JP3566015B2 - Detergent composition for dishwashers - Google Patents
Detergent composition for dishwashers Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、スプレー式、シャワー式等の洗浄方式を採用する自動食器洗浄機に用いられる液体又は固形もしくは粉末の洗浄剤組成物に関する。
【０００２】
【従来の技術】
食器類には食品由来の油脂や蛋白質、澱粉等の汚れが多く付着しているため、洗浄剤には強アルカリを配合して加水分解作用等により汚れを可溶化し、洗浄・除去するようにしている。この際用いられる強アルカリ剤としては、苛性アルカリが代表的であり、これにアルカリの補強のためとアルミ合金製の食器器具やガラス製品の腐食防止のためにケイ酸塩、炭酸塩等が配合される。更に耐硬水性の向上と洗浄力強化のため、キレート剤等を配合するのが一般的である。しかし、業務用の自動食器洗浄機においては、高温洗浄が一般に行われ、このような使用条件下では、洗液が曇ったり、沈澱を生じたりし、洗浄力の低下、スポット汚れの発生或いはスケールの付着が起こったりするという問題がある。
【０００３】
これらの問題に対して、特開平４−１５３００号公報には、ＮａＯＨ又はＫＯＨ、珪酸塩、ポリアクリル酸塩、アミノポリカルボン酸塩及び水を、それぞれ特定比率で含有し、ガラスや金属製の食器表面の腐食防止効果、洗浄力及びスケール付着防止効果を向上させた食器洗浄機用の洗浄剤組成物が開示されている。また、特開平８−１７６５８９号公報には、アルカリ剤とマレイン酸系ポリマーとを含有し、洗浄性能とスケール付着抑制能を有する洗浄剤組成物が開示されている。
【０００４】
【発明が解決しようとする課題】
しかしながら、上記各公報に記載された技術によっても、洗浄力を維持したまま良好なスケール付着防止効果を得ることは困難であり、この両方の効果を満足する食器洗浄機用洗浄剤組成物が要望されている。
【０００５】
【課題を解決するための手段】
本発明者らは上記の目的を達成すべく鋭意研究した結果、アルカリ剤、高分子水溶性分散剤に、更に有機リン系キレート剤を特定比率で配合することにより、洗浄性能とスケール付着防止能の両方に優れた効果を奏する食器洗浄機用洗浄剤組成物が得られることを見出し、本発明を完成した。
【０００６】
すなわち本発明は、アルカリ剤（Ａ）、有機リン系キレート剤（Ｂ）及び高分子水溶性分散剤（Ｃ）を含有し、（Ａ）／（Ｂ）重量比が（Ａ）／（Ｂ）＝１／１〜１０／１、（Ｂ）／（Ｃ）重量比が（Ｂ）／（Ｃ）＝１／１〜１０／１であることを特徴とする食器洗浄機用洗浄剤組成物を提供するものである。
【０００７】
また、本発明は、アルカリ剤（Ａ）、有機リン系キレート剤（Ｂ）、高分子水溶性分散剤（Ｃ）及び水（Ｄ）を含有し、アルカリ剤（Ａ）の含有量が５〜５０重量％、（Ａ）／（Ｂ）重量比が（Ａ）／（Ｂ）＝１／１〜１０／１、（Ｂ）／（Ｃ）重量比が（Ｂ）／（Ｃ）＝１／１〜１０／１であることを特徴とする食器洗浄機用の水性液体洗浄剤組成物を提供するものである。
【０００８】
更に、本発明は、アルカリ剤（Ａ）、有機リン系キレート剤（Ｂ）及び高分子水溶性分散剤（Ｃ）を含有し、アルカリ剤（Ａ）の含有量が４０〜９０重量％であり、（Ａ）／（Ｂ）重量比が（Ａ）／（Ｂ）＝１／１〜１０／１、（Ｂ）／（Ｃ）重量比が（Ｂ）／（Ｃ）＝１／１〜１０／１であることを特徴とする食器洗浄機用の固形又は粉末洗浄剤組成物を提供するものである。
【０００９】
【発明の実施の形態】
本発明に用いられるアルカリ剤（Ａ）としては、アルカリ金属水酸化物、ケイ酸アルカリ金属塩及びアルカリ金属炭酸塩から選ばれる１種又は２種以上が好ましい。具体的には、水酸化ナトリウム、水酸化カリウム、ケイ酸ナトリウム、炭酸ナトリウムが挙げられる。アルカリ剤（Ａ）は組成物中に０．５〜５０重量％、好ましくは１〜５０重量％配合される。この範囲内において、良好な洗浄力が得られ、また食器等に対する浸食、白化が抑制できる。
【００１０】
