JP2008163240A - Detergent composition comprising organic chelating agent as main ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent which is free of surfactants having questions from stand points of the safety to human bodies and the reduction of loading to the environment. <P>SOLUTION: The detergent contains an organic chelating agent as a main agent for detergent action and no surfactants. In an aqueous solution of the detergent, the content of the chelating agent is 0.01-50 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cleaning composition comprising an organic chelating agent as a main cleaning function.

A detergent composition that does not substantially use a surfactant, and has an alkaline buffering agent that has a washing performance equivalent to or better than that of a synthetic detergent that uses a conventional surfactant as a main agent for washing. There is a detergent composition as a washing action main agent and a washing method using the same (Patent Document 1).

Japanese Patent No. 3481615

The problem to be solved by the present invention is a cleaning agent that does not use a surfactant that is questionable from the viewpoint of safety to the human body and environmental load reduction, and the conventional surfactant is used as a cleaning agent. The present invention is to provide a cleaning agent having an organic chelating agent as a main agent for cleaning, which can provide cleaning performance and usability equivalent to or better than the synthetic detergent.

The cleaning composition of the present invention is a cleaning agent that contains an organic chelating agent as a main agent for cleaning and does not contain a surfactant. When the aqueous chelating agent is used as an aqueous solution, the content of the chelating agent is from 0.01% by weight. It is characterized by being 50% by weight.

  According to the present invention, it is possible to provide a cleaning agent having an organic chelating agent as a main cleaning agent and having high cleaning performance and usability equal to or higher than those of a synthetic detergent. In addition, according to the cleaning agent of the present invention, both cleanliness that dislikes filth and health consciousness that dislikes the residue of detergent components on the wash, both seemingly contradictory contemporary Japanese consumer needs are extremely high. It can be satisfied with the standard.

First, the mechanism of cleaning will be described. The force that attracts the substrate (object to be cleaned) and dirt, including intermolecular force, is mostly due to weak electrostatic force. Therefore, if the attracting force is weakened and the dirt is peeled off from the substrate by a physical force and dispersed in the cleaning liquid, the dirt can be removed.

For example, physical power is mainly used in scenes where wiping and cleaning is mainly performed in toilets, bathrooms, kitchen areas, floors, etc., and mainly in scenes where washing machines are used for washing clothes. That means mechanical power. In addition, the cleaning liquid is a concept including what is contained in a wipe.

  However, the polyvalent cations (hardness component) such as calcium ion and magnesium ion in the detergent aqueous solution bridge both the negatively charged substrate and the soil in the detergent aqueous solution (so-called polyvalent cation). In order to attract the two in the form of a cation bridge), it prevents the dirt from peeling off from the substrate.

  The present inventors pay attention to this point, and have come to consider that achieving a high level of ineffectiveness of the hardness component in the cleaning agent aqueous solution is a very important factor in improving the cleaning performance of the object to be cleaned. It was.

  In the course of diligent development based on this concept, the present inventors have found that the hardness component in the cleaning solution is not only contained in the cleaning water but also adheres to the object to be cleaned and dirt. In the process of cleaning, the product has been dissolved in the aqueous solution of the cleaning agent, and I learned that the hardness components including all of them are an obstacle to cleaning power.

  As long as these hardness components are mainly inhibited by an organic chelating agent, the soil can be peeled off by applying physical force. In addition, it is necessary in many cleaning situations by adding a cleaning action in which organic chelating agents decompose and remove stains containing hardness components such as calcium salts, and a stain re-adhesion preventing effect by a dispersant. It has been found that it is possible to provide a cleaning agent having a sufficient cleaning power.

《Organic chelating agent》
The organic chelating agent, which is positioned as the most important component in the present invention, invalidates the hardness component in the aqueous cleaning agent solution by chemically bonding with the polyvalent cation (hardness component) in the aqueous cleaning solution to form a metal ion complex. And a mechanism for decomposing and removing soils containing hardness components such as calcium salts, and plays a role as a cleaning agent in the present invention, and a) a chelation rate is high, and b) a chelation treatment. Satisfying the following conditions: high ability, c) stable chelating effect, d) high safety, e) good biodegradability, f) good solubility Are preferably used.

