
本発明は、少なくとも一部が水不溶性である一次粒子が凝集してなり、（嵩比重）／（真比重）が０．１〜０．６である崩壊性粒子であって、水溶性塩類含有水溶液中において水溶性塩類濃度の低下により該崩壊性粒子の凝集が崩壊する崩壊性粒子を提供する。 The present invention is a disintegrating particle in which at least a part of water-insoluble primary particles are aggregated and (bulk specific gravity) / (true specific gravity) is 0.1 to 0.6, and contains water-soluble salts Disintegrating particles in which agglomeration of the disintegrating particles collapses due to a decrease in the concentration of water-soluble salts in an aqueous solution are provided.
また、本発明は、前記の崩壊性粒子、水溶性塩類、界面活性剤及び水を含有し、該崩壊性粒子の含量が組成物中１〜２５重量％であり、水溶性塩類の濃度が１．０重量％以上飽和溶解度未満であり、すすぎ水により容易に崩壊性粒子が崩壊するため、洗い流し性の極めて良好な化粧料組成物を提供する。 The present invention also includes the disintegrating particles, water-soluble salts, surfactant and water, the content of the disintegrating particles is 1 to 25% by weight in the composition, and the concentration of the water-soluble salts is 1. A cosmetic composition having an excellent washability is provided because the disintegrating particles are easily disintegrated by rinsing water.
本発明の化粧料組成物は、特に物理的（機械的）な洗浄性に優れ、また経時安定性に優れるとともに、使用感も良好である。更に、洗浄過程及びすすぎ過程において、容易に崩壊性粒子が崩壊することにより、洗い流し性が極めて良好である。 The cosmetic composition of the present invention is particularly excellent in physical (mechanical) detergency, is excellent in stability over time, and has a good feeling in use. Furthermore, in the washing process and the rinsing process, the disintegrating particles easily disintegrate, so that the washability is very good.
本発明で用いられる崩壊性粒子の平均粒径は、化粧料の使用時の違和感、皮膚刺激の観点から、好ましくは１００μｍから１０００μｍであり、１２５μｍから８００μｍがより好ましい。 The average particle size of the disintegrating particles used in the present invention is preferably 100 μm to 1000 μm, and more preferably 125 μm to 800 μm, from the viewpoint of discomfort during use of the cosmetic and skin irritation.
本発明の崩壊性粒子を構成する一次粒子としては、少なくとも一部が一種以上の水不溶性一次粒子であればよい。例えば水不溶性一次粒子、又は水不溶性一次粒子と水溶性一次粒子の組合わせが挙げられる。崩壊性の点より好ましい態様として、二種以上、更に好ましくは三種以上の水不溶性一次粒子の組合わせ、又はこれらの組合わせと水溶性一次粒子との組合わせが挙げられる。これら一次粒子は有機粒子でも無機粒子でもよい。ここで「水不溶性」とは、２５℃において水９９重量部に対象粒子１重量部を溶解させたとき、溶解度が５０重量％未満であり、「水溶性」とは同条件での溶解度が５０重量％以上であることを意味する。なお、溶解度は、水溶液を濾紙（Ｎｏ．２）で濾過し、濾液中の固形分量より算出する。水溶性一次粒子としては、当該溶解度が９０重量％以上のものが好ましい。 The primary particles constituting the disintegrating particles of the present invention may be at least a part of one or more water-insoluble primary particles. Examples thereof include water-insoluble primary particles, or a combination of water-insoluble primary particles and water-soluble primary particles. As a more preferable embodiment than the disintegration point, a combination of two or more, more preferably three or more water-insoluble primary particles, or a combination of these and water-soluble primary particles can be given. These primary particles may be organic particles or inorganic particles. Here, “water-insoluble” means that when 1 part by weight of the target particles is dissolved in 99 parts by weight of water at 25 ° C., the solubility is less than 50% by weight, and “water-soluble” means that the solubility under the same conditions is 50 It means that it is more than wt%. The solubility is calculated from the solid content in the filtrate by filtering the aqueous solution with a filter paper (No. 2). The water-soluble primary particles preferably have a solubility of 90% by weight or more.
水不溶性有機一次粒子としては、ポリエチレン、ポリプロピレン、ポリアミド、ポリエチレンテレフタレート、ポリスチレンやポリウレタン及び／又はそれらの架橋体、ポリ（メタ）アクリル酸ナトリウムやポリ（メタ）アクリル酸エステル及び／又はそれらの架橋体等の他、エチレンゴム、プロピレンゴム、スチレン−ブタジエンゴム、ブタジエンゴム、シリコーンゴム等のゴム類及び／又はそれらの架橋体等の合成高分子；セルロース及び／又はその誘導体、キトサン及び／又はその誘導体、澱粉、果実の殻等の天然高分子及び／又はその誘導体が挙げられる。中でも、ポリエチレン、ポリアミド、ポリスチレン、ポリ（メタ）アクリル酸ナトリウムの架橋体、ポリ（メタ）アクリル酸エステルの架橋体、セルロース及び／又はその誘導体、澱粉等が好ましく用いられる。ここで「ポリ（メタ）アクリル酸」は「ポリアクリル酸」と「ポリメタクリル酸」の双方を意味する。 Examples of the water-insoluble organic primary particles include polyethylene, polypropylene, polyamide, polyethylene terephthalate, polystyrene, polyurethane and / or a crosslinked product thereof, sodium poly (meth) acrylate, poly (meth) acrylate ester and / or a crosslinked product thereof. Etc., synthetic polymers such as rubbers such as ethylene rubber, propylene rubber, styrene-butadiene rubber, butadiene rubber, silicone rubber and / or cross-linked products thereof; cellulose and / or derivatives thereof, chitosan and / or derivatives thereof Natural polymers such as starch and fruit shells and / or derivatives thereof. Among these, polyethylene, polyamide, polystyrene, crosslinked poly (meth) acrylate, crosslinked poly (meth) acrylate, cellulose and / or derivatives thereof, starch, and the like are preferably used. Here, “poly (meth) acrylic acid” means both “polyacrylic acid” and “polymethacrylic acid”.
