JP2000063899A - Decayable particle - Google Patents

Decayable particle

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JP2000063899A
JP2000063899A JP24692098A JP24692098A JP2000063899A JP 2000063899 A JP2000063899 A JP 2000063899A JP 24692098 A JP24692098 A JP 24692098A JP 24692098 A JP24692098 A JP 24692098A JP 2000063899 A JP2000063899 A JP 2000063899A
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water
particles
particle
disintegrating
soluble
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JP24692098A
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JP3486114B2 (en )
Inventor
Hideyuki Hanazawa
Yoshihiro Hasebe
Shige Matsumoto
Yoshihei Meiwa
Mamoru Nakamura
Ritsuko Yamazaki
守 中村
律子 山崎
善平 明和
樹 松元
英行 花沢
佳宏 長谷部
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Kao Corp
花王株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a decayable particlewhich gives less damage to skin and itch due to decay of the particle during s process of washing and rinsing and a detergent composition which contains said decayable particle and shows excellent detergency and washing-out ability due to easy decay of the decayable particle by rinsing water and tears.
SOLUTION: A decayable particle is formed by coagulation of a primary particle at least a part of which is insoluble in water and the coagulation is destroyed by decrease of concentration of water soluble salt of an aqueous solution containing a water soluble salt. The detergent composition contains a decayable particle, the water soluble salt, a surface active agent and water wherein the concentration of water soluble salt is less than the concentration of the saturated solubility. The detergent composition shows excellent physical (mechanical) detergency, less time dependence thereof and good availability and further gives less damage and itch to skin and excellent washing-out ability due to ease decay of the decayable particle by rinsing water and tears.
COPYRIGHT: (C)2000,JPO

Description

【発明の詳細な説明】 【0001】 【発明の属する技術分野】本発明は崩壊性粒子に関し、 BACKGROUND OF THE INVENTION [0001] [Technical Field of the Invention The present invention relates to disintegrating particles,
更に詳細には洗浄やすすぎの過程で粒子が崩壊することにより、皮膚の損傷や痒みの発生の少ない崩壊性粒子、 Further by particles in the washing and rinsing process collapses in detail, fewer disintegrating particles occurrence of damage or itching of the skin,
並びにこれを含有し、洗浄性に優れ、すすぎ水や涙により容易に崩壊性粒子が崩壊することにより、洗い流し性の極めて良好な洗浄剤組成物に関する。 And containing it is excellent in detergency, by easily disintegrating particles disintegrated by rinse water or tears, about very good detergent composition rinsability. 【0002】 【従来の技術】粒子(スクラブ剤)を配合した、洗い流しタイプの皮膚洗浄剤(洗顔料、ボディーソープ、マッサージクリーム、固形石鹸)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。 [0002] formulated with BACKGROUND ART particles (scrub agent), wash-off skin cleansing (face wash, body soap, massaging cream, solid soap) is dropped in the usual detergent composition in physical cleaning It entered the hard extra horny (plaque) and pore dirt has a feature that can be dropped. 【0003】また、肌に対する刺激や肌荒れ等の問題を考慮して、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及び低刺激性の洗浄剤もある(特開平2−1 [0003] In consideration of irritation and skin roughness such problems for the skin, there is also a high cleaning properties and mildness of the detergent with controlled size and hardness of the particle size of the scrubbing agent (JP-A-2-1
51693号公報)。 51,693 JP). 【0004】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(特開平6−305951号公報)がある。 On the other hand, by blending the saturated solubility over sodium chloride particles detergent composition, sodium chloride is present as particles, detergency and detergent such as smooth finish skin (JP-A-6-305951 JP ) there is. 【0005】 【発明が解決しようとする課題】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。 [0005] The present invention is, however, the detergent formulated with scrubbing agent to control the size and hardness of the particle size, there is a foreign body sensation in the massage time, challenges Usage of such hard rinse after cleaning It had been left behind. 【0006】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。 Further, the detergent composition containing the saturation solubility or more sodium chloride particles, scrubbing agent aggregation, because prone to sedimentation, there is a problem in dispersibility. 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。 Since containing sodium chloride than the saturation solubility, foamability and at the time of washing, there is a problem decrease in detergency and feel. 【0007】 【課題を解決するための手段】本発明者らは前記従来技術の問題点や欠点について検討した結果、界面活性剤と水に加えて、飽和溶解度未満の水溶性塩類と特定の崩壊性粒子を配合することにより、高い洗浄力を有し、使用感に優れ、更に、洗浄過程及びすすぎ過程において崩壊性粒子が崩壊するため皮膚の損傷や痒みの発生が少なく、またすすぎ水や涙により容易に崩壊性粒子が崩壊するため洗い流し性が極めて良好な洗浄剤組成物が得られることを見出し、本発明を完成するに至った。 [0007] The present inventors have SUMMARY OF THE INVENTION The results of investigation of problems and shortcomings of the prior art, in addition to the surfactant and water, a specific disintegrating water-soluble salts of less than saturation solubility by blending the sex particles, high have detergency, excellent usability, further reduce the occurrence of damage or itching of the skin for disintegrating particles disintegrate in the washing process and rinsing process, also the rinse water or tears found that very good detergent composition is obtained rinsability for easily disintegrating particles disintegrated by, and have completed the present invention. 【0008】すなわち、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る崩壊性粒子(以下、崩壊性粒子)と言う)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ことを特徴とする崩壊性粒子を提供するものである。 