JPH11106797A - Disintegrable particle and detergent composition - Google Patents
Disintegrable particle and detergent compositionInfo
- Publication number
- JPH11106797A JPH11106797A JP9276112A JP27611297A JPH11106797A JP H11106797 A JPH11106797 A JP H11106797A JP 9276112 A JP9276112 A JP 9276112A JP 27611297 A JP27611297 A JP 27611297A JP H11106797 A JPH11106797 A JP H11106797A
- Authority
- JP
- Japan
- Prior art keywords
- water
- particles
- disintegrable
- soluble
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Cosmetics (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は崩壊性粒子及びこれ
を含有する洗浄剤組成物に関し、更に詳細には洗浄過程
及びすすぎ過程において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、並びにこれ
を含有し、物理的（機械的）な洗浄性に優れ、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。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to disintegratable particles and a detergent composition containing the same. More particularly, the present invention relates to disintegrating particles during a washing process and a rinsing process, thereby reducing skin damage and itching. The present invention relates to disintegratable particles and a detergent composition containing the disintegrable particles, which is excellent in physical (mechanical) detergency, easily disintegrates by rinsing water or tears, and has extremely good washability.
【０００２】[0002]
【従来の技術】近年、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）が種々販売され、
使用されている。その理由としては、その新しい使用感
とともに、物理的洗浄効果による余分な角質（垢）や毛
穴に入り込んだ汚れ等の通常の洗浄剤組成物では落とし
難いものが落とせるという利点が挙げられる。2. Description of the Related Art In recent years, particles (scrub agents) have been blended.
Various types of wash-off type skin cleanser (facial cleanser, body soap, massage cream, bar soap) are sold.
in use. The reason for this is that, together with the new feeling of use, it is possible to remove extra keratin (dirt) due to the physical cleaning effect, dirt that has entered pores, and the like, which are difficult to remove with ordinary cleaning compositions.
【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す
ることにより高洗浄性及び低刺激性の洗浄剤の開発も行
われている（特開平２−１５１６９３号公報）。Further, in consideration of problems such as irritation to the skin and roughness of the skin, cleaning agents having high detergency and low irritation have been developed by controlling the size and hardness of the scrub agent. (JP-A-2-151693).
【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、物理的な洗浄力や、皮膚を滑らかに仕上げ
る等の効果を目的とした洗浄剤（特開平６−３０５９５
１号公報）や、水溶性無機塩粒子を洗浄剤組成物に配合
することに加えて、液安定化を目的として、塩化カリウ
ム及び塩化マグネシウムを溶解させ、物理的な洗浄力
や、皮膚を滑らかに仕上げる等の効果を目的とした洗浄
剤（特開平８−２０８４５５号公報）が提案されてい
る。[0004] On the other hand, sodium chloride particles having a saturation solubility or higher are blended in a detergent composition, and sodium chloride is present as particles to provide a physical detergency and an effect of smoothing the skin. (JP-A-6-30595
No. 1) and dissolving potassium chloride and magnesium chloride for the purpose of stabilizing the liquid, in addition to blending the water-soluble inorganic salt particles with the detergent composition, to provide physical detergency and smooth skin. There has been proposed a cleaning agent (JP-A-8-208455) for the purpose of achieving a desired finish.
【０００５】[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。However, a cleaning agent containing a scrub agent having a controlled particle size and hardness has problems in use such as a feeling of foreign matter at the time of massaging and a difficulty in washing off after washing. I was
【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においては、スクラブ剤が凝
集、沈降等を起こしやすいため、液安定性やスクラブ剤
を含む各成分の良好な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、洗浄時に
おいて起泡性が極めて低下し、洗浄性や使用感が低下す
るという問題があった。[0006] In a detergent composition containing sodium chloride particles having a saturation solubility or higher, the scrubbing agent is liable to agglomerate and settle, so that the liquid stability and the good dispersibility of each component including the scrubbing agent are improved. There was a problem. In addition, since sodium chloride is contained in excess of the saturation solubility, there is a problem that the foaming property during washing is extremely reduced, and the washing property and the feeling upon use are reduced.
【０００７】一方、前記の水溶性無機塩粒子に加えて塩
化カリウム及び塩化マグネシウムを配合した洗浄剤組成
物については、スクラブ剤の凝集や、沈降等は改良され
るものの、水溶性無機塩を飽和溶解度以上に配合するた
め、洗浄時において起泡性が極めて低下し、洗浄性や使
用感が低下するという問題があった。On the other hand, in a detergent composition containing potassium chloride and magnesium chloride in addition to the above-mentioned water-soluble inorganic salt particles, although the aggregation and sedimentation of the scrubbing agent are improved, the water-soluble inorganic salt is saturated. Since the amount is more than the solubility, there is a problem that the foaming property during washing is extremely reduced, and the washing property and the usability are reduced.
