JP2006199723A - Liquid detergent composition for automatic washer and washing method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a liquid detergent composition for an automatic washer, which has a desired pH for an automatic washer, excellent stability of an alkali metal hypochlorite, low-temperature stability, stability of metal ion sequestering power, cleaning properties, especially reattachment prevention properties, finishing properties and scale formation control ability and contains no surfactant, and to provide a washing method using the composition. <P>SOLUTION: The detergent composition comprises, as effective components, (A) 0.1-40% by mass of potassium tripolyphosphate, (B) 0.1-20% by mass of sodium tripolyphosphate. (C) 1-20% by mass of potassium silicate having the molar ratio (SiO<SB>2</SB>/K<SB>2</SB>O) of SiO<SB>2</SB>to K<SB>2</SB>O of 0.5-1 and (D) 0.2-3% by mass of an alkali metal hypochlorite calculated as an effective chlorine amount and water. An aqueous solution of the detergent composition prepared in 0.2% by mass according to JIS Z-8802:1984 has pH≥11 at 25°C. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a liquid detergent composition for an automatic washing machine suitable for washing hard surfaces such as tableware, glass, ceramics, metals, plastics, and more particularly, having a desired pH and an alkali metal hypochlorite salt. Liquid detergent composition for automatic washing machine, which has excellent stability, low-temperature stability, stability of sequestering power, and cleanability, and particularly excellent anti-reattachment performance, finish and scale generation suppression capability, and the same The present invention relates to a washing method using

  Conventionally, automatic dishwashers have been widely used in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like in order to efficiently wash used dishes. Further, not only tableware but also various manufacturing factories, processing factories, etc., automatic washing machines are used for washing instruments, containers, plastic containers used for distribution, and the like.

  As the detergent composition for the automatic dishwasher, for example, as an example not containing phosphate, NaOH or KOH, 2-hydroxyethyliminodiacetate, a copolymer of isoamylene and maleic anhydride is essential. Hard surface cleaning composition containing a hard surface cleaning composition (see Patent Document 1), sodium hydroxide or potassium hydroxide, alkali metal salt of nitrotriacetic acid and a copolymer of isoamylene and maleic anhydride An agent (see Patent Document 2) is disclosed.

Also, potassium silicate 1 to 3 to 40% by weight of potassium tripolyphosphate and 10 to 45% by weight of a mixture of sodium tripolyphosphate 0 to 17% by weight, and the SiO ₂ / K ₂ O molar ratio 0.5 to 1 20% by weight, KOH 0 to 20% by weight, about 6 to 13% by weight of hypochlorous acid alkali salt aqueous solution containing effective chlorine 50% by weight as a mixture with 0.2 to 3% by weight, and water A liquid detergent (see Patent Document 3) with little hydrolysis of alkali metal tripolyphosphate, NaOH or KOH 10-25% by weight, polyacrylate 1-5% by weight, and conductivity 0.1 A liquid detergent composition for an automatic dishwasher composed of a micro-Siemens (20 ° C.) or less water residue, which does not precipitate during storage, and has an excellent detergency and scale adhesion prevention effect (see Patent Document 4) Open It is.

  Further, 1 to 30% by weight of a nonionic surfactant, 1 to 50% by weight of a Ca ion capture chelating agent comprising citrate, zeolite, etc., and an optimum action pH for lipase and pullulan is 8.5 to 10, with respect to soluble starch. Starch, fat and protein soil containing an alkali or alkali-resistant bullase having an α-amylase activity having an optimum action pH in the range of 7 to 9.5 and a pH of a 0.2 wt% aqueous solution of 7 to 10 A detergent composition for an automatic dishwashing machine (see Patent Document 5) having excellent detergency even for composite dirt such as non-ionic surfactant 1 to 30% by weight, Ca ion capture chelating agent 1 to 50 Against complex soils such as starch, fats and oils and protein soils, containing 2% by weight, lipase and alkaline pullulanase, and having a 0.2% by weight aqueous solution pH 7-10 Excellent automatic dishwashing detergent compositions detergency is also disclosed (see Patent Document 6).