水不溶性無機一次粒子としては、ベントナイト、タルク、マイカ、カオリン、セピオライト、シリカ、炭酸カルシウム、酸化チタン、無水珪酸、ヒドロキシ・カルシウム・アパタイト等の他、真珠質が挙げられる。中でも、ベントナイト、タルク、マイカ、カオリン、シリカ等が好ましく用いられる。 Examples of the water-insoluble inorganic primary particles include bentonite, talc, mica, kaolin, sepiolite, silica, calcium carbonate, titanium oxide, anhydrous silicic acid, hydroxy / calcium / apatite, and nacre. Among these, bentonite, talc, mica, kaolin, silica and the like are preferably used.
これらの水不溶性一次粒子は、真球状、略球状、平板状、棒状及び、粉砕等により異形の形状のものでも良く、また中空、多孔質の粒子等も用いられる。 These water-insoluble primary particles may be spherical, substantially spherical, flat, rod-shaped, or irregularly shaped by pulverization or the like, and hollow, porous particles and the like are also used.
水溶性有機一次粒子として、ポリビニルアルコール及び／又はその誘導体、ポリ（メタ）アクリル酸アルカリ塩、（メタ）アクリル酸／（メタ）アクリル酸エステル共重合物のアルカリ塩、アクリル酸／マレイン酸共重合物のアルカリ塩、ポリビニルピロリドン等の合成高分子；メチルセルロース、エチルセルロース、カルボキシメチルセルロースナトリウム、ヒドロキシアルキルセルロース、変性澱粉（ヒドロキシアルキル変性澱粉、リン酸エステル変性澱粉等）、ショ糖、乳糖等の糖類；海草類、タンパク質等の天然高分子が用いられる。 As water-soluble organic primary particles, polyvinyl alcohol and / or derivatives thereof, poly (meth) acrylic acid alkali salt, alkali salt of (meth) acrylic acid / (meth) acrylic acid ester copolymer, acrylic acid / maleic acid copolymer Synthetic polymers such as alkali salts of materials, polyvinylpyrrolidone, etc .; methylcellulose, ethylcellulose, sodium carboxymethylcellulose, hydroxyalkylcellulose, modified starch (hydroxyalkyl-modified starch, phosphate ester-modified starch, etc.), sugars such as sucrose, lactose; seaweeds Natural polymers such as proteins are used.
また、水溶性無機一次粒子として、塩化ナトリウム、塩化カリウム、塩化マグネシウム等の塩化物；硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸アルミニウム等の硫酸塩；炭酸ナトリウム、炭酸水素ナトリウム等の炭酸塩が挙げられる。尚、塩化ナトリウムの場合、食塩、高純度精製塩、天然塩等が使用される。中でも塩化ナトリウム、塩化カリウム、塩化マグネシウム、炭酸ナトリウム等の無機系粒子が好ましい。 Examples of water-soluble inorganic primary particles include chlorides such as sodium chloride, potassium chloride, and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate, and aluminum sulfate; carbonates such as sodium carbonate and sodium bicarbonate. It is done. In the case of sodium chloride, salt, highly purified salt, natural salt, etc. are used. Of these, inorganic particles such as sodium chloride, potassium chloride, magnesium chloride, and sodium carbonate are preferred.
これらの水溶性一次粒子もまたその形状は限定されず、単独でも二種以上を用いてもよい。 These water-soluble primary particles are not limited in shape, and may be used alone or in combination of two or more.
本発明崩壊性粒子における水不溶性一次粒子と水溶性一次粒子との重量比率は、（水不溶性一次粒子）／（水溶性一次粒子）＝１／９９〜１００／０の範囲が好ましく、５０／５０〜１００／０が更に好ましい。 The weight ratio of the water-insoluble primary particles to the water-soluble primary particles in the disintegrating particles of the present invention is preferably in the range of (water-insoluble primary particles) / (water-soluble primary particles) = 1/99 to 100/0, 50/50 More preferred is ~ 100/0.
これら一次粒子の平均粒径は被洗浄体の洗浄過程及びすすぎ水によって崩壊した場合の一次粒子の違和感及び洗い流し性の点で７０μｍ以下であることが好ましい。 The average particle diameter of these primary particles is preferably 70 μm or less from the viewpoint of the washing process of the object to be cleaned and the discomfort of the primary particles when they are disintegrated by rinsing water and the washability.