本発明に用いられる有機リン系キレート剤（Ｂ）としては、ホスホン酸誘導体が特に好ましく、例えばイミノジメチルホスホン酸等のイミノジアルキルホスホン酸もしくはその塩、アルキルジホスホン酸もしくはその塩、アミノトリ（メチレンホスホン酸）もしくはその塩、１−ヒドロキシエチリデン−１，１−ジホスホン酸等のヒドロキシアルキリデンジホスホン酸もしくはその塩から選ばれる１種又は２種以上が挙げられる。有機リン系キレート剤（Ｂ）は組成物中に０．１〜５０重量％、好ましくは０．５〜５０重量％配合されるが、前記（Ａ）成分との重量比（Ａ）／（Ｂ）重量比が（Ａ）／（Ｂ）＝１／１〜１０／１、好ましくは１／１〜３／１となる範囲で配合される必要がある。有機リン系キレート剤（Ｂ）をこの範囲で配合することにより、スケール成分の分散力と汚れ成分の分散力の両方が向上し、高洗浄力とスケール付着防止効果が得られる。
【００１１】
本発明に用いられる高分子水溶性分散剤（Ｃ）としては、ポリカルボン酸型ポリマー類、スルホン酸型ポリマー類等が用いられるが、ポリカルボン酸型ポリマー類が好ましい。ポリカルボン酸型ポリマーとしては、ポリアクリル酸、ポリマレイン酸及びアクリル酸−マレイン酸コポリマーから選ばれる１種又は２種以上が好ましい。これらは一部又は全部が塩となっていてもよく、塩としてはナトリウム、カリウム等のアルカリ金属塩や有機アミン塩が好ましい。ポリアクリル酸の重量平均分子量は１，０００〜２０，０００が好ましく、特に好ましくは２，０００〜１５，０００である。また、ポリマレイン酸は、マレイン酸のポリマー、若しくは無水マレイン酸と共重合可能な他のモノマーとのコポリマー、これらの水溶性塩であり、下記の一般式（Ｉ）で表される構造を有する。
【００１２】
【化１】
〔式中、Ｒ１ 、Ｒ２ 、Ｒ３ 、Ｒ４ は、水素、炭素数１〜５のアルキル基、フェニル基、アルコキシ基、又はカルボキシル基を示し、Ｍは、水素、アルカリ金属又は有機アミンであり、ｘ／ｙ（モル比）＝１／１０〜１０／１で、平均分子量は１，０００〜１００，０００である。〕
上記一般式（Ｉ）において、ｘ／ｙ（モル比）は１／１０〜１０／１であり、好ましくは３／７〜７／３である。また、式（Ｉ）で表されるマレイン酸系ポリマーの重量平均分子量は１，０００〜１００，０００であり、好ましくは１，０００〜２０，０００である。上記一般式（Ｉ）で表される構造を有するポリマーのうち、マレイン酸系コポリマーとしては、アクリル酸−マレイン酸コポリマーが好ましい。
【００１４】
本発明において、上記の如き高分子水溶性分散剤（Ｃ）は、有機リン系キレート剤（Ｂ）との重量比が、（Ｂ）／（Ｃ）＝１／１〜１０／１、好ましくは４／１〜９／１となるように用いられる。この範囲で配合することが特に好ましく、これにより洗浄力とスケール付着防止能の向上がより顕著となる。（Ｃ）成分の如き高分子分散剤は、単独では十分なスケール防止効果が得られにくいが、（Ｂ）成分と併用することにより、良好なスケール防止効果が得られる。
【００１５】
本発明の食器洗浄機用洗浄剤組成物は、液体型又は固形もしくは粉末型の形態をとるが、液体型の場合はバランス量の水（Ｄ）が用いられる。
【００１６】
本発明の食器洗浄機用洗浄剤組成物は、上記（Ａ）〜（Ｃ）成分（液体組成物とする場合は更にバランス量の（Ｄ）成分）を含有するが、更に任意成分を含有することができる。任意成分としては、上記（Ｂ）、（Ｃ）成分以外のキレート剤〔エチレンジアミン四酢酸（ＥＤＴＡ）塩、ニトリロ三酢酸（ＮＴＡ）塩、クエン酸塩、グルコン酸塩、トリポリリン酸（ＳＴＰＰ）塩等〕、低泡性の界面活性剤、有効塩素放出物質（次亜塩素酸塩、塩素化イソシアヌル酸塩等）、消泡剤（リン酸エステル類、シリコーン系消泡剤等）、酵素類（プロテアーゼ、アミラーゼ等）、増量剤（無水硫酸ソーダ等）など食器洗浄剤に一般的に配合される成分が挙げられる。
【００１７】
【発明の効果】
本発明では、アルカリ剤（Ａ）と有機リン系キレート剤（Ｂ）と高分子水溶性分散剤（Ｃ）とを、特定の比率で併用することにより、スケール成分（炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、リン酸カルシウム等）と、汚れ成分（食品成分由来の蛋白質、油脂、澱粉汚れ等）の両方の分散力が向上し、洗浄力と食器洗浄機や食器等の被洗物に対するスケール付着防止効果の両方に優れた食器洗浄機用洗浄剤組成物を得ることができる。従って、本発明の食器洗浄機用洗浄剤組成物によれば、食器類の衛生面の改善、洗浄機のメンテナンスの負担軽減が可能となる。
【００１８】
【実施例】
以下、実施例により本発明の効果をより具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、例中「％」は特記しない限り重量％を意味する。
【００１９】
実施例１〜６及び比較例１〜４
表１に示す食器洗浄機用洗浄剤組成物を調製し、下記の方法で性能評価を行った。その結果を表１に示す。