【０００８】[0008]
【課題を解決するための手段】本発明者らは前記従来技
術の問題点や欠点を改良した洗浄剤組成物について鋭意
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。Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a detergent composition which has improved the problems and disadvantages of the above-mentioned prior art. By combining salts and specific disintegrating particles, it has a high detergency, is excellent in usability, and furthermore, the disintegrating particles disintegrate in the washing process and the rinsing process, so that the occurrence of skin damage and itching is small, In addition, the inventors have found that the disintegratable particles are easily disintegrated by rinsing water or tears, so that a cleaning composition having extremely good washability can be obtained, thereby completing the present invention.
【０００９】すなわち、本発明は、水溶性の一次粒子が
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。That is, the present invention relates to disintegrable particles obtained by aggregating water-soluble primary particles (hereinafter referred to as “disintegrable particles”), which reduces the concentration of a water-soluble salt in an aqueous solution containing a water-soluble salt. Accordingly, the present invention provides disintegrable particles characterized in that the disintegration of the disintegrable particles is disintegrated.
【００１０】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。[0010] The present invention also provides a detergent composition comprising the disintegrable particles, a water-soluble salt, a surfactant and water, wherein the concentration of the water-soluble salt is less than the saturation solubility. Is what you do.
【００１１】[0011]
【発明の実施の形態】本発明の崩壊性粒子は、水溶性の
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ほうが崩壊率が高いものである。BEST MODE FOR CARRYING OUT THE INVENTION The disintegrable particles of the present invention are aggregated particles formed by aggregating water-soluble primary particles, and the aggregation is disintegrated in a water-soluble salt-containing aqueous solution due to a decrease in the concentration of the water-soluble salt. That is, the disintegration rate is higher when the water-soluble salt concentration is lower than when the water-soluble salt concentration is higher.
【００１２】本発明の崩壊性粒子を構成する水溶性の一
次粒子としては、有機粒子でも無機粒子でもよい。The water-soluble primary particles constituting the disintegrable particles of the present invention may be organic particles or inorganic particles.
【００１３】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、（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品；澱粉、ショ糖、乳
糖、海草類、タンパク質等の天然高分子が用いられる。
本発明においてアルカリ塩としては、アルカリ金属（Ｎ
ａ、Ｋ、Ｌｉ等）塩、アンモニウム塩、アミン（ヒドロ
キシ基を有していてもよい、総炭素数２〜１０のアミ
ン、例えばモノエタノールアミン、ジエタノールアミ
ン、トリエタノールアミン、モルホリン）塩等が例示さ
れる。The water-soluble organic primary particles include polyvinyl alcohol and / or a derivative thereof, an alkali salt of (meth) acrylic acid, an alkali salt of (meth) acrylic acid / (meth) acrylate copolymer, acrylic acid / maleic acid. Synthetic products such as alkali salts of acid copolymers and polyvinylpyrrolidone; semi-synthetic products such as methylcellulose, ethylcellulose, sodium carboxymethylcellulose, hydroxyalkylcellulose, and starch derivatives; natural polymers such as starch, sucrose, lactose, seaweeds, and proteins Is used.
In the present invention, as the alkali salt, an alkali metal (N
a, K, Li etc.) salts, ammonium salts, amines (amines having a total of 2 to 10 carbon atoms which may have a hydroxy group, for example, monoethanolamine, diethanolamine, triethanolamine, morpholine) salts and the like are exemplified. Is done.
【００１４】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。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。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。The 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; sodium carbonate, sodium hydrogen carbonate and the like. Carbonates. In the case of sodium chloride, commonly sold salt, high-purity purified salt, natural salt and the like are used. Sodium chloride,
Inorganic particles such as potassium chloride, magnesium chloride and sodium carbonate are preferred.
【００１５】これらの水溶性一次粒子は、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。また、これらの水
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。These water-soluble primary particles may have a true spherical shape, a substantially spherical shape, or an irregular shape due to pulverization or the like, and hollow or porous particles may also be used. These water-soluble primary particles may be used alone or in combination of two or more.