本発明崩壊性粒子は、好ましくは前記の一次粒子が水溶性バインダーにより結合して凝集したものである。かかる水溶性バインダーのバインダー成分としては、水溶性塩類水溶液中において、該塩類濃度の低下により溶解し、該塩類濃度の上昇により析出するものであれば特に制限されないが、ポリビニルアルコール及び／又はその誘導体（例えばカルボン酸変性ポリビニルアルコール、スルホン酸変性ポリビニルアルコール等）、ポリ（メタ）アクリル酸アルカリ塩、（メタ）アクリル酸／（メタ）アクリル酸エステル共重合物のアルカリ塩、アクリル酸／マレイン酸共重合物のアルカリ塩、ポリビニルピロリドン等の合成品；メチルセルロース、エチルセルロース、カルボキシメチルセルロース塩（例えばナトリウム塩、カリウム塩等）、ヒドロキシアルキルセルロース、澱粉誘導体等の半合成高分子；澱粉、海草類、植物粘質物、タンパク質等の天然高分子が用いられる。この中でも、カルボン酸変性ポリビニルアルコール（例えば、イタコン酸変性又はマレイン酸変性ポリビニルアルコール等）、スルホン酸変性ポリビニルアルコール又はカルボキシメチルセルロース塩（例えば、エーテル化度０．２〜１．２のもの）が好ましい。これらのバインダー成分は単独でも二種以上を併用してもよい。 The collapsible particles of the present invention are preferably those in which the primary particles are aggregated by binding with a water-soluble binder. The binder component of such a water-soluble binder is not particularly limited as long as it dissolves in a water-soluble salt aqueous solution due to a decrease in the salt concentration and precipitates due to an increase in the salt concentration. (For example, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, etc.), poly (meth) acrylic acid alkali salt, (meth) acrylic acid / (meth) acrylic acid ester copolymer alkali salt, acrylic acid / maleic acid co-polymer Synthetic products such as alkali salts of polymers and polyvinyl pyrrolidone; semi-synthetic polymers such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose salts (for example, sodium salt, potassium salt, etc.), hydroxyalkyl cellulose, starch derivatives; starch, seaweeds, plant mucilage ,protein Natural polymers are used. Among these, carboxylic acid-modified polyvinyl alcohol (for example, itaconic acid-modified or maleic acid-modified polyvinyl alcohol), sulfonic acid-modified polyvinyl alcohol or carboxymethyl cellulose salt (for example, having an etherification degree of 0.2 to 1.2) is preferable. . These binder components may be used alone or in combination of two or more.
本発明の崩壊性粒子においては、前記水溶性一次粒子と水溶性バインダーとは同一種の材料を用いてもよいし、異なる材料を用いてもよい。 In the collapsible particles of the present invention, the water-soluble primary particles and the water-soluble binder may use the same type of material or different materials.
水溶性バインダーは一次粒子の重量に対し、好ましくは０．５〜３０重量％、より好ましくは０．７５〜２５重量％用いる。水溶性バインダーの使用量がこの場合に粒子の崩壊性の点及び崩壊性粒子又はこれを含有する化粧料組成物の製造時の作業性の点から好ましい。 The water-soluble binder is preferably used in an amount of 0.5 to 30% by weight, more preferably 0.75 to 25% by weight, based on the weight of the primary particles. In this case, the amount of the water-soluble binder used is preferable from the viewpoint of the disintegrating property of the particles and the workability during the production of the disintegrating particles or the cosmetic composition containing the disintegrating particles.
本発明の崩壊性粒子は洗浄過程における使用感、マッサージ感及び崩壊性の点から、（嵩比重）／（真比重）が０．１〜０．６、好ましくは０．２〜０．６の範囲である。（嵩比重）／（真比重）が０．６より大きい場合、粒子の空隙率が低下しひいては崩壊率の低い粒子となることから好ましくない。また（嵩比重）／（真比重）が０．１未満の場合、粒子の強度が小さく、例えば乾燥粒子の運搬時や化粧料組成物としての保存時や移送時や配合時において、粒子が崩壊してしまい実使用に耐えがたいものとなり好ましくない。 The collapsible particles of the present invention have a (bulk specific gravity) / (true specific gravity) of 0.1 to 0.6, preferably 0.2 to 0.6, from the viewpoint of use feeling, massage feeling and disintegration in the washing process. It is a range. When (bulk specific gravity) / (true specific gravity) is larger than 0.6, it is not preferable because the void ratio of the particles decreases and the particles have a low disintegration rate. In addition, when (bulk specific gravity) / (true specific gravity) is less than 0.1, the strength of the particles is small. For example, the particles collapse when transporting dry particles, storing them as cosmetic compositions, transporting them, or blending them. This is not preferable because it is difficult to withstand actual use.
本発明の崩壊性粒子の製造法としては、特に制限されないが例えば一次粒子と水溶性バインダーを混合し及び／又は混合しつつ、転動造粒、転動流動造粒、流動層造粒、攪拌転動造粒、溶融造粒、押出造粒法、噴霧乾燥造粒等の造粒法及び／又は、噴霧乾燥等のコーティング法によって製造するのが好ましい。 The method for producing the collapsible particles of the present invention is not particularly limited. For example, while mixing and / or mixing the primary particles and the water-soluble binder, rolling granulation, rolling fluid granulation, fluidized bed granulation, stirring It is preferably produced by a granulation method such as rolling granulation, melt granulation, extrusion granulation method, spray drying granulation and / or a coating method such as spray drying.