（１）ＣＶ値（カルシウムイオン捕捉量）
炭酸塩試験法により測定した。洗浄剤組成物２ｇを約５０ｍｌの蒸留水に溶解する。これに、１０ｍｌの２％炭酸ナトリウム水溶液を加え、必要に応じ０．１規定水酸化ナトリウムにてｐＨを１２に調節し、水を加えて１５０ｍｌとする。これを酢酸カルシウム・一水塩の４４．１ｇ／リットル水溶液で安定な沈澱が確認されるまで滴定する。上記酢酸カルシウム水溶液は、２５ｍｇ／ｍｌの炭酸カルシウムと当量なので、洗浄剤１ｇ当りのマスクされた炭酸カルシウムのｍｇ数（ＣＶ値）は以下の式により算出できる。
ＣＶ値＝〔２５×（酢酸カルシウムの滴定量）〕／試料のｇ数。
【００２０】
（２）スケール成分分散力
０．２％洗浄剤水溶液を１００ｍｌ調製し、塩化カルシウム４００ｐｐｍ、炭酸ナトリウム４０ｍｇを溶解する。これを６０℃に加温し、１２時間放置後の溶液状態を観察した。沈澱を生成したものは×、均一分散を維持していたものは○で表した。
【００２１】
（３）スケール付着量
上記評価（２）において、ステンレステストピースを洗浄剤水溶液中に浸漬し、付着したスケール重量を測定した。スケール付着重量はｍｇ／１００ｃｍ２ で表した。
【００２２】
（４）洗浄力
洗浄機として１ドアタイプの業務用食器洗浄機（三洋電機ＤＷ−２３０Ｌ型）を用い、複合モデル汚れ（蛋白質、油脂、デンプンの混合物）を塗布乾燥した磁性皿について、洗浄温度６０℃、洗浄剤濃度０．２％、洗浄時間４０秒、すすぎ温度８０℃、濯ぎ時間１５秒の条件で洗浄し、乾燥後、下記の基準で目視判定した。
判定基準
◎：完全に汚れが除去された
○：殆ど汚れが除去された
△：汚れの除去が不十分である
×：殆ど汚れが除去されない。
【００２３】
（５）洗浄剤適性
上記（１）〜（４）の結果から、食器洗浄機用洗浄剤組成物としての適性を総合評価し、食器洗浄機用洗浄剤組成物として優れている場合は「○」、適さない場合は「×」で表した。
【００２４】
【表１】
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a liquid, solid, or powder detergent composition used in an automatic dishwasher employing a washing method such as a spray method or a shower method.
[0002]
[Prior art]
Tableware has a large amount of dirt such as fats and oils, proteins, and starches from foods, so a strong alkali is added to the detergent to solubilize the dirt by hydrolysis, etc., and wash and remove it. ing. Caustic alkali is a typical example of the strong alkali used at this time, and silicates and carbonates are added to the mixture to reinforce the alkali and prevent corrosion of tableware and glass products made of aluminum alloy. Is done. Further, a chelating agent or the like is generally blended for improving the hard water resistance and enhancing the detergency. However, in a commercial automatic dishwasher, high-temperature washing is generally performed, and under such use conditions, the washing liquid becomes cloudy or precipitates, resulting in a decrease in washing power, generation of spot stains or scale. There is a problem that the adherence of the resin occurs.