Namely, the present invention is at least partially disintegrating particles primary particles are water-insoluble is aggregated (hereinafter, disintegrating particles) A ​​say), soluble in water-soluble salts in the aqueous solution containing the decrease in salt concentration and provides a disintegrating particles, wherein the aggregate of the disintegrating particles disintegrate. 【0009】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、水溶性塩類の濃度が飽和溶解度未満であることを特徴とする洗浄剤組成物を提供するものである。 [0009] The present invention also provides the decay particles, water-soluble salts, containing a surfactant, and water, the detergent composition concentration of the water-soluble salts and less than saturation solubility it is intended to. 【0010】 【発明の実施の形態】本発明の崩壊性粒子は、少なくとも一部が水不溶性である一次粒子が凝集して形成された凝集粒子であり、水溶性塩類含有水溶液中において水溶性塩濃度の低下によりその凝集が崩壊するもの、すなわち水溶性塩濃度が高い場合に比べて低い場合の方が崩壊率が高いものである。 DETAILED DESCRIPTION OF THE INVENTION disintegrating particles of the present invention, at least a portion is agglomerated particles of primary particles are formed by aggregation of water-insoluble, water-soluble salts in the water-soluble salts in the aqueous solution containing which collapses the aggregation due to a decrease in concentration, i.e. towards the case lower than in the case where a water-soluble salt concentration high those high decay rate. 【0011】本発明の崩壊性粒子を構成する一次粒子としては、少なくとも一部が水不溶性一次粒子であればよく、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好ましい。 [0011] As the primary particles constituting the disintegrating particles of the present invention may be any at least partially water-insoluble primary particles, for example, water-insoluble primary particles, or a combination of water-insoluble primary particles and water-soluble primary particles preferable. これら一次粒子は有機粒子でも無機粒子でもよい。 These primary particles may be inorganic particles in the organic particles. ここで「水不溶性」 Here, the "water-insoluble"
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、 And, when dissolved target particles 1 part by weight to 99 parts by weight of water at 25 ° C., the solubility is less than 50 wt%,
「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。 By "water-soluble" means that solubility under the same conditions is 50 wt% or more. なお、溶解度は、水溶液を濾紙(N Incidentally, solubility, solution filter paper (N
o. o. 2)で濾過し、濾液中の固形分量より算出する。 Filtered through a 2), it is calculated from the solid content in the filtrate. 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。 Examples of the water-soluble primary particles, the solubility is preferably not less than 90 wt%. 【0012】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− [0012] As the water-insoluble organic primary particles include polyethylene, polypropylene, polyamide, polyethylene terephthalate, polystyrene and polyurethane and / or their crosslinked product, sodium poly (meth) acrylate or poly (meth) acrylic acid esters and / or their another such as a crosslinked body, an ethylene rubber, propylene rubber, styrene -
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。 Butadiene rubber, butadiene rubber, synthetic polymer rubbers, and / or their crosslinked products, such as silicone rubber or the like; cellulose and / or derivatives thereof, chitosan and / or derivatives thereof, starch, and natural polymers shells such fruit / or derivatives thereof. 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、ポリ(メタ)アクリル酸エステル、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。 Of these, polyethylene, polyamide, polystyrene, sodium poly (meth) acrylate, poly (meth) acrylic acid esters, cellulose and / or derivatives thereof, starch and the like are preferably used. ここで「ポリ(メタ)アクリル酸」は「ポリアクリル酸」と「ポリメタアクリル酸」の双方を意味する。 Here "poly (meth) acrylic acid" means both a "polyacrylic acid" "polymethacrylic acid." 【0013】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。 [0013] As water-insoluble inorganic primary particles, bentonite, talc, mica, kaolin, sepiolite, silica, calcium carbonate, titanium oxide, silicic anhydride, other such hydroxy calcium apatite, and a mother-of-pearl. 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。 Of these, bentonite, talc, mica, kaolin, silica and the like are preferably used. 【0014】これらの水不溶性一次粒子は、真球状、略球状及び、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。 [0014] These water-insoluble primary particles, spherical, substantially spherical and may be of irregular shape by grinding or the like, also hollow, porous particles, etc. are also used. また、これらの水不溶性一次粒子は単独で用いても、二種以上を併用しても良い。 Moreover, even with these water-insoluble primary particles alone or in combination of two or more. 【0015】水溶性有機一次粒子としては、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、 Examples of the water-soluble organic primary particles, polyvinyl alcohol and / or derivatives thereof, poly (meth) alkali salts of acrylic acid, (meth) alkali salts of acrylic acid / (meth) acrylic acid ester copolymer, acrylic acid / alkali salts of maleic acid copolymers, synthetic polymers such as polyvinylpyrrolidone; cellulose, ethyl cellulose,
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。 Sodium carboxymethyl cellulose, hydroxyalkyl cellulose, modified starch (hydroxyalkyl-modified starch, phosphoric acid ester-modified starch, etc.), sucrose, saccharides such as lactose; seaweeds, natural polymers such as proteins can be used. 【0016】また、水溶性無機一次粒子としては、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。 [0016] Examples of the water-soluble inorganic primary particles include sodium chloride, potassium chloride, chlorides such as magnesium chloride; sodium sulfate, potassium sulfate, magnesium sulfate, sulfates such as aluminum sulfate; sodium carbonate, sodium hydrogen carbonate They include carbonates. 尚、塩化ナトリウムの場合、一般に販売されている食塩、高純度精製塩、天然塩等が使用される。 In the case of sodium chloride, common salt is generally sold, highly purified salt, natural salt and the like are used. 中でも塩化ナトリウム、 Among them, sodium chloride,