かくして得られた本発明の崩壊性粒子は、前記の如く、水溶性塩類含有水溶液中において、水溶性塩類濃度の低下により、又は水溶性塩類濃度の低下とともに崩壊性粒子に荷重が加えられることにより崩壊率が高くなるという特性を有する。従って、この崩壊性粒子を、化粧料組成物に配合した場合、該化粧料組成物中では崩壊性粒子は崩壊することなく安定に分散しており、洗浄過程及びすすぎ過程における水溶性塩類濃度の低下とともに崩壊性粒子は崩壊する。このような化粧料組成物への配合を考慮すれば、本発明崩壊性粒子の崩壊特性は、水溶性塩類濃度が１．０重量％未満、より好ましくは１．５重量％未満の水溶液中で少なくとも一部が崩壊するように設計するのが好ましく、すすぎ水による洗い流し性の点から、更に水溶性塩類濃度１．０重量％未満、より好ましくは１．５重量％未満の水溶液中で、洗浄前（すなわち崩壊前）の崩壊性粒子に対し７０重量％以上が崩壊するように設計されるのがより好ましい。また、このときの崩壊された粒子は平均粒径７４μｍ以下となるのが好ましい。 As described above, the collapsible particles of the present invention thus obtained are obtained by reducing the concentration of the water-soluble salts in the water-soluble salt-containing aqueous solution or by applying a load to the collapsible particles as the water-soluble salt concentration decreases. It has the characteristic that the decay rate becomes high. Therefore, when the disintegrating particles are blended in a cosmetic composition, the disintegrating particles are stably dispersed without being disintegrated in the cosmetic composition, and the concentration of water-soluble salts in the washing process and the rinsing process is reduced. The collapsible particles disintegrate with the decrease. In consideration of the blending into such a cosmetic composition, the disintegrating properties of the disintegrating particles of the present invention are as follows in an aqueous solution having a water-soluble salt concentration of less than 1.0% by weight, more preferably less than 1.5% by weight. It is preferably designed so that at least a part thereof is disintegrated. From the viewpoint of rinsing with rinsing water, washing is performed in an aqueous solution having a water-soluble salt concentration of less than 1.0% by weight, more preferably less than 1.5% by weight. It is more preferable that 70% by weight or more is designed to be disintegrated with respect to the previous (ie, before disintegrating) disintegrating particles. Moreover, it is preferable that the particle | grains collapsed at this time become an average particle diameter of 74 micrometers or less.
本発明化粧料組成物は、前記の崩壊性粒子、水溶性塩類、界面活性剤及び水を含有し、該崩壊性粒子の含量は感触及び物理的（機械的）洗浄性の点から組成物中１〜２５重量％、好ましくは２〜２０重量％である。 The cosmetic composition of the present invention contains the above-described disintegrating particles, water-soluble salts, surfactant and water, and the content of the disintegrating particles is in the composition from the viewpoint of touch and physical (mechanical) detergency. 1 to 25% by weight, preferably 2 to 20% by weight.
本発明化粧料組成物に用いられる水溶性塩類としては、水溶性無機塩及び水溶性有機塩が挙げられ、水溶性無機塩が好ましい。 Examples of water-soluble salts used in the cosmetic composition of the present invention include water-soluble inorganic salts and water-soluble organic salts, with water-soluble inorganic salts being preferred.
水溶性無機塩としては、例えば塩化ナトリウム、塩化カリウム、塩化マグネシウム等の塩化物；硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸アルミニウム等の硫酸塩；炭酸ナトリウム、炭酸水素ナトリウム等の炭酸塩が挙げられる。尚、塩化ナトリウムの場合、食塩、高純度精製塩、天然塩等が使用される。中でも塩化ナトリウム、塩化カリウム、塩化マグネシウム、硫酸ナトリウム、炭酸ナトリウムが特に好ましく用いられる。 Examples of the water-soluble inorganic salt include chlorides such as sodium chloride, potassium chloride and magnesium chloride; sulfates such as sodium sulfate, potassium sulfate, magnesium sulfate and aluminum sulfate; carbonates such as sodium carbonate and sodium hydrogen carbonate. . In the case of sodium chloride, salt, highly purified salt, natural salt, etc. are used. Of these, sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, and sodium carbonate are particularly preferably used.
水溶性有機塩としては、例えばクエン酸塩、コハク酸塩、マレイン酸塩、フマル酸塩、リンゴ酸塩等や、脂肪酸石鹸、エステル系燐酸塩類、アシル化アミノ酸塩類、スルホコハク酸塩類、タウレート系活性剤等のアニオン界面活性剤又はステアリルジメチルアミノ酢酸ベタイン、トリメチルグリシン、ラウリルヒドロキシスルホベタイン等の両性界面活性剤が使用される。これらの水溶性無機塩及び水溶性有機塩は併用することもでき、その場合には、重量比率にして（水溶性無機塩）／（水溶性有機塩）＝１００／０〜５／９５の範囲が洗浄性向上の点で好ましく、９０／１０〜１０／９０がより好ましい。 Examples of water-soluble organic salts include citrate, succinate, maleate, fumarate, malate, fatty acid soaps, ester phosphates, acylated amino acid salts, sulfosuccinates, and taurate activities. An anionic surfactant such as an agent, or an amphoteric surfactant such as stearyldimethylaminoacetic acid betaine, trimethylglycine, lauryl hydroxysulfobetaine is used. These water-soluble inorganic salts and water-soluble organic salts can be used in combination, and in that case, the weight ratio is (water-soluble inorganic salt) / (water-soluble organic salt) = 100/0 to 5/95. Is preferable from the viewpoint of improving the cleaning property, and 90/10 to 10/90 is more preferable.
これらの水溶性塩類の配合量は、化粧料組成物中の水に対して飽和溶解度未満であるが、崩壊性粒子の組成物中での安定性、すすぎによる崩壊性及び化粧料の起泡性の点から、１．０重量％以上飽和溶解度未満が好ましく、１．５重量％以上飽和溶解度未満がより好ましく、更に２重量％以上飽和溶解度の０．８倍量以下が特に好ましい。 The amount of these water-soluble salts is less than the saturated solubility in water in the cosmetic composition, but the stability of the disintegrating particles in the composition, disintegration due to rinsing and foaming of the cosmetic. From this point, it is preferably 1.0% by weight or more and less than the saturation solubility, more preferably 1.5% by weight or more and less than the saturation solubility, and particularly preferably 2% by weight or more and 0.8 times the saturated solubility or less.