【００１６】これら水溶性の一次粒子の平均粒径は７０
μｍ以下であることが好ましく、更に好ましくは５０μ
ｍ以下である。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。The average particle size of these water-soluble primary particles is 70
μm or less, more preferably 50 μm
m or less. If the average primary particle size is in this range,
This is preferable from the viewpoint of the discomfort of the primary particles and the washability when the disintegrating particles are disintegrated by the washing process of the object to be washed and the rinse water or tears.
【００１７】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、１５０μｍから
５００μｍがより好ましい。該崩壊性粒子の平均粒径が
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。The average particle size of the disintegrable particles of the present invention is preferably from 100 μm to 800 μm, more preferably from 150 μm to 500 μm. When the average particle size of the disintegrating particles is in the range of 100 μm to 800 μm, the discomfort and skin irritation during use of the cleaning agent are particularly low, which is preferable.
【００１８】本発明崩壊性粒子は、水溶性の一次粒子が
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。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、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、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
等の半合成品；澱粉、海草類、植物粘質物、タンパク質
等の天然高分子が水溶性バインダーとして用いられる。The disintegrable particles of the present invention are preferably those in which water-soluble primary particles are bonded and aggregated by a water-soluble binder. Such a water-soluble binder is not particularly limited as long as it dissolves in a water-soluble salt aqueous solution by decreasing the salt concentration and precipitates by increasing the salt concentration, but polyvinyl alcohol and / or a derivative thereof, poly ( Alkali (meth) acrylate, (meth)
Synthetic products such as alkali salts of acrylic acid / (meth) acrylic acid ester copolymers, alkali salts of acrylic acid / maleic acid copolymers, polyvinylpyrrolidone, etc .; methyl cellulose, ethyl cellulose, sodium carboxymethyl cellulose, hydroxyalkyl cellulose, starch derivatives, etc. Semi-synthetic products; natural polymers such as starch, seaweed, plant mucilage, and protein are used as the water-soluble binder.
【００１９】本発明の崩壊性粒子においては、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。例えば水溶性一
次粒子として水溶性バインダーよりも溶解性の低いもの
を用いた場合には、水溶性塩類水溶液中において、該塩
類濃度の低下により水溶性バインダーが溶解することに
より凝集が崩壊して水溶性一次粒子となり、次いで該水
溶性一次粒子が水に溶解する。In the disintegrable particles of the present invention, the water-soluble primary particles and the water-soluble binder may use the same kind of material or different materials. For example, when a water-soluble primary particle having a lower solubility than a water-soluble binder is used, in a water-soluble salt aqueous solution, the water-soluble binder dissolves due to a decrease in the salt concentration, so that aggregation is disintegrated and water is dissolved. Primary particles, and then the water-soluble primary particles dissolve in water.
【００２０】水溶性バインダーは水溶性一次粒子の重量
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 used in an amount of from 0.5% by weight to 30% by weight based on the weight of the water-soluble primary particles in view of the disintegration property of the particles and the production of the disintegrable particles or the detergent composition containing the same. It is preferable from the viewpoint of workability.
【００２１】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水溶性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 disintegrable particles of the present invention is not particularly limited. For example, while mixing and / or mixing the water-soluble primary particles and the water-soluble binder, tumbling granulation, tumbling flow granulation, It is preferably produced by a granulation method such as layer granulation, stirring rolling granulation, melt granulation, extrusion granulation, spray drying granulation and / or a coating method such as spray drying.
【００２２】水溶性バインダーとして前記した物質を、
水溶性一次粒子として使用する場合、該水溶性一次粒子
表面に水を加えれば、一次粒子の表面がバインダー機能
を有することになる。従って、水溶性一次粒子表面に水
及び／又は炭素数１〜５のアルコール（メタノール、エ
タノール、イソプロパノール、ブタノール等）を噴霧す
ることによって、新たにバインダーを添加することな
く、本発明所望の崩壊性粒子を得ることができる。The above-mentioned substance as a water-soluble binder is
When used as water-soluble primary particles, if water is added to the surface of the water-soluble primary particles, the surface of the primary particles will have a binder function. Therefore, by spraying water and / or an alcohol having 1 to 5 carbon atoms (methanol, ethanol, isopropanol, butanol, etc.) on the surface of the water-soluble primary particles, the desired disintegration property of the present invention can be obtained without newly adding a binder. Particles can be obtained.