Further, 0.5 to 30% by weight of an alkali agent such as one kind or two or more kinds of potassium hydroxide and sodium hydroxide, and an acrylic acid and / or maleic acid polymer substance 0.5 having a metal ion scavenging ability Washing for automatic dishwashers with excellent washing and bleaching effects, containing ~ 30% by weight and bleaching agents such as sodium hypochlorite 0.1 to 10% by weight, without impairing the appearance of dishes An agent composition is disclosed (see Patent Document 7).
JP 58-198598 A JP 59-227997 JP-B-2-29720 JP-A-4-15299 Japanese Patent Publication No. 6-99714 Japanese Patent Publication No. 6-99715 JP-A-8-199194

  However, these cleaning compositions each satisfy only a specific performance, and it is the actual situation that comprehensively satisfactory products are not obtained. In consideration of continuous supply of the cleaning agent to the automatic cleaning machine, it is preferable to use a liquid cleaning agent for handling, but depending on the type of the surfactant, each component of the cleaning composition may be Some cannot be maintained in a uniformly dissolved state and are difficult to prepare as liquid detergents.

  Therefore, the development of a liquid detergent composition that has excellent cleaning performance against various types of food stains even without a surfactant, especially with anti-redeposition performance, finish, and scale formation suppression capability is strong. It is desired.

  The present invention has been made in view of such circumstances, has a desired pH for an automatic washing machine, stability of alkali metal hypochlorite, low temperature stability, stability of sequestering power. Providing a liquid detergent composition for automatic washing machines that does not contain surfactants and has excellent detergency, in particular, anti-redeposition performance, finish, and scale generation suppression ability, and a cleaning method using the same For that purpose.

In order to achieve the above object, the present invention is a cleaning composition containing the following components (A) to (D) as active ingredients and water, and is prepared according to JIS Z-8802: 1984. A liquid detergent composition for an automatic washing machine in which the pH at 25 ° C. of a 0.2% by mass aqueous solution of the above-described detergent composition is 11 or more is a first gist.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount.

Moreover, this invention is the cleaning composition which contains the following (A)-(E) component as an active ingredient, and contains water, Comprising: The said cleaning composition prepared according to JISZ-8802: 1984 The second gist of the present invention is a liquid detergent composition for automatic washing machines in which a 0.2 mass% aqueous solution of the product has a pH of 11 or more at 25 ° C.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount.
(E) 1-20 mass% of potassium hydroxide.

Furthermore, this invention is the cleaning composition which contains the following (A)-(F) component as an active ingredient, and contains water, Comprising: The said cleaning composition prepared according to JISZ-8802: 1984 A third aspect of the present invention is a liquid detergent composition for an automatic washing machine in which a 0.2 mass% aqueous solution of the product has a pH of 11 or more at 25 ° C.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount.
(E) 1-20 mass% of potassium hydroxide.
(F) 0.1-5 mass% of polymer electrolyte polymer.

  In the present invention, among the liquid cleaning compositions for automatic washing machines according to any one of the first to third aspects, in particular, the total amount of the active ingredients is 10 to 50% by mass. And a liquid cleaning composition for an automatic cleaning machine according to any one of the first to fourth aspects described above as an aqueous solution of 0.1 to 0.5% by mass of an automatic cleaning machine. The fifth gist is a cleaning method for cleaning an object to be cleaned.

  That is, since the cleaning composition of the present invention has the above-mentioned special composition, in a specific pH range of pH 11 or higher, the stability of alkali metal hypochlorite, low temperature stability, sequestering power Excellent stability and cleanability, especially excellent anti-redeposition performance, finish and scale generation inhibiting ability.

  In addition, compared to conventional cleaning compositions, it has excellent cleaning performance against various food stains even without a surfactant, has excellent anti-redeposition performance, and scale formation suppression capability, Even when a molecular electrolyte polymer is blended, the stability of the desired alkali metal hypochlorite can be ensured.