本発明化粧料組成物に用いる界面活性剤（上記の水溶性有機塩として使用されるものを除く）は特に限定されないが、例えば脂肪酸石鹸、燐酸エステル類、アシル化アミノ酸類、スルホコハク酸類、タウレート系活性剤、ポリオキシエチレンアルキル硫酸塩等のアニオン系界面活性剤；アルキルサッカライド類、ＥＯ付加型界面活性剤等の非イオン性界面活性剤等が挙げられる。中でも燐酸エステル類、アシル化アミノ酸類、アルキルサッカライド等が皮膚刺激が少なく好ましい。 The surfactant used in the cosmetic composition of the present invention (excluding those used as the above-mentioned water-soluble organic salt) is not particularly limited. For example, fatty acid soaps, phosphate esters, acylated amino acids, sulfosuccinic acids, taurates Activating agents, anionic surfactants such as polyoxyethylene alkyl sulfates; nonionic surfactants such as alkyl saccharides and EO addition type surfactants. Of these, phosphoric acid esters, acylated amino acids, alkyl saccharides and the like are preferable because of less skin irritation.
尚、本発明化粧料に用いる界面活性剤と水溶性有機塩は一部重複しているが、イオン性界面活性剤であって塩として機能するものは、水溶性塩類として使用することができる。かかる界面活性剤の配合量は特に限定されないが、洗浄剤が固形状のとき６０〜９０重量％、ペースト状のとき４０〜７０重量％、ゲル状のとき４０〜７０重量％、液状のときは１０〜５０重量％配合することが好ましい。更に起泡性向上剤としてアミンオキサイド、イミダゾリン系界面活性剤、ベタイン系界面活性剤を用いることも好ましい。 The surfactant used in the cosmetic of the present invention and the water-soluble organic salt partially overlap, but an ionic surfactant that functions as a salt can be used as a water-soluble salt. The amount of the surfactant is not particularly limited, but is 60 to 90% by weight when the cleaning agent is solid, 40 to 70% by weight when pasty, 40 to 70% by weight when gelling, and when liquid. It is preferable to mix 10 to 50% by weight. Furthermore, it is also preferable to use an amine oxide, an imidazoline-based surfactant, or a betaine-based surfactant as a foamability improver.
上記成分の他、化粧料に通常用いる成分、例えば、油剤、増粘剤、湿潤剤、着色剤、防腐剤、感触向上剤、香料、消炎剤、殺菌剤、紫外線吸収剤、保湿剤等を、本発明の効果を損なわない範囲で用いることができる。 In addition to the above components, components usually used in cosmetics, such as oils, thickeners, wetting agents, coloring agents, preservatives, feel improvers, fragrances, anti-inflammatory agents, bactericides, UV absorbers, moisturizers, etc. It can use in the range which does not impair the effect of this invention.
本発明の崩壊性粒子は、洗顔料、全身洗浄料、固形石鹸等の皮膚洗浄料、シャンプー、頭皮洗浄剤、食器用洗浄剤、コンタクトレンズ用洗浄剤、歯磨き、育毛剤などのほかマッサージ剤にも幅広く用いることができる。 The disintegrating particles of the present invention can be used as a facial cleanser, whole body cleanser, skin cleanser such as bar soap, shampoo, scalp cleanser, dish cleanser, contact lens cleaner, toothpaste, hair restorer and other massage agents. Can also be used widely.
以下に記載の部とは重量部をさす。 The parts described below refer to parts by weight.
崩壊性粒子の製造例１
ＬＦＳ−ＧＳ−２Ｊ型ハイスピードミキサー（深江工業（株）製）に、一次粒子としてＷ−４００Ｇ ２００ｇを仕込み、予備混合後、回転しつつ、バインダーとして有効分１５％のＴ−３３０ １３３ｇを徐々に添加し造粒した。造粒物を７０℃、２４時間乾燥し、篩にて平均粒径３００μｍの崩壊性粒子（１）３４ｇを得た。
Production Example 1 of Disintegrating Particles
LFS-GS-2J type high speed mixer (manufactured by Fukae Kogyo Co., Ltd.) was charged with 200 g of W-400G as primary particles, and after premixing, 133 g of T-330 having an effective content of 15% was gradually added while rotating. And granulated. The granulated product was dried at 70 ° C. for 24 hours, and 34 g of disintegrating particles (1) having an average particle size of 300 μm was obtained with a sieve.
崩壊性粒子の製造例２〜４
一次粒子の種類と量、及びバインダーの種類と量を表１に示すごとく変化させること以外は製造例１と同様にして、崩壊性粒子（２）〜（４）を製造した。尚、表中の量比は、有効分の重量部を表す。
Production Examples 2 to 4 of disintegrating particles
Disintegrating particles (2) to (4) were produced in the same manner as in Production Example 1 except that the kind and amount of primary particles and the kind and amount of binder were changed as shown in Table 1. In addition, the quantity ratio in a table | surface represents the weight part of an effective part.
崩壊性粒子の製造例５
ＳＰＲＡＹ ＤＲＹＥＲ ＳＤ−１（ＥＹＥＬＡ社製）に、一次粒子としてＷ−４００Ｇ １５０ｇ及びＰＥ−１０８０ ５０ｇを用い、バインダーとして６％ＨＰＣ ３３０ｇと５％ＫＬ−５０６ ４００ｇを添加し噴霧乾燥した。得られた粒子を更に７０℃で２４時間乾燥し、篩にて平均粒径２５０μｍの崩壊性粒子（５）６１ｇを得た。
Production example 5 of collapsible particles
To SPRAY DRYER SD-1 (manufactured by EYELA), W-400G 150 g and PE-1080 50 g were used as primary particles, 330 g of 6% HPC and 400 g of 5% KL-506 were added and spray dried. The obtained particles were further dried at 70 ° C. for 24 hours, and 61 g of disintegrating particles (5) having an average particle diameter of 250 μm were obtained with a sieve.