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。 Potassium chloride, magnesium chloride, inorganic particles such as sodium carbonate are preferable. 【0017】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。 [0017] These water-soluble primary particles is also the shape is not limited, may be used two or more in combination. 【0018】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の範囲が好ましい。 [0018] The present invention the weight ratio of water-insoluble primary particles and water-soluble primary particles in disintegrating particles (water-insoluble primary particles) / (water-soluble primary particles) = 1 / 99-100 / 0 is preferably in the range of. 【0019】これら一次粒子の平均粒径は70μm以下であることが好ましい。 [0019] It is preferable that the average particle diameter of the primary particles is 70μm or less. 一次粒子の平均粒径がこの範囲の場合、被洗浄体の洗浄過程及びすすぎ水や涙によって崩壊性粒子が崩壊した場合において、一次粒子の違和感及び洗い流し性の点で好ましい。 When the average particle diameter of the primary particles is in this range, when the disintegrating particles by washing process and rinse water and tears of the cleaning body collapsed, preferred in terms of discomfort and washout of the primary particles. 【0020】本発明の崩壊性粒子の平均粒径は、好ましくは100μmから800μmであり、125μmから600μmがより好ましく、150μmから360μm The average particle diameter of the disintegrating particles of the present invention is preferably 800μm from 100 [mu] m, more preferably from 600μm from 125 [mu] m, 360 .mu.m from 150μm
が特に好ましい。 It is particularly preferred. 該崩壊性粒子の平均粒径が100μm The average particle diameter of the disintegrating particles 100μm
から800μmの範囲にある場合、洗浄剤の使用時における違和感、皮膚刺激が特に低く好ましい。 If in the range of 800μm from discomfort during use of the cleaning agent, skin irritation is preferred particularly low. 【0021】本発明崩壊性粒子は、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のが望ましい。 [0021] The present invention disintegrating particles, the primary particles is desirably obtained by aggregating bound by a water-soluble binder. かかる水溶性バインダーとしては、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、 Such water-soluble binder, in a water-soluble salt solution was dissolved by reduction of the salt compound concentration,
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(イタコ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、マレイ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、 It is not particularly limited as long as it precipitated by increasing the salt compound concentrations, polyvinyl alcohol and / or derivatives thereof (itaconic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, maleic acid-modified polyvinyl alcohol, etc.), poly (meth) acrylic acid alkali salt,
(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ナトリウム、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、 (Meth) alkali salts of acrylic acid / (meth) acrylic acid ester copolymer, alkali salts of acrylic acid / Mullen acid copolymer, synthetic products such as polyvinylpyrrolidone; cellulose, ethyl cellulose, sodium carboxymethyl cellulose, hydroxyalkyl cellulose, starch, seaweed, plant mucilage; semisynthetic polymers such as starch derivatives
タンパク質等の天然高分子が用いられる。 Natural polymers such as proteins can be used. 【0022】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。 [0022] In disintegrating particles of the present invention, said water-soluble primary particles and the water-soluble binder may be using the same type of material, different materials may be employed. 【0023】水溶性バインダーは一次粒子の重量に対し、0.5重量%から30重量%用いるのが粒子の崩壊性の点及び崩壊性粒子又はこれを含有する洗浄剤組成物の製造時の作業性の点から好ましい。 The water-soluble binder is based on the weight of the primary particles, the work at the time of manufacture of the detergent composition to use from 0.5 wt% 30 wt% containing this point and disintegrating particles or the disintegration of the particles preferable from the sexual point. 【0024】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。 [0024] As a production method for disintegrating particles of the present invention, although not particularly limited mixing, for example primary particles and the water-soluble binder and / or while mixing, tumbling granulation, tumbling fluidized granulation, fluidized bed granulation Tablets, stirring rolling granulation, melt granulation, extrusion granulation, spray drying granulation or the like granulation and / or preferably produced by coating method such as spray drying. 【0025】かくして得られた本発明の崩壊性粒子は、 The disintegrating particles of the present invention thus obtained is,
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崩壊率が高くなるという特性を有する。 Wherein As, in water-soluble salts in the aqueous solution containing, has a characteristic of disintegration rate increases due to a decrease in the water-soluble salt concentration. 従って、この崩壊性粒子を、洗浄剤組成物に配合した場合、該洗浄剤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。 Thus, the disintegrating particles, when incorporated into the detergent composition, the disintegrating particles in the detergent composition is stably dispersed without disintegrating, water-soluble salts concentration kicking the washing process and rinsing process disintegrating particles with decreasing collapses. このような洗浄剤組成物への配合を考慮すれば、 Considering the incorporation into such detergent compositions,
本発明崩壊性粒子の崩壊特性は、水溶性塩類濃度が1. Disintegration properties of the present invention disintegrating particles, a water-soluble salt concentration of 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、すすぎ水や涙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. Less than 0 wt%, is preferably at least partially designed to disintegrate more preferably in an aqueous solution of less than 1.5 wt%, the rinsability of points by rinse water or tears, further water-soluble salt concentration of 1. less than 0 wt%, more preferably 1.