[0003]
To cope with these problems, Japanese Patent Application Laid-Open No. 4-15300 discloses that a specific ratio of NaOH or KOH, silicate, polyacrylate, aminopolycarboxylate and water is contained, and Disclosed is a detergent composition for a dishwasher which has an improved effect of preventing corrosion of a dish surface, a detergency, and an effect of preventing scale adhesion. Japanese Patent Application Laid-Open No. 8-176589 discloses a detergent composition containing an alkali agent and a maleic acid-based polymer, and having a cleaning performance and a scale adhesion suppressing ability.
[0004]
[Problems to be solved by the invention]
However, even with the techniques described in each of the above publications, it is difficult to obtain a good scale adhesion preventing effect while maintaining the detergency, and there is a need for a detergent composition for a dishwasher that satisfies both of these effects. Have been.
[0005]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and as a result, by mixing an organic phosphorus-based chelating agent in a specific ratio with an alkali agent and a water-soluble polymer dispersant, the cleaning performance and the scale adhesion preventing ability have been improved. It has been found that a detergent composition for a dishwasher having both excellent effects can be obtained, and the present invention has been completed.
[0006]
That is, the present invention contains an alkali agent (A), an organic phosphorus chelating agent (B) and a polymer water-soluble dispersant (C), and the weight ratio of (A) / (B) is (A) / (B). = 1/1 to 10/1, wherein the weight ratio of (B) / (C) is (B) / (C) = 1/1 to 10/1. To provide.
[0007]
Further, the present invention contains an alkali agent (A), an organic phosphorus chelating agent (B), a polymer water-soluble dispersant (C) and water (D), and the content of the alkali agent (A) is 5 to 5. 50% by weight, (A) / (B) weight ratio (A) / (B) = 1/1 to 10/1, (B) / (C) weight ratio (B) / (C) = 1 / The present invention provides an aqueous liquid detergent composition for a dishwasher, wherein the composition is 1 to 10/1.
[0008]
Further, the present invention contains an alkali agent (A), an organic phosphorus chelating agent (B) and a polymer water-soluble dispersant (C), and the content of the alkali agent (A) is 40 to 90% by weight. , (A) / (B) weight ratio (A) / (B) = 1/1 to 10/1, (B) / (C) weight ratio (B) / (C) = 1/1 to 10 The present invention provides a solid or powder detergent composition for a dishwasher, characterized in that the ratio is / 1.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
As the alkali agent (A) used in the present invention, one or more selected from alkali metal hydroxides, alkali metal silicates and alkali metal carbonates are preferable. Specific examples include sodium hydroxide, potassium hydroxide, sodium silicate and sodium carbonate. The alkaline agent (A) is incorporated in the composition in an amount of 0.5 to 50% by weight, preferably 1 to 50% by weight. Within this range, good cleaning power can be obtained, and erosion and whitening of tableware and the like can be suppressed.
[0010]
As the organic phosphorus chelating agent (B) used in the present invention, phosphonic acid derivatives are particularly preferable. For example, iminodialkylphosphonic acid such as iminodimethylphosphonic acid or a salt thereof, alkyldiphosphonic acid or a salt thereof, and aminotri (methylenephosphonic acid) Acid) or a salt thereof, and one or more selected from hydroxyalkylidene diphosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof. The organophosphorus chelating agent (B) is incorporated in the composition in an amount of 0.1 to 50% by weight, preferably 0.5 to 50% by weight, and the weight ratio of the component (A) to the component (A) / (B) ) It is necessary to be blended in a weight ratio of (A) / (B) = 1/1 to 10/1, preferably 1/1 to 3/1. By blending the organophosphorus chelating agent (B) in this range, both the dispersing power of the scale component and the dispersing power of the dirt component are improved, and a high detergency and an effect of preventing scale adhesion can be obtained.