試験例
製造例で得られた崩壊性粒子の平均粒径及び塩溶液中での崩壊率を測定した。得られた結果を表１に示す。
Test Example The average particle diameter of the disintegrating particles obtained in the production example and the disintegration rate in the salt solution were measured. The obtained results are shown in Table 1.
（１）平均粒径の測定方法
レーザ回析／散乱式粒度分布測定装置ＬＡ−９１０（堀場製作所製）にて測定した。平均粒径はメジアン径を用いた。
(1) Measuring method of average particle diameter It measured with the laser diffraction / scattering type particle size distribution measuring device LA-910 (made by Horiba Seisakusho). The median diameter was used as the average particle diameter.
（２）崩壊性粒子の崩壊率の測定方法
（０．９％食塩水崩壊率Ａ（％）、１０％食塩水崩壊率Ｂ（％））０．９％食塩水２９．７ｇにそれぞれの崩壊性粒子を０．３ｇ加え、３５℃の恒温槽に１５時間保存した。次いでこの試料６ｇを人工皮革上に計り取り、更にもう１枚の人工皮革で覆い、５ｇ／cm2 の荷重をかけ前後に５往復した後、２００メッシュ（篩径７４μｍ）の篩で濾過し、残渣の乾燥重量を測定する。このときに崩壊性粒子が２００メッシュの篩を通過した量比を重量百分率で表し、０．９％食塩水崩壊率Ａ（％）とした。同様の操作を１０％食塩水で行い、１０％食塩水崩壊率Ｂ（％）とした。
(2) Method of measuring disintegration rate of disintegrating particles (0.9% saline disintegration rate A (%), 10% saline disintegration rate B (%)) Each disintegration into 0.9% saline 29.7 g 0.3 g of the functional particles was added and stored in a constant temperature bath at 35 ° C. for 15 hours. Next, 6 g of this sample was weighed on an artificial leather, covered with another piece of artificial leather, subjected to a load of 5 g / cm 2 and reciprocated five times before and after, and then filtered with a 200 mesh (sieving diameter 74 μm) sieve. Measure the dry weight of the residue. At this time, the ratio by which the disintegrating particles passed through a 200-mesh sieve was expressed as a percentage by weight, which was defined as 0.9% saline disintegration rate A (%). The same operation was performed with 10% saline to obtain a 10% saline collapse rate B (%).
（３）崩壊性粒子の嵩比重の測定方法
ＪＩＳ Ｋ３３６２記載の「見掛け密度測定器」を水平に置き、漏斗から秤量済みのカップに約１２０mLの崩壊性粒子を自然落下させる。カップから盛り上がった試料をすり落とし、カップの重さを計る。嵩比重は〔カップの中の試料の重量（ｇ）〕／〔カップの容量（mL）〕である。
(3) Method for Measuring Bulk Specific Gravity of Disintegrating Particles An “apparent density measuring device” described in JIS K3362 is placed horizontally, and about 120 mL of disintegrating particles are spontaneously dropped from a funnel into a weighed cup. Remove the sample from the cup and weigh the cup. The bulk specific gravity is [weight of sample in cup (g)] / [cap volume (mL)].
（４）崩壊性粒子の真比重の測定方法
崩壊性粒子約１．３ｇをサンプルカップに入れて精秤した後、マルチボリウム密度計１３０５（ＭＩＣＲＯＭＥＲＩＴＩＣＳ ＩＮＳＴＲＵＭＥＮＴ社製）にて、ヘリウムガスを用いて測定した。測定数は各３点とし平均値を採用した。
(4) Method for measuring true specific gravity of disintegrating particles After about 1.3 g of disintegrating particles are put in a sample cup and precisely weighed, it is measured with a multi-volume density meter 1305 (made by MICROMERITIC INSTRUMENT) using helium gas. did. The number of measurements was 3 points each, and the average value was adopted.
＊１：一次粒子中の配合割合
＊２：〔（バインダー重量）／（一次粒子重量）〕×１００
Ｔ−３３０：マレイン酸変性ポリビニルアルコール、日本合成化学工業（株）製
塩化ナトリウム：特級塩、ナイカイ塩業（株）製
ＫＬ−５０６：イタコン酸変性ポリビニルアルコール、クラレ（株）製
カオリン：和光純薬工業（株）製
Ｌ−３６００：カルボキシメチルセルロースナトリウム（エーテル化度０．４４）、日本製紙（株）製
コーンスターチ：日本薬局方トウモロコシデンプン、松谷化学工業（株）製
ＭＫ−１００：合成雲母、コープケミカル（株）製
Ｋ−１５：ポリビニルピロリドン、和光純薬工業（株）製
ＳＰＣ−２０Ａ：マレイン酸変性ポリビニルアルコール、信越化学工業（株）製
ＨＰＣ：ヒドロキシプロピルセルロース、和光純薬工業（株）製
ＫＮ−１１１：ポリビニルアルコール、クラレ（株）製
* 1: Mixing ratio in primary particles * 2: [(binder weight) / (primary particle weight)] × 100
T-330: Maleic acid modified polyvinyl alcohol, Nippon Synthetic Chemical Industry Co., Ltd. sodium chloride: Special grade salt, Naikai Shigyo Co., Ltd. KL-506: Itaconic acid modified polyvinyl alcohol, Kuraray Co., Ltd. Kaolin: Wako Jun L-3600 manufactured by Yakuhin Kogyo Co., Ltd .: sodium carboxymethyl cellulose (degree of etherification 0.44), corn starch manufactured by Nippon Paper Industries Co., Ltd .: Japanese pharmacopoeia corn starch, MK-100 manufactured by Matsutani Chemical Industry Co., Ltd .: synthetic mica, Cop Chemical Co., Ltd. K-15: Polyvinylpyrrolidone, Wako Pure Chemical Industries, Ltd. SPC-20A: Maleic acid-modified polyvinyl alcohol, Shin-Etsu Chemical Co., Ltd. HPC: Hydroxypropyl cellulose, Wako Pure Chemical Industries, Ltd. ) KN-111: Polyvinyl alcohol, Kuraray Co., Ltd.