  Examples of substances that can be used as the organic chelating agent according to the present invention include oxalic acid (OA), citric acid (CA), tartaric acid (TA), and gluconic acid (GA). : Organic carboxylic acids such as gluconic acid) and organic carboxylic acid sodium salts, dihydroxyethyl glycine (DEG: N- (2-hydroxylethyl) glycine), triethanolamine (TEA: triethanolamine), N- (2-hydroxyethyl) Hydroxyaminocarboxylic acid-based chelating agents such as iminodiacetic acid (HEIDA: N- (2-hydroxyethyl) iminodiacetic acid) and hydroxyethylethylenediaminetetraacetic acid (HEDTA), carboxymethyl Ate which is a sodium salt such as tartronic acid (CMT: O-carboxymethyltartronic acid) and carboxymethyloxysuccinic acid (CMOS). Carboxylic acid chelating agent, vinyl type polyelectrolyte chelating agent which is sodium salt such as polyacrylic acid and acrylic acid / maleic acid copolymer (copolymer), NTA (Nitrilo Triacetic Acid), DTPA (Diethylenetriaminepentaacetic acid: Diethylene Triamine Pentaacetic Acid), HEDTA (Hydroxyethyl Ethylene Diamine Triacetic Acid), EDTA (Ethylene Diamine Tetraacetic Acid), MGDA (MethylGlycine Diacetic Acid), GLDA (L-glutamate diacetic acid: Dicarboxymethyle Glutamic Acid), ASDA (Aspartate Diacetic Acid), EDDS (Ethylenediamine Disuccinic Acid), HIDS (Hydroxye Iminodisuccinic Acid), IDS (iminodisuccinic acid: Iminodisuccinic Acid) Acid chelating agent is sodium salt is preferably used. Of these, MGDA, GLDA, ASDA, EDDS, HIDS, IDS, etc., which have good biodegradability, are preferred from the viewpoint of reducing environmental impact.

  In addition, the organic chelating agent referred to in the present invention is a concept encompassing both an embodiment in which an organic chelating agent as described above is used alone and an embodiment in which a plurality of organic chelating agents are used in combination. .

  As a quantitative condition when selecting an organic chelating agent suitable for use in the present invention from the aspect of cleaning performance, a substance having a larger maximum calcium complexing ability in a pH range according to the application is used from the viewpoint of reducing the amount used. preferable.

<Dispersant>
Dispersing agents are important in taking dirt that has peeled from the substrate into the cleaning solution and preventing re-adhesion. However, by using a water-soluble polymer that has a surface tension-reducing effect, a metal soap (soap with a water repellent effect) is used. A chelating agent can be made to act effectively on scum and oily dirt.

Examples of substances that can be used as the dispersant according to the present invention include water-soluble polymer substances such as sodium polyacrylate, polyethylene glycol, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinyl pyrrolidone. Further, as a dispersant having a surface tension reducing action, methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, partially saponified polyvinyl alcohol, polypropylene glycol, polyoxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, etc. Nonionic water-soluble polymer substances can be mentioned.

《Thickener》
The thickener is important for suppressing the dripping, allowing the cleaning agent to remain on the object to be washed for as long as possible, and exerting the effect of the cleaning component sufficiently.

  Since the water-soluble polymer described in the section of the dispersant also has a viscosity increasing action, the effect of the dispersant and the thickener can be expected with one agent. In the case of mainly having a viscosity increasing action, it is preferable from the viewpoint of reducing the amount of use because the viscosity can be increased with a small amount if a material having a high molecular weight is used.

  Further, by using an inorganic thickener, it is possible to give a viscosity that cannot be obtained with an organic thickener, and an effect of reducing the amount of organic matter used can be expected.