  Therefore, this cleaning composition is suitable for cleaning hard surfaces such as glass, ceramics, metals and plastics. Moreover, it can be used not only for tableware but also as an automatic washing machine for washing instruments and containers in various manufacturing factories, processing factories, and plastic containers used for distribution. In addition, it can also be preferably used for cleaning hard surfaces such as tiles and floors in food factories and food processing factories, cleaning containers such as glass bottles and beer bottles for beverages, and cleaning metal surfaces. In particular, it is suitable for use in automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias and the like.

  Next, the best mode for carrying out the present invention will be described in detail.

First, the liquid detergent composition for automatic washing machines of the present invention (hereinafter referred to as “the present detergent composition”) comprises (A) potassium tripolyphosphate, (B) sodium tripolyphosphate, (C) SiO ₂ and K ₂ O. In addition to containing four components of potassium silicate having a molar ratio (SiO ₂ / K ₂ O) of 0.5 to 1 and (D) alkali metal hypochlorite as active ingredients, it also contains water. . Moreover, this cleaning composition can contain (E) potassium hydroxide as an active ingredient as needed with said (A)-(D). Furthermore, (F) polyelectrolyte polymer can be contained as an active ingredient with said (A)-(E) as needed.

  As potassium tripolyphosphate that is the component (A), potassium tripolyphosphate that is commonly used, such as powder, granules, and granules, can be used. The said potassium tripolyphosphate is mix | blended in the range of 0.1-40 mass% with respect to this cleaning composition whole. If the blending amount is less than 0.1% by mass, the low-temperature stability is inferior, and if it exceeds 40% by mass, desired performance cannot be obtained from the balance with other components. In particular, potassium tripolyphosphate can increase the solubility of sodium tripolyphosphate by using it together with sodium tripolyphosphate which is the component (B), so that sodium tripolyphosphate can be blended at a high concentration. And when said potassium tripolyphosphate is used in a small amount of less than 3% by mass, it has excellent detergency and finish, and in particular, appearance (color change) during storage and hypochlorous acid used as component (D) The stability of sodium acid is remarkably excellent, which is preferable.

  As the sodium tripolyphosphate that is the component (B), commonly used sodium tripolyphosphate in the form of powder, granules, granules or the like can be used. The said sodium tripolyphosphate is mix | blended in the range of 0.1-20 mass% with respect to this cleaning composition whole. If the blending amount exceeds 20% by mass, desired performance cannot be obtained from the balance with other components. Especially, it is preferable that it is the range of 0.1-15 mass% from the balance with another component.

  In addition, industrially produced tripolyphosphates such as potassium tripolyphosphate and sodium tripolyphosphate usually contain orthophosphate, pyrophosphate, highly condensed phosphate, etc., and these by-products are In order to affect the low temperature stability and discoloration of the cleaning composition, the (A) component and the (B) component of the cleaning composition are those in which the amount of these by-products is kept as low as possible. It is desirable to use it.

Further, as potassium silicate having a molar ratio of SiO ₂ and K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 as the component (C), commercially available potassium metasilicate and orthosilicate are used. be able to. Alternatively, by mixing silicon dioxide (SiO ₂ ) and potassium hydroxide (KOH) in advance, or by adding these two components together with other components as appropriate, the molar ratio of SiO ₂ and K ₂ O is as described above. Any potassium silicate that falls within the range may be prepared.

  The potassium silicate which is said (C) component is mix | blended in 1-20 mass% with respect to this cleaning composition whole. When the blending amount is less than 1% by mass, the stability of the alkali metal hypochlorite as the component (D) is poor, and the desired cleaning power against tea astringent stains cannot be obtained. On the other hand, even when blending in excess of 20% by mass, the stability of the alkali metal hypochlorite is poor and the low temperature stability cannot be obtained. Especially, it is preferable that it is the range of 1-10 mass% from the balance with another component.

  Examples of the alkali metal hypochlorite as the component (D) include commonly used 12% by mass sodium hypochlorite, 6% by mass sodium hypochlorite and the like. A concentration of sodium hypochlorite is preferred. And 0.2-3 mass% alkali metal hypochlorite is mix | blended with respect to the whole this cleaning composition as an effective chlorine amount. Especially, it is preferable that it is the range of 0.5-1.5 mass% from the balance with another component.