表１から判るように、本発明の崩壊性粒子は、水溶性塩類含有水溶液中において、水溶性塩類濃度が高い場合に比較して該塩類濃度が低い方が崩壊性粒子の崩壊率が上昇することがわかる。 As can be seen from Table 1, in the disintegrating particles of the present invention, in the water-soluble salt-containing aqueous solution, the disintegration rate of the disintegrating particles increases when the salt concentration is lower than when the water-soluble salt concentration is high. I understand that.
実施例１〜６及び比較例１〜３
崩壊性粒子１〜５及び粉末状シリカ（平均粒径２１０μｍ）、ＣＬ−５００７（平均粒径３６０μｍ、ポリエチレンビーズ、住友精化（株）製）又は崩壊性粒子６を配合し、表２記載の組成を有する化粧料組成物を調製した。これらの化粧料組成物を用い、実施例１〜５及び比較例１〜３について、それぞれ下記測定法により、崩壊率Ｃ、洗浄率、泡立ち性、マッサージ感、洗い流し性を評価した。結果を表３に示す。
Examples 1-6 and Comparative Examples 1-3
Disintegrating particles 1 to 5 and powdered silica (average particle size 210 μm), CL-5007 (average particle size 360 μm, polyethylene beads, manufactured by Sumitomo Seika Co., Ltd.) or disintegrating particles 6 are blended, and listed in Table 2 A cosmetic composition having a composition was prepared. Using these cosmetic compositions, Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated for the disintegration rate C, the cleaning rate, the foaming property, the feeling of massage, and the wash-out property by the following measurement methods. The results are shown in Table 3.
（ａ）化粧料組成物中の崩壊性粒子の崩壊率の測定方法（崩壊率Ｃ（％））
人工皮革上に化粧料組成物２ｇと水道水４ｇを計り取り、更にもう１枚の人工皮革で覆い、５ｇ／cm2 の荷重をかけ前後に５往復した後、２００メッシュ（粒径７４μｍ）の篩で濾過し、残渣の乾燥重量を測定する。崩壊率は前記の測定方法（２）に準ずる。
（ｂ）洗浄率（％）
人工皮革上に１−〔（ｐ−フェニルアゾ）−フェニル〕アゾ〔２−ナフトール〕で染色した固体脂を直径１５mm、厚さ０．１mmに塗布し、崩壊性粒子又はその他の粒子を含む実施例及び比較例の化粧料、又は崩壊性粒子又はその他の粒子の代わりに精製水を配合した化粧料で洗浄処理を施し、残った固体脂を有機溶媒に溶かしたものを吸光度測定して、未洗浄処理物の固体脂の吸光度測定値と比較することで洗浄率を求めた。これらを次式に入れ、洗浄率を求めた。
(A) Measuring method of disintegration rate of disintegrating particles in cosmetic composition (disintegration rate C (%))
2 g of cosmetic composition and 4 g of tap water are weighed on artificial leather, covered with another piece of artificial leather, applied 5 g / cm 2 and back and forth 5 times, and then 200 mesh (particle size 74 μm). Filter through a sieve and measure the dry weight of the residue. The decay rate conforms to the measurement method (2).
(B) Cleaning rate (%)
Example in which solid fat dyed with 1-[(p-phenylazo) -phenyl] azo [2-naphthol] is coated on artificial leather to a diameter of 15 mm and a thickness of 0.1 mm, and contains disintegrating particles or other particles Washing with cosmetics of comparative examples or cosmetics containing purified water instead of disintegrating particles or other particles, and measuring the absorbance of the remaining solid fat dissolved in an organic solvent, unwashed The washing rate was determined by comparing with the measured absorbance of the solid fat of the treated product. These were put into the following formula and the washing rate was calculated.
ここで、Ｗ＝洗浄率
Ｗ1＝崩壊性粒子又はその他の粒子を含む化粧料の吸光度
ＷO＝精製水を含む化粧料の吸光度
Where W = washing rate W 1 = absorbance of cosmetics containing disintegrating particles or other particles W O = absorbance of cosmetics containing purified water
（ｃ）泡立ち性
化粧料組成物２０ｇと水道水２０ｇを１２０mLのガラス容器（直径４０mm）に取り、２０回振とう後放置し、３０秒後と５分後の泡の高さ（mm）から、泡立ち性を見た。
(C) Foaming property 20 g of cosmetic composition and 20 g of tap water are placed in a 120 mL glass container (diameter 40 mm), left after shaking 20 times, and the height of the foam (mm) after 30 seconds and after 5 minutes. Saw foaming.