  Examples of inorganic thickeners include magnesium aluminum silicate, synthetic hectorite, bentonite (Na-montmorillonite), synthetic smectite, and sepiolite.

<PH adjuster>
The cleaning agent according to the present invention can have an appropriate pH depending on the application. For example, for toilet cleaning applications for the purpose of removing urinary stones, it is possible to design a cleaning agent in an acidic region intended to chelate urinary stones with an acid and chelate hardness components such as calcium salts of the eluted soil. .

  In addition, it is possible to design a neutral region cleaning agent in consideration of safety at the time of skin contact or assuming the use of laundry of animal fiber clothing.

  Alternatively, a cleaning agent in an alkaline region that is specifically intended for cleaning oils and fats, protein stains, and the like can be designed for cleaning applications such as ventilation fans, windows, and floors.

  Here, it is needless to say that the above-described specific uses and the correspondence relationship between the liquid regions are merely examples, and the respective uses and stains can correspond to the respective liquid regions.

  In the pH adjustment, when it is desired to lower the liquidity, for example, an organic acid such as citric acid or malic acid, or an inorganic acid such as hydrochloric acid can be used as a pH adjusting agent. More preferable. When it is desired to increase the liquidity, sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide can be used as a pH adjuster. Bicarbonate or the like may be added for the purpose of enhancing the pH buffering action.

  For the selection of the organic chelating agent, an organic chelating agent having the highest chelating ability and high stability within the pH range according to the application may be selected. By combining with such a pH adjusting agent, for example, An appropriate organic chelating agent can be selected without being restricted by the liquidity of the organic chelating agent itself, such as using an organic alkaline chelating agent in an acid to neutral region.

《Concept of cleaning composition and usage concentration》
When proposing the above-mentioned cleaning agent to the market, how to set the cleaning agent composition and the standard usage amount becomes a problem.

  First, the case of washing with the largest amount of cleaning liquid relative to the amount of dirt and the object to be washed will be exemplified.

When cleaning an object to be cleaned, the appropriate cleaning composition and amount used depend greatly on the hardness of the cleaning water, and therefore the cleaning composition and amount used must be different for each country. For example, the actual situation is that water of high hardness exceeding 110 ppm in the United States and higher than 180 ppm in Europe is usually used in the vicinity of 70 ppm in Japan. Then, the required amount of the organic chelating agent changes according to the hardness of the cleaning water, and the standard usage amount needs to be adjusted.

  Therefore, in the present invention, for example, A) a region having a low hardness and a small hardness range (about 0 to 120 ppm) and B) a region having a high hardness and a large hardness range (over 120 to 350 ppm), By setting the standard usage amount for each region, it was decided to absorb the above-mentioned problems caused by differences in the cleaning situation due to changes in the hardness of the cleaning water.

  In the case of the former area A, if the detergent composition and standard use amount are set using Japanese standard washing water with a hardness of 90 ppm, and the use amount is appropriately increased in a very limited high hardness region, Good.

  In the case of the latter area B, assuming the type II (125-250 ppm) of hardness classification in Europe, the detergent composition and the standard use amount are set using the European standard cleaning water with a hardness of 250 ppm. What is necessary is just to respond | correspond by changing the usage-amount suitably according to the hardness classification | category in and the grade of dirt.

  Specifically, for example, in the case where a chelating agent having a chelating ability (maximum calcium complexing ability) of 200 mg / g is to be blended, in Japanese standard cleaning water (hardness: 90 ppm), The minimum required amount is 0.45 g / L.

Washing water hardness / chelating ability of organic chelating agent used (maximum calcium scavenging ability) = 90/200 = 0.45 g / L
The chelating ability exemplified above is a value at a pH of 11.0, and when used in a neutral range of liquidity, the reduced chelating ability must be corrected. About twice the concentration used for washing in the weak alkaline range is recommended.

  Of the cleaning agent according to the present invention, the concentration of the dispersant used is 0.001 wt% to 0.05 wt% regardless of the hardness of the cleaning water.