5重量%未満の水溶液中で60体積%以上が崩壊するように設計されるのがより好ましい。 5 of more than 60% by volume in aqueous solution of less than% by weight is designed to collapse more preferable. また、このときの崩壊された粒子は平均粒径80μm以下となるのが好ましい。 Further, disintegration particles at this time is preferably equal to or less than the average particle size of 80 [mu] m. 【0026】本発明洗浄剤組成物は、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、該水溶性塩類の濃度が飽和溶解度未満である。 The detergent composition of the present invention, the decay particles, water-soluble salts, containing a surfactant, and water, the concentration of the water-soluble salts is less than the saturation solubility. 【0027】本発明洗浄剤組成物への崩壊性粒子の配合量は、感触及び物理的(機械的)洗浄性の点から1〜2 The amount of the disintegrating particles of the present invention the detergent composition, from the viewpoint of feel and physical (mechanical) cleanability 1-2
5重量%、特に2〜20重量%が好ましい。 5 wt%, in particular 2 to 20% by weight. 【0028】本発明洗浄剤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。 [0028] water-soluble salts used in the present invention the detergent composition may include water-soluble inorganic salts and water-soluble organic salts, preferably water-soluble inorganic salts. 【0029】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。 Examples of the water-soluble inorganic salts such as sodium chloride, potassium chloride, chlorides such as magnesium chloride; sodium sulfate, potassium sulfate, magnesium sulfate, sulfates such as aluminum sulfate; sodium carbonate, carbonates such as sodium hydrogen carbonate and the like. 尚、塩化ナトリウムの場合、一般に市販されている食塩、高純度精製塩、天然塩等が使用される。 In the case of sodium chloride, generally salt which is commercially available, highly purified salt, natural salt and the like are used. 中でも塩化ナトリウム、塩化カリウム、塩化マグネシウム、炭酸ナトリウムが特に好ましく用いられる。 Among them, sodium chloride, potassium chloride, magnesium chloride, sodium carbonate is particularly preferably used. 【0030】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系界面活性剤が使用される。 Examples of the water-soluble organic salts, such as citrate, succinate, maleate, fumarate, malate or the like and, fatty acid soap, ester type phosphates, acylated amino acid salts, sulfosuccinic acid salts, anionic surfactants such as taurates based active agent is used. 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の範囲が好ましい。 These water-soluble inorganic salts and water-soluble organic salt can be used in combination. In this case, in the weight ratio (water-soluble inorganic salt) / range (water-soluble organic salt) = 100 / 0-5 / 95 It is preferred. 【0031】これらの水溶性塩類の配合量は、洗浄剤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、すすぎや涙による崩壊性及び洗浄剤の起泡性の点から、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 salt, but less than the saturated solubility in water in the detergent composition, stability in the composition of the disintegrating particles, disintegration and washing with rinsing and tear from the viewpoint of foaming agent is preferably less than 1.0 wt% or more saturation solubility, more preferably less than 1.5 wt% or more saturation solubility, especially following further 0.8 times the saturated solubility than 2% by weight preferable. 【0032】本発明洗浄剤組成物に用いる界面活性剤は特に限定されないが、主界面活性剤としては例えば脂肪酸石鹸、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。 [0032] The present invention surfactant used in the detergent composition is not particularly limited, as the primary surfactant such as fatty acid soaps, phosphate esters, acylated amino acids, sulfosuccinic acids, taurate type active agents, polyoxyethylene anionic surfactants such as alkyl sulfates, alkyl saccharides include, nonionic surfactants such as EO adduct type surfactants, and the like. 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。 Among these phosphoric esters, acylated amino acids, alkyl saccharides are preferred less skin irritation. 【0033】なお、本発明洗浄剤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。 It should be noted, surfactant and water-soluble organic salts used in the present invention detergent partially overlap, but which functions as a salt an ionic surfactant, be used as a water-soluble salt can. かかる主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 But not according amount of main surfactant is particularly limited, when the cleaning agent is a solid 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% Wt%, pasty 40-70 wt% when the gel-like 40-70 wt% when, when in liquid form 10 to 50 wt%
配合することが好ましい。 It is preferably blended. 更に主界面活性剤の他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を用いることも好ましい。 Further amine oxide Other foaming improvers main surfactant, it is also preferable to use a imidazoline surfactant. 【0034】上記成分の他、洗浄剤に通常用いる成分、 [0034] Besides the above components, components that normally used in detergent,