【００２３】また、崩壊性粒子を得る場合における作業
性を改善する等の目的のため水溶性一次粒子表面に該水
溶性一次粒子より小粒径の水不溶性微粒子を被覆しても
よい。ここで用いられる、水不溶性微粒子としてはベン
トナイト、タルク、カオリン、シリカ、酸化珪素、炭酸
カルシウム、酸化チタン、無水珪酸、ポリエチレン、ポ
リプロピレン、セルロース、澱粉等が挙げられ、その使
用量は水溶性一次粒子重量に対し、０〜２０重量％であ
る。The surface of the water-soluble primary particles may be coated with water-insoluble fine particles having a particle diameter smaller than that of the water-soluble primary particles for the purpose of improving workability when obtaining the disintegrable particles. The water-insoluble fine particles used here include bentonite, talc, kaolin, silica, silicon oxide, calcium carbonate, titanium oxide, silicic anhydride, polyethylene, polypropylene, cellulose, starch, and the like, and the amount used is water-soluble primary particles. It is 0 to 20% by weight based on the weight.
【００２４】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、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。このような洗浄剤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．
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１．５重量％未満の
水溶液中で８０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。The disintegrable particles of the present invention thus obtained are:
As described above, in an aqueous solution containing a water-soluble salt, the water-soluble salt has a characteristic that the disintegration rate increases due to a decrease in the concentration of the water-soluble salt. Therefore, when the disintegrable particles are incorporated into a detergent composition, the disintegrable particles are stably dispersed without disintegration in the detergent composition, and the water-soluble salt concentration in the washing step and the rinsing step is reduced. The disintegrable particles disintegrate as the particle size decreases. Considering the formulation into such a detergent composition,
The disintegration characteristics of the disintegratable particles of the present invention are as follows.
It is preferable to design such that at least a part thereof disintegrates in an aqueous solution of less than 5% by weight. From the viewpoint of rinsing with water or tears, furthermore, 80 volumes in an aqueous solution having a water-soluble salt concentration of less than 1.5% by weight. More preferably, it is designed so that at least% disintegrates.
【００２５】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 contains the above-mentioned disintegrable particles, a water-soluble salt, a surfactant and water, and the concentration of the water-soluble salt is less than the saturation solubility.
【００２６】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
５重量％、特に２〜２０重量％が好ましい。The amount of the collapsible particles to be added to the detergent composition of the present invention is from 1 to 2 in terms of feel and physical (mechanical) detergency.
5% by weight, especially 2-20% by weight, is preferred.
【００２７】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
るが、水溶性無機塩が好ましい。The water-soluble salts used in the detergent composition of the present invention include water-soluble inorganic salts and water-soluble organic salts, with water-soluble inorganic salts being preferred.
【００２８】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、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。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。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. Is mentioned. In the case of sodium chloride, commercially available salt, high-purity purified salt, natural salt and the like are generally used. Among them, sodium chloride, potassium chloride, magnesium chloride and sodium carbonate are particularly preferably used.
【００２９】水溶性有機塩としては、例えば脂肪酸石
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が、これらは上記水溶性無機塩と
併用するのが好ましい。この場合に、重量比率にして
（水溶性無機塩）／（水溶性有機塩）＝１００／０〜２
０／８０の範囲が好ましい。Examples of the water-soluble organic salts include fatty acid soaps, ester-based phosphates, acylated amino acid salts, sulfosuccinates, and anionic surfactants such as taurate-based surfactants. It is preferable to use together with an inorganic salt. In this case, the weight ratio of (water-soluble inorganic salt) / (water-soluble organic salt) = 100/0 to 2
A range of 0/80 is preferred.
【００３０】これらの水溶性塩類の配合量は、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、
１．５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倍量が特に好ましい。The content of these water-soluble salts is less than the saturation solubility, but from the viewpoint of the stability of the disintegratable particles in the composition, disintegration by rinsing or tearing, and foaming property of the detergent.
The solubility is preferably 1.5% by weight or more and less than the saturation solubility, and more preferably 2% by weight or more and 0.8 times the saturation solubility.
【００３１】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、エステル系燐酸類、アシル化アミノ酸類、アル
キルエーテルサルフェート、スルホコハク酸類、タウレ
ート系活性剤等のアニオン系界面活性剤；ベタイン類等
の両性界面活性剤；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。中でもエステル系燐酸類、アシル化アミノ酸類、ア
ルキルサッカライド、アルキルエーテルサルフェート、
アミドアルキルベタイン等が皮膚刺激が少なく好まし
い。The surfactant used in the detergent composition of the present invention is not particularly limited. Examples of the main surfactant include fatty acid soaps, ester-based phosphoric acids, acylated amino acids, alkyl ether sulfates, sulfosuccinic acids, and taurate-based surfactants. Surfactants; amphoteric surfactants such as betaines; and nonionic surfactants such as alkyl saccharides and EO addition surfactants. Among them, ester-based phosphoric acids, acylated amino acids, alkyl saccharides, alkyl ether sulfates,
Amidoalkyl betaines and the like are preferred because they cause less skin irritation.