  On the other hand, assuming the use of European standard cleaning water (hardness: 250 ppm), for example, when trying to add a chelating agent having a chelating ability (maximum calcium complexing ability) of 200 mg / g, the minimum amount of chelating agent is necessary. The amount (concentration) is 1.25 g / L.

  As described above, when setting in the neutral range, the chelating agent concentration should be about twice.

  In addition to the essential components of the present invention, for example, when adding additives such as cleaning enzymes, oxygen bleaches, bactericides, fragrances, foaming agents, etc., the amount used is the amount of the added additives. Increase it.

  Except for the case of washing as described above, in most cases, a cleaning agent is sprayed around the dirt adhering to the object to be washed, and the dirt is rubbed off with a brush or wiping cloth, or the cleaning cloth is impregnated with the cleaning agent. Since it is a wiping method, the amount of the cleaning agent aqueous solution used is small, but the necessary concentration of the chelating agent and the dispersant contained in the cleaning liquid around the dirt and the object to be cleaned is considered to be basically the same. However, when water other than the cleaning agent is present, such as in the case of toilet bowl or bathroom cleaning, the chelating agent is consumed by the polyvalent cation contained in the water, or the chelating agent or dispersing agent is diluted. Therefore, it is necessary to set a higher density in consideration of this. When the cleaning agent is used in an aqueous solution having an actual use concentration, the minimum content of the chelating agent, which is the main cleaning agent, is 0.01% by weight, and the minimum content of the dispersing agent is 0.001% by weight. Moreover, when diluting each time it is used as a concentrated cleaning solution, the concentration depends on the solubility of the chelating agent that is a main agent for cleaning, but it can be concentrated about 5000 times the necessary minimum concentration.

  In the case of commercialization as a powder cleaning agent, it is not necessary to consider the solubility, so the content rate is calculated from the total weight excluding the solvent that is the remainder of the total content rate of each drug exemplified above.

"Additive"
The cleaning agent of the present invention is a thickening agent, a foaming agent, a polishing agent, a fragrance, a coloring agent, a sterilizing component, an abrasive, an alcohol, a glycerin, or the like, as necessary, without departing from the spirit of the present invention. Depending on the application, it may further contain substances contained as usual components in various conventional detergents, such as agents, cleaning enzymes, and bleaching agents.

  Among these additives, the thickener has been described above. Similarly, the foaming agent makes it difficult for the cleaning agent to flow down, thereby reducing the amount of cleaning agent used. The cleaning enzyme is useful for removing dirt components that are difficult to remove in the cleaning system of the present invention, which contains an organic chelating agent as an essential component. Examples of washing enzymes include proteolytic enzymes (proteases), lipolytic enzymes (lipases), cellulose-degrading enzymes (cellulases), and starch-degrading enzymes (amylases). The blending amount of the enzyme may be about 0.3% to 3% by weight per enzyme with respect to the total amount of the cleaning agent.

  In addition, when examining the formulation of the enzyme, it is necessary to select an enzyme whose activity value does not decrease in the pH range.

  Examples of the bleaching agent include oxygen-based bleaching agents such as sodium percarbonate, sodium perborate, and hydrogen peroxide, and chlorine-based bleaching agents such as sodium hypochlorite.

  Disinfectants are formulated for the purpose of preventing the decay and mold of cleaning agents containing organic substances in addition to the sterilization of the objects to be cleaned, and they can be used for benzalkonium chloride, parabens, propylene glycol, ethyl alcohol, etc. It can be appropriately selected depending on the case. In consideration of safety to the human body, it is desirable to add an extract extracted from citrus fruit seeds. Here, the citrus fruit is a grapefruit whose scientific name is citrus paradeshi, and the extract itself is highly viscous. It is preferable to use a dispersant. Citruparadesi seed extract has antibacterial effects such as sterilization of bacteria and microorganisms and antibacterial effects. Therefore, when it is added as an antibacterial additive to the cleaning agent of the present invention, an antibacterial effect on the object to be cleaned can be expected. As other fungicides, natural fungicides obtained from tea leaves or bamboo may be blended.