[0011]
As the polymer water-soluble dispersant (C) used in the present invention, polycarboxylic acid type polymers, sulfonic acid type polymers and the like are used, and polycarboxylic acid type polymers are preferable. As the polycarboxylic acid type polymer, one or more kinds selected from polyacrylic acid, polymaleic acid and acrylic acid-maleic acid copolymer are preferable. Some or all of these may be salts, and the salts are preferably alkali metal salts such as sodium and potassium and organic amine salts. The weight average molecular weight of polyacrylic acid is preferably from 1,000 to 20,000, particularly preferably from 2,000 to 15,000. Polymaleic acid is a maleic acid polymer or a copolymer of maleic anhydride and another monomer copolymerizable with maleic anhydride, or a water-soluble salt thereof, and has a structure represented by the following general formula (I).
[0012]
Embedded image
[Wherein, R 1 , R 2 , R 3 , and R 4 represent hydrogen, an alkyl group having 1 to 5 carbon atoms, a phenyl group, an alkoxy group, or a carboxyl group, and M represents hydrogen, an alkali metal, or an organic amine. Where x / y (molar ratio) = 1/10 to 10/1 and the average molecular weight is 1,000 to 100,000. ]
In the above general formula (I), x / y (molar ratio) is from 1/10 to 10/1, preferably from 3/7 to 7/3. The weight-average molecular weight of the maleic acid-based polymer represented by the formula (I) is from 1,000 to 100,000, preferably from 1,000 to 20,000. Among the polymers having the structure represented by the general formula (I), the maleic acid-based copolymer is preferably an acrylic acid-maleic acid copolymer.
[0014]
In the present invention, the weight ratio of the polymer water-soluble dispersant (C) to the organic phosphorus chelating agent (B) is (B) / (C) = 1/1 to 10/1, preferably It is used so as to be 4/1 to 9/1. It is particularly preferable to mix in this range, whereby the improvement in the detergency and the ability to prevent scale adhesion becomes more remarkable. A polymer dispersant such as the component (C) is unlikely to provide a sufficient scale preventing effect by itself, but a good scale preventing effect can be obtained by using the polymer dispersant in combination with the component (B).
[0015]
The detergent composition for a dishwasher according to the present invention may be in the form of a liquid, a solid or a powder. In the case of the liquid, a balanced amount of water (D) is used.
[0016]
The detergent composition for a dishwasher of the present invention contains the above components (A) to (C) (the component (D) in a more balanced amount when a liquid composition is used), but further contains optional components. be able to. As optional components, chelating agents other than the above components (B) and (C) [ethylenediaminetetraacetic acid (EDTA) salt, nitrilotriacetic acid (NTA) salt, citrate, gluconate, tripolyphosphate (STPP) salt, etc. ], Low-foaming surfactant, effective chlorine releasing substance (hypochlorite, chlorinated isocyanurate, etc.), defoaming agent (phosphate ester, silicone antifoaming agent, etc.), enzyme (protease , Amylase, etc.) and extenders (anhydrous sodium sulfate, etc.) such as components generally used in dishwashing detergents.
[0017]
【The invention's effect】
In the present invention, the scale component (calcium carbonate, magnesium carbonate, silica, etc.) is used by using the alkali agent (A), the organic phosphorus chelating agent (B) and the polymer water-soluble dispersant (C) in a specific ratio. Dispersion of both calcium acid, calcium phosphate, etc.) and soil components (proteins derived from food components, oils, starch stains, etc.) are improved, and the detergency and the effect of preventing scale from adhering to dishes such as dishwashers and dishes. In both cases, an excellent dishwashing detergent composition can be obtained. Therefore, according to the detergent composition for a dishwasher of the present invention, it becomes possible to improve sanitary aspects of dishes and reduce the burden of maintenance of the washer.
[0018]
【Example】
Hereinafter, the effects of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the examples, "%" means% by weight unless otherwise specified.
[0019]
Examples 1 to 6 and Comparative Examples 1 to 4
The cleaning compositions for dishwashers shown in Table 1 were prepared and evaluated for performance by the following methods. Table 1 shows the results.
(1) CV value (calcium ion trapping amount)
It was measured by the carbonate test method. 2 g of the detergent composition is dissolved in about 50 ml of distilled water. To this, 10 ml of a 2% aqueous sodium carbonate solution is added, if necessary, the pH is adjusted to 12 with 0.1 N sodium hydroxide, and water is added to make 150 ml. This is titrated with a 44.1 g / liter aqueous solution of calcium acetate monohydrate until a stable precipitate is confirmed. Since the above-mentioned aqueous solution of calcium acetate is equivalent to 25 mg / ml of calcium carbonate, the number of mg of masked calcium carbonate per 1 g of the detergent (CV value) can be calculated by the following formula.
CV value = [25 × (titer of calcium acetate)] / g of sample.