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。 For example, oils, thickeners, wetting agents, coloring agents, preservatives, texture enhancing agents, perfumes, anti-inflammatory agents, fungicides, UV absorbers and the like may be used in a range that does not impair the effects of the present invention. 【0035】本発明の洗浄剤組成物は、例えば、洗顔料、全身洗浄料、固形石鹸等の皮膚洗浄料、シャンプー、食器用洗浄剤、コンタクトレンズ用洗浄剤、歯磨きなどのほかマッサージクリーム等にも幅広く用いることができる。 The detergent composition of the present invention, for example, facial cleansers, body cleansers, skin cleanser, such as bar soaps, shampoos, dishwashing detergents, cleaners for contact lenses, or the like, as well as massage creams, such as toothpaste it can also be used widely. 【0036】 【実施例】以下に記載の部とは重量部をさす。 [0036] refers to parts by weight and parts described in EXAMPLES below. 【0037】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、一次粒子としてカオリン(和光純薬工業(株)製)200gを仕込み、予備混合の後、回転しつつ、バインダーとして有効分5%のFT−3(カルボキシメチルセルロースナトリウム、M/C 6 =0.9、日本製紙(株)製)40gを徐々に添加し、造粒した。 [0037] Production of disintegrating particles 1 LFS-GS-2J type high-speed mixer (Fukae Kogyo Co.) was charged with kaolin (manufactured by Wako Pure Chemical Industries, Ltd.) 200 g as primary particles, of premixed after, while rotating, FT-3 for the active component a 5% as a binder (carboxymethyl cellulose sodium, M / C 6 = 0.9, Nippon Paper Industries Co., Ltd.) was added 40g slowly and granulated. 造粒物を70℃、24時間乾燥し、篩いにて平均粒径35 Granulation product 70 ° C., then dried for 24 hours, an average particle diameter of 35 at a sieve
0μmの崩壊製粒子(1)45gを得た。 Disintegration made particles of 0 .mu.m (1) was obtained 45 g. 【0038】崩壊性粒子の製造例2〜5 崩壊性粒子の製造例1に準じ、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、 [0038] according to Production Example 1 Production Example 2-5 disintegrating particles of disintegrating particles, the kind and amount of the primary particles, and the type and amount of binder was varied as shown in Table 1,
崩壊性粒子(2)〜(5)を製造した。 Disintegrating particles (2) were prepared to (5). 尚、表中の量比は、有効分の重量部を表す。 The amount ratio in the table represent parts by weight of the active component. 【0039】崩壊性粒子の製造例6 SPRAY DRYER SD−1(EYELA社製) The collapse of the production example of the particle 6 SPRAY DRYER SD-1 (EYELA Co., Ltd.)
に、一次粒子としてUCN−5170D(ポリウレタンビーズ、大日精化(株)製)100gとショ糖(和光純薬工業(株)製)粉砕品100gを用い、5%HPC To, UCN-5170D as primary particles with (polyurethane beads, Dainichi Seika Co., Ltd.) 100 g sucrose (manufactured by Wako Pure Chemical Industries, Ltd.) pulverized product 100 g, 5% HPC
(ヒドロキシプロピルセルロース、和光純薬工業(株) (Hydroxypropyl cellulose, Wako Pure Chemical Industries, Ltd.
製)800g徐々に添加し噴霧乾燥した。 Etsu Chemical Co., Ltd.) was 800g gradually added spray-dried. 得られた粒子を更に70℃で24時間乾燥し、篩にて平均粒径400 The resulting particles were dried for 24 hours at an additional 70 ° C., an average particle diameter of 400 at a sieve
μmの崩壊性粒子(6)56gを得た。 μm was obtained in the disintegrating particles (6) 56 g. 【0040】試験例製造例で得られた崩壊性粒子の平均粒径及び水又は塩溶液中での崩壊率を測定した。 The measured average particle size and disintegration rate in water or salt solution of disintegrating particles obtained in Test Example Preparation. 得られた結果を表1に示す。 The results obtained are shown in Table 1. 【0041】(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)にて測定した。 [0041] (1) was measured by the average particle diameter of the measuring method a laser diffraction / scattering particle size distribution analyzer LA-910 (manufactured by Horiba). 平均粒径はメジアン径を用いた。 The average particle size was used median diameter. 【0042】(2)崩壊性粒子の崩壊率の測定方法(精製水崩壊率A(%)、10%食塩水崩壊率B [0042] (2) Measurement method of decay rates of decay particles (purified water disintegration rate A (%), 10% brine decay rate B
(%))精製水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。 (%)) Of each of the disintegrating particles in purified water 29.7g was added 0.3 g, were stored for 15 hours in a thermostat at 35 ° C.. 次いでこの試料6gを人工皮革上に計り取り、1秒間片手でマッサージ(前後1往復)した後、レーザ回析/散乱式粒度分布測定装置LA−910にて粒径を測定した。 Then weighed sample 6g on artificial leather, after massage (about one reciprocation) with one hand for 1 second, the particle size was determined by laser diffraction / scattering particle size distribution analyzer LA-910.
この時に崩壊性粒子が80μm以下に崩壊した量比を体積百分率で表し、精製水崩壊率A(%)とした。 It represents the amount ratio disintegrating particles disintegrated to 80μm or less when the volume percentage, and the purified water disintegration rate A (%). 同様の操作を10%食塩水で行い、10%食塩水崩壊率B The same operation performed in 10% brine, 10% brine decay rate B
(%)とした。 It was (%). 【0043】 【表1】 [0043] [Table 1] 【0044】カオリン:和光純薬工業(株)製W−400G:セルロースパウダー、日本製紙(株)製PE−1080:ポリエチレンビーズ、住友精化(株) [0044] Kaolin: Wako Pure Chemical Industries, Ltd. W-400G: cellulose powder, Nippon Paper Industries Co., Ltd. PE-1080: polyethylene beads, Sumitomo Seika Chemicals Co., Ltd.