Hereinafter, a specific example in which the cleaning performance of the cleaning agent or the cleaning agent aqueous solution of the present invention is compared with that of the conventional cleaning agent and the cleaning agent aqueous solution will be described.

However, the specific numerical values shown below exemplarily disclose a part of the cleaning performance obtained by using the cleaning agent of the present invention, and are not intended to limit the present invention. Note that the cleaning power of the examples or comparative examples relating to the cleaning power test in the case of washing disclosed in this specification may vary depending on the lot number of the dirty cloth to be used. It should be noted that it is desirable to keep the level of reference when comparing the detergency between tests with different lot numbers.

  Moreover, since it is difficult to make a relative comparison of the visual evaluation by the tester with an objective numerical value except for washing, the scoring evaluation was made based on the tester's sense.

(1) Detergency test part 1 (washing textile clothes designated as neutral detergent)
"Test conditions"
The washing machine is a fully automatic washing machine manufactured by Hitachi, Ltd. (NW-7P5 CP, 7 kg type, water level setting 50 liters, towel 1.5 kg as a load), and tap water (Fujisawa City Waterworks, A soft course (for wool clothing) was set at pH 7.5, total hardness 60 ppm, washing was performed for 9 minutes (weak washing), water rinsing was performed once, and dewatering was performed twice for 1 minute × 2.

  As the contaminated cloth, a wet artificial contaminated cloth (manufactured by the Laundry Science Association) with an artificial sebum soil adhered thereto was mainly used. At this time, for the purpose of averaging the difference in cleaning rate between different production lots, two contaminated cloths with different production lots are prepared, and each of these 5 contaminated cloths (convenient 10 sheets) is used as a towel. Sewed and washed. In addition to this wet artificially contaminated cloth, in some tests, a contaminated cloth with blood attached (EMPA 111), a contaminated cloth with protein cacao (EMPA 112), a contaminated cloth with red wine attached (EMPA 114), and A contaminated cloth (EMPA 116) to which blood, milk and carbon black adhered was used. At this time, 3 sheets of EMPA-contaminated cloth (18 sheets for convenience) were sewn on a towel and washed.

《Calculation of cleaning rate》
The cleaning rate was calculated by the following formula.

Washing rate% = (Whiteness of contaminated cloth after washing−Whiteness of contaminated cloth before washing)
÷ (whiteness of uncontaminated fabric−whiteness of contaminated fabric before washing) × 100
The whiteness was obtained by measuring 10 points on the front and back of each contaminated cloth using a whiteness meter (CR-14, Whiteness Index Color Reader, manufactured by Minolta Co., Ltd.) and averaging the measured values.

<< pH of cleaning agent aqueous solution >>
The pH of the cleaning agent aqueous solution was measured at 25 ° C. with a glass electrode pH meter (manufactured by Horiba, Ltd.) after adding the cleaning agent to the cleaning water. At this time, the pH of the aqueous cleaning solution was determined so that the indicated value was sufficiently stable.

Example 1
50 liters of tap water, 42.5 g of acrylic acid / maleic acid copolymer as organic chelating agent, 5 g of citric acid as organic chelating agent and pH adjusting agent, 16.7 g of sodium bicarbonate as pH adjusting agent, reduced surface tension It consists of each component composition of 2.2 g of partially saponified polyvinyl alcohol as an action and dispersant and 0.3 g of carboxymethyl cellulose as a dispersant, and the detergent concentration is 66.7 g. A washing liquid having 1.33 g / L and a pH of 7.39 was obtained. The washing rate of the wet artificially contaminated cloth and the EMPA contaminated cloth before and after washing when washing with this washing liquid was determined. The results are shown in Table 1.