（ｄ）マッサージ感
女性の専門パネラー１０人に洗顔を行ってもらい、マッサージ感を官能評価し、以下の基準で判定した。
(D) Feeling of massage Ten female panelists performed face washing, sensory evaluation of the feeling of massage was performed, and the following criteria were used.
◎：８〜１０人が良好と評価した。
○：６〜７人が良好と評価した。
△：５人以下が良好と評価した。
×：１人でも、違和感、刺激感を感じると評価した。
A: 8 to 10 people evaluated it as good.
A: 6 to 7 people evaluated it as good.
(Triangle | delta): Five or less people evaluated it as favorable.
X: It was evaluated that even one person felt discomfort and irritation.
（ｅ）洗い流し性
女性の専門パネラー１０人に洗顔を行ってもらい、洗顔及びすすぎ時における粒子の存在感から洗い流し性を官能評価し、以下の基準で判定した。
(E) Wash-off property 10 female panelists performed face-wash, sensory evaluation of the wash-out property from the presence of particles at the time of washing and rinsing, and the following criteria were used.
◎：８〜１０人が良好と評価した。
○：６〜７人が良好と評価した。
△：５人以下が良好と評価した。
×：１人でも、粒子が残留すると評価した。
A: 8 to 10 people evaluated it as good.
A: 6 to 7 people evaluated it as good.
(Triangle | delta): Five or less people evaluated it as favorable.
X: Even one person evaluated that particles remained.
表３から判るように、本発明の化粧料組成物中の崩壊性粒子は、崩壊性を有さない粒子及び（嵩比重）／（真比重）が本発明の範囲外である崩壊性粒子に比べて、洗浄過程及びすすぎ過程において崩壊し、洗い流し性に優れていることが明らかである。また、本発明の化粧料組成物を用いた場合の洗浄率が高く、マッサージ感も良好であった。更に、本発明の化粧料組成物中の水溶性塩類濃度が飽和塩濃度未満であることから、極めて高い泡立ち性を維持し、洗浄性や使用感にも優れている。本発明の化粧料組成物中の崩壊性粒子は、化粧料組成物の５０℃における保存試験による配合安定性において、いずれも良好であった。 As can be seen from Table 3, the disintegrating particles in the cosmetic composition of the present invention are particles that do not have disintegrating properties and disintegrating particles whose (bulk specific gravity) / (true specific gravity) is outside the scope of the present invention. Compared with the cleaning process and the rinsing process, it is apparent that the material is disintegrated and has excellent washability. Moreover, the cleaning rate when using the cosmetic composition of the present invention was high, and the feeling of massage was also good. Furthermore, since the water-soluble salt concentration in the cosmetic composition of the present invention is less than the saturated salt concentration, it maintains extremely high foaming properties and is excellent in cleanability and usability. The disintegrating particles in the cosmetic composition of the present invention were all good in the blending stability of the cosmetic composition according to a storage test at 50 ° C.
Claims (7)
(b)水溶性塩類 １．０重量％以上飽和溶解度未満、
(c)界面活性剤、並びに
(d)水を含有する化粧料組成物。 (a) 1 to 25% by weight of disintegrating particles according to any one of claims 1 to 5,
(b) Water-soluble salts 1.0% by weight or more and less than saturated solubility,
(c) a surfactant, and
(d) A cosmetic composition containing water .
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| JP2007277279A JP2008031187A (en) | 2007-10-25 | 2007-10-25 | Disintegrative particle |
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| JP2007277279A JP2008031187A (en) | 2007-10-25 | 2007-10-25 | Disintegrative particle |
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| Application Number | Title | Priority Date | Filing Date |
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| JP3467999A Division JP2000229807A (en) | 1999-02-12 | 1999-02-12 | Disintegrable particle |
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| JP2008031187A true JP2008031187A (en) | 2008-02-14 |
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| JP2012092065A (en) * | 2010-10-28 | 2012-05-17 | Kao Corp | Dentifrice |
| JP2012233057A (en) * | 2011-04-28 | 2012-11-29 | Suzuki Yushi Kogyo Kk | Biodegradable scrubbing agent and skin cleansing agent |
| JP2014108951A (en) * | 2012-12-03 | 2014-06-12 | Kao Corp | Pigment granule |
| JP2014108952A (en) * | 2012-12-03 | 2014-06-12 | Kao Corp | Pigment granule |
| US9202572B2 (en) | 2006-11-29 | 2015-12-01 | Rambus Inc. | Thermal anneal using word-line heating element |
| EP3009125A4 (en) * | 2013-06-13 | 2017-01-25 | Kao Corporation | Detergent composition |
| KR20190026478A (en) * | 2017-09-05 | 2019-03-13 | (주)프랜드 | Manufacture method of starch antibiosis scrub beads |
| WO2020050426A1 (en) * | 2018-09-03 | 2020-03-12 | 주식회사 프랜드 | Method for preparing starch antibacterial scrub beads |
| US11244727B2 (en) | 2006-11-29 | 2022-02-08 | Rambus Inc. | Dynamic memory rank configuration |
| US12002513B2 (en) | 2022-01-03 | 2024-06-04 | Rambus Inc. | Self-annealing data storage system |
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| US9202572B2 (en) | 2006-11-29 | 2015-12-01 | Rambus Inc. | Thermal anneal using word-line heating element |
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| WO2020050426A1 (en) * | 2018-09-03 | 2020-03-12 | 주식회사 프랜드 | Method for preparing starch antibacterial scrub beads |
| US12002513B2 (en) | 2022-01-03 | 2024-06-04 | Rambus Inc. | Self-annealing data storage system |
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