製塩化ナトリウム:ナイカイ塩業(株)製(特級塩) アクリルビーズ:ラウリルアクリレート/ジビニルベンゼン=93/7、合成品澱粉A−55:ソルファレックスA−55、松谷化学工業(株)製UCN−5170D:架橋型ウレタン微粉体、大日精化(株)製ショ糖:和光純薬工業(株)製FT−3:カルボキシメチルセルロースナトリウム、日本製紙(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KM−118:ポリビニルアルコール、クラレ(株)製GL−05:ポリビニルアルコール、日本合成(株)製【0045】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 Salt production Sodium: inner bounds salt industry Co. (special grade salt) acrylic beads: Lauryl acrylate / divinylbenzene = 93/7, synthetic Starch A-55: Sorufa Rex A-55, manufactured by Matsutani Chemical Industry Co. UCN- 5170D: crosslinked polyurethane fine powder, Dainichi Seika Co., Ltd. sucrose: produced by Wako Pure Chemical Industries, Ltd. FT-3: sodium carboxymethyl cellulose, manufactured by Nippon Paper Industries Co., Ltd. HPC: hydroxypropylcellulose, Wako Pure Chemical Industries, Ltd. KM-118: polyvinyl alcohol, Kuraray Co., Ltd. GL-05: as can be seen from polyvinyl alcohol, manufactured by Nippon synthetic Co. [0045] table 1, disintegrating particles of the present invention, water soluble salts as compared with the case water-soluble salt concentration is high in an aqueous solution containing it is divided to better salt such concentration is low decay rate of the disintegrating particles is increased る。 That. 【0046】実施例1〜7及び比較例1〜3 崩壊性粒子1〜6及び粉末状シリカ(平均粒径210μ [0046] Examples 1 to 7 and Comparative Examples 1 to 3 disintegrating particles 6 and powdered silica (average particle diameter 210μ
m)又はCL−5007(360μm)を配合し、表2 m) or CL-5007 a (360 .mu.m) were blended, Table 2
記載の組成を有する洗浄剤組成物を調製した。 The detergent composition was prepared having the composition set forth. これらの洗浄剤組成物を用い、実施例1〜7及び比較例1〜3について、それぞれ下記測定法により、配合安定性、崩壊率C、洗浄効果、泡立ち性、使用感(マッサージ効果)、皮膚の痒み、洗い流し性を評価した。 Using these detergent compositions for Examples 1 to 7 and Comparative Examples 1 to 3, respectively by the following measuring method, formulation stability, decay rate C, cleaning effect, foaming properties, feeling (massaging effect), skin itchy, it was to evaluate the rinsability. 結果を表3 The results in Table 3
に示す。 To show. 【0047】(a)洗浄剤組成物中の崩壊性粒子の崩壊率の測定方法(崩壊率C(%)) 人工皮革上に洗浄剤組成物3gと水道水3gを計り取り、15秒間片手でモデル洗浄を行った後、300gの水道水で洗い流し、全量を30分間放置した後、レーザ回析/散乱式粒度分布測定装置LA−910にて粒径測定した。 [0047] (a) Measurement method (decay rate C (%)) of the decay rate of the disintegrating particles in the detergent composition weighed detergent compositions 3g and tap water 3g on artificial leather, with one hand for 15 seconds after model wash, rinse with tap water 300 g, after leaving the total amount for 30 minutes and the particle size measured by a laser diffraction / scattering particle size distribution analyzer LA-910. 崩壊率は前記の測定方法(2)に準ずる。 The decay rates pursuant to the method of measurement (2). (b)配合安定性洗浄剤組成物を100mlの密閉容器に各50g入れ、5 (B) putting the 50g of formulation stability detergent composition in a closed container 100 ml, 5
0℃の恒温相に1週間放置した時の崩壊性粒子及び、粉末状シリカ、CL−5007の安定性を崩壊率じ表した。 0 ℃ disintegrating particles and when allowed to stand for one week in a constant temperature phase, powdered silica, expressed Ji stability decay rate of CL-5007. 崩壊率は前記の測定方法(2)に準ずる。 The decay rates pursuant to the method of measurement (2). (c)洗浄向上率(%) 人工皮革上に1−〔(p−フェニルアゾ)−フェニル〕 (C) washing improvement rate (%) 1 on the artificial leather - [(p- phenylazo) - phenyl]
アゾ〔2−ナフトール〕で染色した固定脂を直径15m Azo [2-naphthol] stained with a fixed fat diameter 15m
m、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洗浄剤、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洗浄剤で洗浄処理を施し、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。 m, was applied to a thickness of 0.1 mm, cleaning with disintegrating particles or cleaning agents of Examples and Comparative Examples including other particles, or disintegrating particles or detergent formulated with purified water in place of other particles alms and the remaining solid fat and by measuring absorbance those dissolved in an organic solvent to obtain the cleaning rate by comparing the absorbance measurement of solid fat unwashed treated. これらを次式に入れ、洗浄効率を求めた。 These were placed in the following formula to determine the cleaning efficiency. 【0048】 【数1】 [0048] [number 1] 【0049】ここで、W=洗浄向上率W=崩壊性粒子又はその他の粒子を含む洗浄剤の吸光度W O =精製水を含む洗浄剤の吸光度【0050】(d)泡立ち性洗浄剤組成物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、3 [0049] Here, W = absorbance of the cleaning improvement rate W = disintegrating particles or cleaning agent containing the absorbance W O = distilled water detergent containing other particles [0050 (d) The foaming detergent composition 20g and tap water 20g placed in a glass container (diameter 40 mm) of 120 ml, was left after shaking 20 times, 3