[0020]
(2) Dispersing power of scale component 100% of a 0.2% aqueous detergent solution is prepared, and 400 ppm of calcium chloride and 40 mg of sodium carbonate are dissolved therein. This was heated to 60 ° C., and the state of the solution after standing for 12 hours was observed. Those that produced a precipitate were represented by x, and those that maintained uniform dispersion were represented by ○.
[0021]
(3) Amount of Scale Attached In the above evaluation (2), a stainless test piece was immersed in an aqueous detergent solution, and the weight of the attached scale was measured. The scale weight was expressed in mg / 100 cm 2 .
[0022]
(4) Using a 1-door type dishwasher (Sanyo Electric DW-230L type) as a washing power washer, and applying a composite model stain (a mixture of protein, oil and starch) to a dried magnetic dish. Washing was performed under the conditions of 60 ° C., a detergent concentration of 0.2%, a washing time of 40 seconds, a rinsing temperature of 80 ° C., and a rinsing time of 15 seconds. After drying, the film was visually judged according to the following criteria.
Criteria ◎: Dirt was completely removed 殆 ど: Almost dirt was removed Δ: Dirt was not sufficiently removed x: Dirt was hardly removed.
[0023]
(5) Suitability of detergent Based on the results of (1) to (4) above, the suitability as a detergent composition for dishwashers was comprehensively evaluated. ", And" x "when not suitable.
[0024]
[Table 1]
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03184597A JP3566015B2 (en) | 1997-02-17 | 1997-02-17 | Detergent composition for dishwashers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03184597A JP3566015B2 (en) | 1997-02-17 | 1997-02-17 | Detergent composition for dishwashers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10226800A JPH10226800A (en) | 1998-08-25 |
| JP3566015B2 true JP3566015B2 (en) | 2004-09-15 |
Family
ID=12342401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03184597A Expired - Fee Related JP3566015B2 (en) | 1997-02-17 | 1997-02-17 | Detergent composition for dishwashers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3566015B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1192789A (en) * | 1997-09-22 | 1999-04-06 | Onodera Naohito | Detergent |
| JP4907180B2 (en) * | 2006-01-27 | 2012-03-28 | 花王株式会社 | Aqueous liquid detergent composition |
| JP2008163079A (en) * | 2006-12-27 | 2008-07-17 | Kao Corp | Liquid detergent composition for automatic dish washer |
| EP2264136B1 (en) * | 2009-06-19 | 2013-03-13 | The Procter & Gamble Company | Liquid hand dishwashing detergent composition |
| ES2412707T5 (en) | 2009-06-19 | 2023-06-12 | Procter & Gamble | Liquid detergent composition for hand dishwashing |
| ES2581934T3 (en) * | 2009-12-10 | 2016-09-08 | The Procter & Gamble Company | Method for measuring the dirt removal capacity of a cleaning product |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2613378A1 (en) * | 1987-04-03 | 1988-10-07 | Sandoz Sa | DETERGENT COMPOSITIONS FOR DISHWASHER |
| JP2505515B2 (en) * | 1988-02-03 | 1996-06-12 | 花王株式会社 | Detergent for automatic dishwasher |
| CH679311A5 (en) * | 1989-01-07 | 1992-01-31 | Sandoz Ag | |
| CA2023529A1 (en) * | 1989-08-22 | 1991-02-23 | Guido Waschenbach | Dish-washer detergent composition |
| JPH0415300A (en) * | 1990-05-09 | 1992-01-20 | Kao Corp | Liquid detergent composition for use in automatic dishwasher |
| DE4112075A1 (en) * | 1991-04-12 | 1992-10-15 | Henkel Kgaa | METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
| JPH05105900A (en) * | 1991-08-27 | 1993-04-27 | Kao Corp | Cleaning agent for cleaning apparatus |
| JPH05214396A (en) * | 1992-02-07 | 1993-08-24 | Kao Corp | Detergent for washer |
| JP3268339B2 (en) * | 1992-04-20 | 2002-03-25 | ライオン株式会社 | Dishwasher detergent composition |
| JPH07118689A (en) * | 1993-10-20 | 1995-05-09 | Lion Corp | Cleaning agent composition for hard surface |
| GB9423952D0 (en) * | 1994-11-24 | 1995-01-11 | Unilever Plc | Cleaning compositions and their use |
-
1997
- 1997-02-17 JP JP03184597A patent/JP3566015B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10226800A (en) | 1998-08-25 |
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