【００３２】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。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
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。Although the surfactant and the water-soluble organic salt used in the detergent of the present invention partially overlap, an ionic surfactant which functions as a salt should be used as a water-soluble salt. Can be. Although the amount of the main surfactant is not particularly limited, it is 60 to 90 when the detergent is solid.
% By weight, 40-70% by weight in paste form, 40-70% by weight in gel form, 10-50% by weight in liquid form
It is preferable to mix them. Further, it is preferable to use an amine oxide or imidazoline-based surfactant as a foaming property improver in addition to the main surfactant.
【００３３】上記成分の他、洗浄剤に通常用いる成分、
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。[0033] In addition to the above components, components commonly used in detergents,
For example, oils, thickeners, wetting agents, coloring agents, preservatives, feel improvers, fragrances, anti-inflammatory agents, bactericides, ultraviolet absorbers, and the like can be used as long as the effects of the present invention are not impaired.
【００３４】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等に幅広
く用いることができる。The detergent composition of the present invention can be widely used, for example, as a facial cleanser, a whole body detergent, a skin detergent such as a solid soap, a shampoo, a dish detergent, a contact lens detergent, and the like.
【００３５】[0035]
【実施例】以下、実施例、比較例により本発明を詳細に
説明するが、本発明はこれら実施例により何ら限定され
るものではない。なお、以下に記載の部とは重量部をさ
す。EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, the part described below means a weight part.
【００３６】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、一次粒子として塩化ナトリウム（特級
塩、ナイカイ塩業（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Ｋ
Ｍ−１１８（ポリビニルアルコール、クラレ（株）製）
５３．３ｇを徐々に添加し、造粒した。造粒物を７０
℃、２４時間乾燥し、篩いにて平均粒径１７０μｍの崩
壊製粒子（１）５５ｇを得た。Production Example 1 of Disintegrable Particles 200 g of sodium chloride (special grade salt, manufactured by Naikai Salt Industry Co., Ltd.) was charged as primary particles into an LFS-GS-2J type high speed mixer (manufactured by Fukae Kogyo Co., Ltd.). After pre-mixing, while rotating, 5% of K
M-118 (polyvinyl alcohol, manufactured by Kuraray Co., Ltd.)
53.3 g was gradually added and granulated. 70 granules
C. for 24 hours, and sieved to obtain 55 g of disintegrated particles (1) having an average particle size of 170 .mu.m.
【００３７】崩壊性粒子の製造例２、３、５ 崩壊性粒子の製造例１に順じ、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、
崩壊性粒子（２）、（３）、（５）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, 3, and 5 of Disintegrable Particles In accordance with Production Example 1 of disintegrable particles, the type and amount of primary particles and the type and amount of binder were changed as shown in Table 1,
Disintegrable particles (2), (3) and (5) were produced. The ratios in the tables represent parts by weight of the effective components.
【００３８】崩壊性粒子の製造例４ ＳＰＲＡＹ ＤＲＹＥＲ ＳＤ−１（ＥＹＥＬＡ社製）
に、一次粒子としてショ糖（和光純薬工業（株）製）粉
砕品２００ｇを用い、２０％ＧＬ−０５（ポリビニルア
ルコール、日本合成（株）製）１５０ｇ徐々に添加し噴
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３２０μｍの崩壊性粒子（４）６１
ｇを得た。Production Example 4 of Disintegrable Particles SPRAY DRYER SD-1 (manufactured by EYELA)
Using 200 g of crushed sucrose (manufactured by Wako Pure Chemical Industries, Ltd.) as primary particles, 150 g of 20% GL-05 (polyvinyl alcohol, manufactured by Nippon Gosei Co., Ltd.) was gradually added, followed by spray drying. The obtained particles are further dried at 70 ° C. for 24 hours, and are sieved with a sieve.
g was obtained.
【００３９】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。得られた結果を表１に示
す。Test Example The average particle size of the disintegrable particles obtained in Production Example and the disintegration rate in water or salt solution were measured. Table 1 shows the obtained results.