0秒後と5分後の泡の高さ(mm)から、泡立ち性を見た。 0 seconds after and 5 minutes after the foam height from (mm), I saw the foaming properties. 【0051】(e)使用感(マッサージ効果) 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。 [0051] (e) feeling Have carried out the cleansing in ten expert panelists of (massage effect) women, a sense of massage and sensory evaluation, was judged by the following criteria. 【0052】 ◎:8〜10人が良好と評価した。 [0052] ◎: 8~10 people was evaluated as good. ○:6〜7人が良好と評価した。 ○: 6~7 people was evaluated as good. △:5人以下が良好と評価した。 △: 5 people or less was evaluated as good. ×:1人でも、違和感、刺激感を感じると評価した。 ×: even one person, was evaluated as feel discomfort, a feeling of stimulation. 【0053】(f)皮膚の痒み洗浄剤組成物を下腕部の特定部位に対して、テフロン棒による洗浄処理を朝夕各1回ずつ、連続14回行った後、落せつ、光沢について肉眼観察を行った。 [0053] with respect to (f) specific site lower arm itching detergent composition of the skin, a washing treatment with Teflon rod one time each morning and evening, after 14 consecutive times, One Otose, visual observation Gloss It was carried out. 【0054】 ◎:何の変化も認められない。 [0054] ◎: not observed any change. ○:落屑の増加が認められる。 ○: increase of desquamation is observed. △:皮膚の赤味、落屑の著しい増加が認められる。 △: of skin redness, a significant increase of desquamation is observed. ×:発疹か化膿が認められる。 ×: rash or suppuration is observed. 【0055】(g)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。 [0055] (g) in ten expert panelists washout of women Have been washing the face, the rinsability from the presence of particles at the time of cleansing and rinsing and sensory evaluation, was judged by the following criteria. 【0056】 ◎:8〜10人が良好と評価した。 [0056] ◎: 8~10 people was evaluated as good. ○:6〜7人が良好と評価した。 ○: 6~7 people was evaluated as good. △:5人以下が良好と評価した。 △: 5 people or less was evaluated as good. ×:1人でも、粒子が残留すると評価した。 ×: even one person, it was evaluated as particle remains. 【0057】 【表2】 [0057] [Table 2] 【0058】 【表3】 [0058] [Table 3] 【0059】表3から判るように、本発明の洗浄剤組成物中の崩壊性粒子は、洗浄剤組成物の50℃における保存試験による配合安定性は高く、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。 [0059] As can be seen from Table 3, disintegrating particles in the detergent composition of the present invention, the mixing stability during storage test at 50 ° C. of the detergent composition is high, collapsed in the washing process and rinsing process, it is clear that is excellent in rinsability. また、本発明の洗浄剤組成物を用いた場合の洗浄向上率が高く、使用感(マッサージ感)も良好であり、皮膚の痒みも無い。 Also, high cleaning improvement rate in the case of using the detergent composition of the present invention, usability (massage feeling) is also good, there is no itchy skin. 更に、本発明の洗浄剤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、水溶性塩類が飽和塩濃度以上の比較例1に比べ、極めて高い泡立ち性を維持することから、洗浄性や使用感にも優れている。 Further, since the water soluble salts concentration of the detergent composition of the present invention is less than the saturated salt concentration, since the water-soluble salts than in Comparative Example 1 above saturated salt concentration to maintain a very high foaming properties, It is also excellent in cleaning properties and feel. 【0060】 【発明の効果】本発明の洗浄剤組成物は、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。 [0060] the detergent composition of the present invention exhibits particularly excellent in physical (mechanical) detergency, also excellent in stability over time, it is better feeling. 更に、洗浄過程及びすすぎ過程において崩壊性粒子が崩壊することにより、皮膚の損傷や痒みの発生が少なく、すすぎ水や涙により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。 Further, by disintegrating particles disintegrate in the washing process and rinsing process, less occurrence of damage or itching of the skin, by easily disintegrating particles disintegrated by rinse water or tears, rinsability is very good .