<< Comparative Example 1 >>
As a comparative example of Example 1, a washing liquid in which 67 ml of a commercially available liquid synthetic detergent was dissolved in 50 liters of tap water at a standard concentration (Acron, detergent concentration 1.34 ml / L, manufactured by Lion Corporation, 23% surfactant) The washing rate of wet artificially contaminated cloth and EMPA contaminated cloth before and after washing was determined when washing was carried out using the contained pH 7.31). The results are shown in Table 1.

《考察》
実施例１は、比較例１に比べ、人口皮脂汚れに対する洗浄力がほぼ同等であることを除き、すべての汚れにおいて明らかに洗浄力が勝っていた。とりわけ、タンパク質であるカカオが付着した汚染布（ＥＭＰＡ１１２）及び血液とミルクとカーボンブラックが付着した汚染布（ＥＭＰＡ１１６）において、その洗浄力の差は２〜３倍であった。

<Discussion>
In Example 1, the detergency was clearly superior to that in Comparative Example 1 except that the detergency against artificial sebum soil was almost the same. In particular, the difference in detergency between the contaminated cloth (EMPA 112) to which cacao, which is a protein, and the contaminated cloth (EMPA 116) to which blood, milk, and carbon black were adhered was 2-3 times.

(2) Detergency test 2 (Bathroom detergent test)
Example 2
To 77.28 g of purified water, 2.5 g of organic chelating agent GLDA · 4Na, 0.2 g of citric acid that is organic chelating agent and pH adjusting agent, and hydroxypropyl that is a dispersant having a surface tension reducing action and a thickening action A total amount of 22.72 g of the detergent composed of 0.02 g of methylcellulose and 20 g of the sodium bicarbonate electrolytic cleaning solution was dissolved to obtain a cleaning solution having a cleaning agent concentration of 29.4 wt% and a pH of 10.

30 cc of this cleaning liquid was put into a beaker, and 5 mg of oleic acid Ca (soap residue) was added thereto and stirred with a stirrer for 30 minutes to observe the state of decomposition and dispersion (soap residue decomposition / dispersion test). The results are shown in Table 2.

Moreover, the cleaning liquid of Example 2 was sprayed on the dirt attached to the upper part of the water line of the bathtub, wiped off after 30 seconds, and the trace was observed (wiping test of sebum dirt). The results are shown in Table 3.

<< Comparative Example 2 >>
As a comparative example of Example 2, decomposition and dispersion of soap residue under the same conditions as Example 2 using a commercially available synthetic detergent for baths (Bath Magiclin, manufactured by Kao Corporation, containing 10% surfactant) A test and a wiping test for sebum soil were conducted. The results are shown in Table 2 and Table 3, respectively.

<< Reference Example 1 >>
As a reference example of Example 2, using a sodium bicarbonate electrolytic cleaning solution (5% aqueous solution of electrolyzed water of 7.5% aqueous solution of sodium bicarbonate), which is an alkaline agent having a pH of 9.8, under the same conditions as in Example 2, Decomposition / dispersion test and sebum dirt wiping test were conducted. The results are shown in Table 2 and Table 3, respectively.

《考察》
実施例２及び比較例２は、参考例１に比べ、石鹸カスの分解・分散力において勝っていた。実施例２及び比較例２が、石鹸糟を完全に分解し溶解させたのに対して、
参考例１では、石鹸糟が撥水し洗浄液の表面において浮いている状態であった。皮
脂汚垢の拭き取りにおいては、実施例２、比較例２、参考例１のどれもが完全に除
去した。

<Discussion>
Example 2 and Comparative Example 2 were superior to Reference Example 1 in the decomposition and dispersion power of soap scum. Whereas Example 2 and Comparative Example 2 completely decomposed and dissolved soap candy,
In Reference Example 1, the soap candy was water repellent and floated on the surface of the cleaning liquid. In wiping off sebum dirt, all of Example 2, Comparative Example 2, and Reference Example 1 were completely removed.