【００４０】（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。平均粒径はメジアン径を用いた。(1) Measurement method of average particle diameter The average particle diameter was measured by a laser diffraction / scattering type particle size distribution analyzer LA-910 (manufactured by Horiba). The median diameter was used as the average particle diameter.
【００４１】（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
（％））精製水２９．７ｇにそれぞれの崩壊性粒子を
０．３ｇ、内部標準としてポリスチレンビーズ（粒径１
μｍ）０．１ｇ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、１秒
間片手でマッサージ（前後に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。この時にポリスチレンビーズを内部標準とし、
崩壊性粒子が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。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 the disintegration rate of disintegrable particles (Purified water disintegration rate A (%), 10% saline disintegration rate B
(%)) 0.3 g of each disintegrable particle in 29.7 g of purified water, and polystyrene beads (particle diameter 1
μm) and stored in a thermostat at 35 ° C. for 15 hours. Next, 6 g of this sample was weighed on artificial leather, massaged with one hand for one second (one reciprocation back and forth), and the particle size was measured with a laser diffraction / scattering type particle size distribution analyzer LA-910. At this time, polystyrene beads were used as the internal standard,
The ratio by which the disintegrable particles were disintegrated was represented by volume percentage, and was defined as the purified water disintegration rate A (%). The same operation was performed using a 10% saline solution to obtain a 10% saline solution disintegration rate B (%).
【００４２】[0042]
【表１】 [Table 1]
【００４３】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 塩化ナトリウム：ナイカイ塩業（株）製（特級塩） Ｂ♯１５２：ブリティッシュガム♯１５２、澱粉、松谷
化学工業（株）製 ショ糖：和光純薬工業（株）製、粉砕品 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 Ａ０２ＳＨ：カルボキシメチルセルロースナトリウム、
日本製紙（株）製Kaolin: W-400G: manufactured by Wako Pure Chemical Industries, Ltd. Cellulose powder, sodium chloride manufactured by Nippon Paper Industries Co., Ltd .: Nakai Salt Industry Co., Ltd. (special grade salt) B # 152: British gum 152, starch Sucrose manufactured by Matsutani Chemical Industry Co., Ltd .: pulverized product manufactured by Wako Pure Chemical Industries, Ltd. KM-118: polyvinyl alcohol; GL-05: polyvinyl alcohol manufactured by Kuraray Co., Ltd. A02SH: carboxy manufactured by Nippon Gohsei Co., Ltd. Sodium methylcellulose,
Nippon Paper Industries Co., Ltd.
【００４４】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, the disintegrable particles of the present invention have a lower disintegration ratio of the disintegrable particles when the salt concentration is lower in the aqueous solution containing the salt. Is found to rise.
【００４５】実施例１〜５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２１０μ
ｍ）又はＣＬ−５００７（３６０μｍ）を配合し、表２
記載の組成を有する洗浄剤組成物を調製した。これらの
洗浄剤組成物を用い、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、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。結果を表３
に示す。Examples 1 to 5 and Comparative Examples 1 to 3 Disintegrable particles 1 to 5 and powdery silica (average particle size 210 μm)
m) or CL-5007 (360 μm), as shown in Table 2.
A cleaning composition having the described composition was prepared. Using these detergent compositions, for Examples 1 to 5 and Comparative Examples 1 to 3, the formulation stability, disintegration rate C, washing effect, foaming property, feeling of use (massage effect), skin were determined by the following measurement methods, respectively. Itching and washability were evaluated. Table 3 shows the results
Shown in
【００４６】（ａ）洗浄剤組成物中の崩壊性粒子の崩壊
率の測定方法（崩壊性Ｃ（％）） 人工皮革上に洗浄剤組成物３ｇ、内部標準としてポリス
チレンビーズ０．１ｇ及び水道水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。
崩壊率は前記の測定方法（２）に準ずる。 （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
０℃の恒温相に１週間放置した時の崩壊性粒子、粉末状
シリカ及びＣＬ−５００７の安定性を崩壊率で表した。
崩壊率は前記の測定方法（２）に準ずる。 （ｃ）洗浄向上率（％） 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。これらを次式に入
れ、洗浄効率を求めた。(A) Method for measuring the disintegration rate of disintegrable particles in detergent composition (disintegrable C (%)) 3 g of detergent composition on artificial leather, 0.1 g of polystyrene beads as internal standard and tap water Weigh 3 g, 15
The model was washed with one hand for one second, rinsed with 300 g of tap water, the whole amount was left for 30 minutes, and the particle size was measured with a laser diffraction / scattering type particle size distribution analyzer LA-910.