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl. 7識別記号 FI テーマコート゛(参考) C11D 3/37 C11D 3/37 (72)発明者 松元 樹 和歌山県和歌山市湊1334 花王株式会社研 究所内(72)発明者 長谷部 佳宏 和歌山県和歌山市湊1334 花王株式会社研 究所内(72)発明者 花沢 英行 東京都墨田区文花2−1−3 花王株式会 社研究所内(72)発明者 山崎 律子 東京都墨田区文花2−1−3 花王株式会 社研究所内Fターム(参考) 4C083 AB051 AB271 AB332 AB442 AC122 AC242 AC482 AC542 AC562 AC902 AD022 AD072 AD092 AD112 AD222 AD242 AD262 AD272 AD282 BB01 BB25 BB36 CC23 DD23 EE06 EE07 FF01 4H003 AB38 AC15 BA10 BA12 DA02 DA05 DA16 DA17 EA19 EA27 EB05 EB09 EB14 EB28 EB29 EB33 EB41 EB42 ED02 FA01 FA15 FA23 ────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. 7 identification mark FI theme Court Bu (reference) C11D 3/37 C11D 3/37 (72) inventor Matsumoto tree Wakayama Prefecture Wakayama Minato 1334 Kao Corporation research house (72) inventor Yoshihiro Hasebe Wakayama Prefecture Wakayama Minato 1334 Kao Corporation research house (72) inventor Hideyuki Hanazawa Sumida-ku, Tokyo Bunka 2-1-3 Kao stock company within the Institute (72) inventor Yamazaki Ritsuko Sumida-ku, Tokyo Bunka 2-1-3 Kao stock Company Institute in the F-term (reference) 4C083 AB051 AB271 AB332 AB442 AC122 AC242 AC482 AC542 AC562 AC902 AD022 AD072 AD092 AD112 AD222 AD242 AD262 AD272 AD282 BB01 BB25 BB36 CC23 DD23 EE06 EE07 FF01 4H003 AB38 AC15 BA10 BA12 DA02 DA05 DA16 DA17 EA19 EA27 EB05 EB09 EB14 EB28 EB29 EB33 EB41 EB42 ED02 FA01 FA15 FA23

Claims (1)

  1. 【特許請求の範囲】 【請求項1】 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。 [Claims 1 wherein at least a portion is a disintegrating particles primary particles are water-insoluble is aggregated, the disintegration due to a decrease in the water-soluble salt concentration in the water-soluble salts in the aqueous solution containing disintegrating particles agglomeration of the particles to collapse. 【請求項2】 一次粒子が、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混合物である請求項1記載の崩壊性粒子。 Wherein primary particles, disintegrating particles of claim 1 wherein the mixture of water-insoluble primary particles, or a water-insoluble primary particles and water-soluble primary particles. 【請求項3】 崩壊性粒子が、一次粒子が水溶性バインダーにより結合して凝集してなる粒子である請求項1又は2記載の崩壊性粒子。 3. A disintegrating particles, disintegrating particles according to claim 1 or 2, wherein the particles primary particles formed by agglomerating linked by a water-soluble binder. 【請求項4】 請求項1〜3のいずれか1項記載の崩壊性粒子、水溶性塩類、界面活性剤及び水を含有し、該水溶性塩類の濃度が飽和溶解度未満であることを特徴とする洗浄剤組成物。 4. disintegrating particles of any one of claims 1 to 3, water-soluble salts, containing a surfactant, and water, and wherein the concentration of the water-soluble salts is less than saturation solubility detergent composition. 【請求項5】 水溶性塩類が無機塩であり、該無機塩の濃度が1.0重量%以上飽和溶解度未満である請求項4 5. A water-soluble salt is an inorganic salt, according to claim 4 concentration of the inorganic salt is less than 1.0 wt% or more saturation solubility
    記載の洗浄剤組成物。 Detergent composition. 【請求項6】 崩壊性粒子が、被洗浄体の洗浄過程及びすすぎ過程においてその少なくとも一部が崩壊するものである請求項4又は5記載の洗浄剤組成物。 6. The disintegrating particles according to claim 4 or 5 detergent composition according at least in part in the washing process and rinsing process of cleaning object is intended to disintegrate.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1700619A1 (en) 2005-03-08 2006-09-13 Kao Corporation Detergent composition
JP2006282659A (en) * 2005-03-08 2006-10-19 Kao Corp Detergent composition
JP2007077311A (en) * 2005-09-15 2007-03-29 Asahi Kasei Chemicals Corp High detergency abrasive detergent
JP2007513112A (en) * 2003-12-05 2007-05-24 ユニリーバー・ナームローゼ・ベンノートシヤープ Massage of cosmetic solid soap with a collapse of aggregate
WO2008029500A1 (en) 2006-08-29 2008-03-13 Kao Corporation Gel cosmetic composition
JP2008081495A (en) * 2006-08-29 2008-04-10 Kao Corp Gel cosmetic
JP2012233057A (en) * 2011-04-28 2012-11-29 Suzuki Yushi Kogyo Kk Biodegradable scrubbing agent and skin cleansing agent

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007513112A (en) * 2003-12-05 2007-05-24 ユニリーバー・ナームローゼ・ベンノートシヤープ Massage of cosmetic solid soap with a collapse of aggregate
EP1700619A1 (en) 2005-03-08 2006-09-13 Kao Corporation Detergent composition
JP2006282659A (en) * 2005-03-08 2006-10-19 Kao Corp Detergent composition
JP2007077311A (en) * 2005-09-15 2007-03-29 Asahi Kasei Chemicals Corp High detergency abrasive detergent
WO2008029500A1 (en) 2006-08-29 2008-03-13 Kao Corporation Gel cosmetic composition
JP2008081495A (en) * 2006-08-29 2008-04-10 Kao Corp Gel cosmetic
US7795195B2 (en) 2006-08-29 2010-09-14 Kao Corporation Gel cosmetic composition comprising disintegrable particles, a polyol, a thickening polymer and water
JP2012233057A (en) * 2011-04-28 2012-11-29 Suzuki Yushi Kogyo Kk Biodegradable scrubbing agent and skin cleansing agent

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