(3) Detergency test # 3 (washing toilet bowl (urine stone))
Example 3
Dispersant with 98.35 g of purified water, 0.85 g of acrylic acid / maleic acid copolymer as organic chelating agent, 0.7 g of citric acid as organic chelating agent and pH adjusting agent, surface tension reducing action and thickening action A total amount of 2.65 g of the detergent composed of 0.1 g of hydroxypropylcellulose as a component was dissolved to obtain a detergent having a detergent concentration of 2.7% by weight and a pH of 4.1.

<< Comparative Example 3 >>
As a comparative example of Example 3, a commercially available toilet detergent (toilet magic phosphorus, manufactured by Kao Corporation, containing 4% surfactant) was used.

  Spray the cleaning agent of Example 3 on the left side from the center of the men's urinal with urine stone, and the synthetic detergent of Comparative Example 3 on the right side from the center. After 1 minute rubbing with a brush, rinse with water, The trace was observed. The results are shown in Table 4.

《考察》
実施例３及び比較例３は、尿石汚れをほぼ完全に除去し、尿石汚れを完全に除去した。

<Discussion>
In Example 3 and Comparative Example 3, urine stone stains were almost completely removed, and urine stone stains were completely removed.

(4) Detergency test 4 (point washing of clothes)
When washing clothes, it is difficult to remove dirt, and it is difficult to remove dirt. Dirty stains on shirts are usually washed after brushing with a high-concentration detergent only on the area. Be taken. The cleaning agent of the present invention does not contain a surfactant, and by blending a high concentration chelating agent, it is possible to obtain a cleaning power equivalent to or higher than a so-called point washing detergent containing a high concentration surfactant. I can do it.

"Test method"
Apply a washing agent for point washing to an artificially contaminated cloth that assumes stains on the collar and a commercially available synthetic detergent for point washing (a product of Kao Corporation, attack point washing, surfactant concentration 52%) for comparison. went.

"Test conditions"
Using a tartometer (stirring type detergency test device, Model TM-4, manufactured by Daiei Kagaku Seiki Seisakusho), tap water with a water temperature of 25 ° C (Fujisawa City Waterworks, pH 7.5, total hardness 60ppm), water volume of 1L, rotation Several 120 rpm, washing 10 minutes, rinsing 3 minutes × 2 times were performed.

The washing liquid of Example 4 was applied to the central part (width about 1 cm) of an artificially contaminated cloth (WFK30D / Soil sebum 5 cm × 5 cm) in which artificial sebum dirt adhered to a polyester base cloth, and washing was performed.

Example 4
Components of 97.90 g of GLDA · 4Na as an organic chelating agent, 2.0 g of citric acid as an organic chelating agent and a pH adjusting agent, and 0.1 g of hydroxypropyl cellulose as a dispersant having a surface tension reducing action and a thickening action A high-concentration cleaning solution having a total amount of 100 g comprising the composition and a pH of 10.3 was obtained.

To 1 liter of water used for “washing” after application, 0.67 g of a cleaning agent mainly containing a chelating agent was added in advance. The composition of the cleaning agent mainly composed of the chelating agent used here is MGDA-3Na 10 g, layered sodium silicate 7.2 g, hydrogen carbonate Na 0.8 g, partially saponified PVA 1.3 g, CMC 0.2 g, protease 0.2 g, sulfite. Na 0.3g, total amount 20g.

<< Comparative Example 4 >>
As a comparative example of Example 4, a commercially available synthetic detergent for point washing (attack point washing, manufactured by Kao Corporation, containing 52% surfactant) was used.

  To 1 liter of water used for “washing” after application, 0.67 g of a commercial powder detergent (manufactured by Kao Corporation / powder attack) was added in advance.

<Discussion>
In all cases, the washing rate was 10% or less in normal washing alone, but a washing rate exceeding 90% was obtained after application of the point washing detergent.

  In Example 4, the dirt on the portion where the cleaning liquid was applied was almost removed.

  In Comparative Example 4, the dirt on the portion where the cleaning liquid was applied was almost removed.