The decay rate conforms to the above-mentioned measuring method (2). (B) Formulation stability 50 g each of the detergent composition was placed in a 100 ml closed container.
The stability of the disintegrable particles, powdered silica and CL-5007 when left in a constant temperature phase at 0 ° C. for one week was represented by the disintegration rate.
The decay rate conforms to the above-mentioned measuring method (2). (C) Improvement rate of cleaning (%) 1-[(p-phenylazo) -phenyl] on artificial leather
Solid fat dyed with azo [2-naphthol] is 15m in diameter
m, applied to a thickness of 0.1 mm, and washed with detergents of Examples and Comparative Examples containing collapsible particles or other particles, or detergents containing purified water instead of collapsible particles or other particles. The remaining solid fat was dissolved in an organic solvent, the absorbance was measured, and the measured value was compared with the measured absorbance of the solid fat of the unwashed product to determine the washing rate. These were put into the following equation to determine the cleaning efficiency.
【００４７】[0047]
【数１】 (Equation 1)
【００４８】ここで、Ｗ＝洗浄向上率 Ｗ1＝崩壊性粒子又はその他の粒子を含む洗浄剤の吸光
度 ＷO＝精製水を含む洗浄剤の吸光度Here, W = Wash improvement ratio W 1 = Absorbance of detergent containing disintegrating particles or other particles W O = Absorbance of detergent containing purified water
【００４９】（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
０秒後と５分後の泡の高さ（mm）から、泡立ち性を見
た。(D) Foaming property 20 g of the detergent composition and 20 g of tap water were placed in a 120 ml glass container (40 mm in diameter), shaken 20 times, and allowed to stand.
From the height (mm) of the foam after 0 seconds and 5 minutes, the foamability was checked.
【００５０】（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
サージ感を下記評価基準に従い、評価した。(E) Feeling of Use (Massage Effect) Ten female professional panelists performed face washing, and the massage feeling was evaluated according to the following evaluation criteria.
【００５１】 ◎：極めて良好。 ○：良好。 △：普通。 ×：違和感、刺激感を感じる。A: Very good. ：: good. Δ: Normal. X: Discomfort and irritation are felt.
【００５２】（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い、結果を得点
の平均とした（ｎ＝１０）(F) Itching of the skin The cleaning composition was washed with a Teflon stick once a day in the morning and evening for 14 consecutive times on the specific part of the lower arm, and then visually observed for dropping and gloss. And the results were averaged (n = 10)
【００５３】 ◎：変化無し。 ○：軽度。 △：中程度。 ×：重度。A: No change. ：: Mild. Δ: Medium. X: severe.
【００５４】（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下
記評価基準に従い、評価した。(G) Rinseability Ten female professional panelists performed face-washing, and based on the presence of particles during face-washing and rinsing, the washability was evaluated according to the following evaluation criteria.
【００５５】 ◎：極めて良好。 ○：良好。 △：粒子の除去に時間のかかる場合有り。 ×：粒子が残留する場合がある。A: Very good. ：: good. Δ: It may take time to remove particles. X: Particles may remain.
【００５６】[0056]
【表２】 [Table 2]
【００５７】[0057]
【表３】 [Table 3]
【００５８】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。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。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。As can be seen from Table 3, the disintegrable particles in the detergent composition of the present invention have a high formulation stability in a storage test at 50 ° C. of the detergent composition, and disintegrate in the washing step and the rinsing step. It is clear that the washability is excellent. In addition, when the cleaning composition of the present invention is used, the cleaning improvement rate is high, the feeling of use (massage feeling) is good, and there is no itching of the skin. Furthermore, since the water-soluble salt concentration in the detergent composition of the present invention is less than the saturated salt concentration, the water-soluble salts maintain extremely high foaming properties as compared with Comparative Example 1 having a saturated salt concentration or more. Also has excellent cleaning properties and usability.
【００５９】[0059]
【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。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。The cleaning composition of the present invention is particularly excellent in physical (mechanical) detergency, excellent in stability over time, and has a good feeling in use. Furthermore, since the disintegrating particles are disintegrated in the washing process and the rinsing process, the occurrence of skin damage and itching is small, and the disintegrating particles are easily disintegrated by rinsing water or tears, so that the washability is extremely good. .