（５）洗浄力試験その５（スチール壁の汚れ）
スチール壁に付いたヤニ汚れを左右二区画に分け、キレート剤を主剤とする洗浄剤と市販の住居用洗浄剤で拭き取り比較する。

(5) Detergency test # 5 (Steel wall dirt)
The dirt on the steel wall is divided into two sections, left and right, and then compared with a cleaning agent based on a chelating agent and a commercial residential cleaning agent.

Example 5
0.9 g of methyl glycine diacetic acid trisodium salt (MGDA-3Na) which is an organic chelating agent,
A cleaning agent having a total amount of 100 g and a pH of 9.80, each composed of 0.17 g of citric acid, which is a chelating agent and pH adjusting agent, and 98.93 g of purified water.

  The cleaning solution was sprayed and immediately wiped with a dry cotton cloth 5 times.

<< Comparative Example 5 >>
As a comparative example in Example 5, a wiping test was conducted in the same manner as in Example 5 with a commercially available residential cleaner (Easy Mypet, manufactured by Kao Corporation, surfactant 0.3%).

<Discussion>
In both Example 5 and Comparative Example 5, the dirt was almost completely removed.

なお、本明細書中に開示している洗浄力試験は、特にことわらない限り本試験条件に則して実施されている。

The detergency test disclosed in the present specification is performed in accordance with the test conditions unless otherwise specified.

<Identification of drugs used>
The followings were used for the drugs used in the present specification.

1. Sodium bicarbonate: E grade (Tokuyama)
2. Polyvinyl alcohol (PVA): POVAL JP-05S (Nippon Vinegar-Poval)
3. Carboxymethylcellulose (CMC): Serogen BSH-12 (Daiichi Kogyo Seiyaku Co., Ltd.)
4). Citric acid (anhydrous): Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
5. Hydroxypropyl methylcellulose (HPMC): Metroz 90SH-400 (manufactured by Shin-Etsu Chemical Co., Ltd.)
6). GLDA-4Na: Cylest CMG-40 (manufactured by Cylest) 40% aqueous solution Acrylic acid / maleic acid copolymer: Socaran CP7 (BASF)
8). HPC: HPC M (Nippon Soda Co., Ltd.)
9, MGDA-3Na: Torriron M (manufactured by BASF)
10. Sodium sulfite (anhydrous): Reagent (manufactured by Wako Pure Chemical Industries)

Claims (12)

A cleaning composition comprising an organic chelating agent as a main cleaning agent and containing no surfactant, wherein the content of the chelating agent is 0.01 wt% to 50 wt% when it is made into an aqueous solution. . The cleaning composition according to claim 1, wherein the chelating agent is a carboxylic acid chelating agent. The cleaning composition according to claim 1 or 2, wherein the content of the dispersant is 0.001 wt% to 5 wt% when the dispersant is contained in an aqueous solution. The detergent composition according to any one of claims 1 to 3, wherein the dispersant is a water-soluble polymer having an action of reducing the surface tension of the detergent aqueous solution. The cleaning composition according to any one of claims 1 to 3, wherein the dispersant is a water-soluble polymer having an action of increasing the viscosity of the cleaning solution. The said dispersing agent is one or a combination of two or more water-soluble polymers having an action of lowering the surface tension of an aqueous cleaning agent solution and an action of increasing the viscosity. The cleaning composition as described. The cleaning composition according to any one of claims 1 to 6, wherein a thickener is added. The cleaning composition according to claim 7, wherein the thickener is an inorganic thickener. The cleaning composition in any one of Claims 1-8 which added the disinfection component. The cleaning composition in any one of Claims 1-9 which added the fragrance | flavor and the coloring agent. The cleaning composition according to any one of claims 1 to 10, wherein the cleaning composition is used for washing animal fibrous clothing, wherein the pH of the cleaning solution having an actual use concentration is adjusted to 6 to 8. The cleaning composition according to claim 11, wherein the actual use concentration is from 0.15 g / L to 15 g / L.