───────────────────────────────────────────────────── フロントページの続き (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 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Yoshihiro Hasebe 1334 Minato, Wakayama City, Wakayama Prefecture Inside the Kao Research Institute (72) Inventor Hideyuki Hanasawa 2-1-3 Bunka, Sumida-ku, Tokyo Research by Kao Corporation In-house (72) Inventor Ritsuko Yamazaki 2-1-3 Bunka, Sumida-ku, Tokyo Inside Kao Research Institute
Claims (12)
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こ
とを特徴とする崩壊性粒子。1. Disintegrating particles formed by aggregating water-soluble primary particles, wherein the aggregation of the disintegrating particles is disintegrated in a water-soluble salt-containing aqueous solution by lowering the concentration of the water-soluble salts. Disintegrable particles.
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記載の崩壊性粒子。2. The disintegrable particles according to claim 1, wherein the disintegrable particles are particles formed by aggregating water-soluble primary particles by binding with a water-soluble binder.
μｍである請求項１又は２記載の崩壊性粒子。3. The disintegrable particles have an average particle size of 100 to 800.
3. The disintegrable particle according to claim 1, which has a particle size of μm.
ｍ以下である請求項１〜３のいずれか１項記載の崩壊性
粒子。4. The water-soluble primary particles have an average particle size of 70 μm.
The disintegrable particle according to any one of claims 1 to 3, which is not more than m.
一次粒子に対し０．５〜３０重量％である請求項２記載
の崩壊性粒子。5. The disintegrable particles according to claim 2, wherein the content of the water-soluble binder is 0.5 to 30% by weight based on the water-soluble primary particles.
液中で崩壊性粒子の少なくとも一部が崩壊するものであ
る請求項１〜５のいずれか１項記載の崩壊性粒子。6. The disintegrable particle according to claim 1, wherein at least a part of the disintegrable particle disintegrates in an aqueous solution having a water-soluble salt concentration of less than 1.5% by weight.
液中で、崩壊性粒子が崩壊し、その崩壊率が８０体積％
以上である請求項６記載の崩壊性粒子。7. Disintegrating particles are disintegrated in an aqueous solution having a water-soluble salt concentration of less than 1.5% by weight, and the disintegration rate is 80% by volume.
The disintegrable particle according to claim 6, which is the above.
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。8. A dispersible particle according to claim 1, comprising a water-soluble salt, a surfactant and water, wherein the concentration of the water-soluble salt is less than the saturation solubility. Cleaning composition.
濃度が１．５重量％以上飽和溶解度未満である請求項８
記載の洗浄剤組成物。9. The water-soluble salt is an inorganic salt, and the concentration of the inorganic salt is 1.5% by weight or more and less than the saturation solubility.
The cleaning composition according to the above.
重量％を含むものである請求項８又は９記載の洗浄剤組
成物。10. The composition according to claim 1, wherein the disintegrable particles are contained in an amount of from 1% by weight to 25%.
The cleaning composition according to claim 8, wherein the cleaning composition contains about 10% by weight.
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８〜１０のいずれか１項記載の洗浄剤組
成物。11. The cleaning composition according to claim 8, wherein at least a part of the disintegrable particles is disintegrated in a washing step and a rinsing step of the object to be washed.
びすすぎ過程において崩壊し、崩壊率が、洗浄前の崩壊
性粒子に対し８０体積％以上である請求項８〜１１のい
ずれか１項記載の洗浄剤組成物。12. The disintegrable particle according to claim 8, wherein the disintegrable particle is disintegrated in the washing step and the rinsing step of the object to be washed, and the disintegration rate is 80% by volume or more based on the disintegrable particle before washing. 9. The cleaning composition according to item 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9276112A JPH11106797A (en) | 1997-10-08 | 1997-10-08 | Disintegrable particle and detergent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9276112A JPH11106797A (en) | 1997-10-08 | 1997-10-08 | Disintegrable particle and detergent composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11106797A true JPH11106797A (en) | 1999-04-20 |
Family
ID=17564971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9276112A Pending JPH11106797A (en) | 1997-10-08 | 1997-10-08 | Disintegrable particle and detergent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11106797A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000077158A1 (en) * | 1999-06-14 | 2000-12-21 | Kao Corporation | Granular base and particulate detergent |
| JP2001293354A (en) * | 2000-04-12 | 2001-10-23 | Kao Corp | Method for manufacturing breakable particles |
| JP2002053459A (en) * | 2000-08-11 | 2002-02-19 | Kao Corp | Scrub granule |
| JP2006282659A (en) * | 2005-03-08 | 2006-10-19 | Kao Corp | Detergent composition |
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| JP2006282659A (en) * | 2005-03-08 | 2006-10-19 | Kao Corp | Detergent composition |
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