  And as potassium hydroxide which is the said (E) component, potassium hydroxide of liquid form, a granular form, granule shape, flake shape, etc. which are used normally can be used. The said potassium hydroxide is an active ingredient which can be arbitrarily mix | blended as needed, and can be mix | blended in the range of 1-20 mass% with respect to this cleaning agent composition whole. If the blending amount exceeds 20% by mass, the desired performance is poor from the balance with other components. Especially, it is preferable that it is the range of 4-10 mass% from the balance with another component.

  Furthermore, the polyelectrolyte polymer which is the component (F) includes polyacrylic acid or its alkali metal salt, methyl vinyl ether and maleic acid copolymer or its alkali metal salt, and the like. Polymers or alkali metal salts thereof, such as copolymers of olefins having 5 carbon atoms and maleic acid or alkali metal salts thereof, copolymers of polystyrene sulfonic acid and maleic acid or alkali metal salts thereof, acrylic acid and the like Examples thereof include a copolymer with 2-hydroxy-3-allyloxypropanesulfonic acid or an alkali metal salt thereof. These alkali metal salts may be partially neutralized products.

  The average molecular weight of the polymer electrolyte polymer as the component (F) is 1,000 to 60,000 in the case of polyacrylic acid or an alkali metal salt thereof, for example, from the viewpoint of the ability to suppress scale adhesion. Preferably, it is 2,000-15,000. Moreover, when it is a copolymer of acrylic acid and maleic acid or its alkali metal salt, it is preferable that it is 30,000-150,000, More preferably, it is 40,000-80,000.

  The polymer electrolyte polymer may be used alone or in combination of two or more. And this thing is an active ingredient which can be arbitrarily mix | blended as needed, and is 0.1-5 mass% with respect to this cleaning agent composition whole, Preferably it is the range of 0.5-3 mass%. Can be blended. When the blending amount is less than 0.1% by mass, the effect of improving the cleaning performance, finish performance, and scale adhesion suppressing ability of the article to be cleaned is not sufficient. On the other hand, when it exceeds 5 mass%, it is unpreferable from the point of balance with other components, and economical efficiency. In addition, the residual monomer amount of the polymer electrolyte polymer is preferably 0.5% by mass or less, more preferably 0.1% by mass or less from the viewpoint of storage stability of the alkali metal hypochlorite. preferable.

  And the sum total of the active ingredient amount which added (E) component or (E) component, and (F) component to the said (A)-(D) component or this is 10 to the whole this cleaning composition. It is preferably 50% by mass. That is, if it is less than 10% by mass, the cleaning composition will not be compact, requiring a large storage space, and there is a possibility that the cleaning power against various types of dirt and the ability to suppress scale formation will be poor. Because there is. On the other hand, when it exceeds 50 mass%, the hydrolysis of phosphate is promoted and the low-temperature stability may be poor.

  And this cleaning composition is prepared as a liquid with water. Examples of the water include pure water, ion exchange water, soft water, distilled water, and tap water. These may be used alone or in combination of two or more. Of these, tap water and ion-exchanged water are preferably used from the viewpoint of economy and storage stability.

  The “water” is the sum of water contained in the form of crystal water or aqueous solution derived from each component constituting the cleaning composition of the present invention and water added from the outside, and the composition. The remaining mass% excluding the above active ingredients and other optional ingredients added as appropriate is blended so that the whole becomes 100%.

  Examples of the optional components added as appropriate include pH adjusters, fragrances, metal corrosion inhibitors, bactericides, deodorants, and antistatic agents.

  The present cleaning composition obtained by using each of the above components, according to JIS Z-8802: 1984, if the pH of the aqueous solution of the cleaning composition prepared to 0.2% by mass at 25 ° C. is not 11 or more. Don't be. That is, the present cleaning composition is characterized by being excellent in oil and fat dirt and protein dirt cleaning performance at a pH of 11 or more, and excellent in stability of sodium hypochlorite.

  Thus, the present detergent composition is a liquid detergent composition having a pH of 11 or more, and is excellent in stability of alkali metal hypochlorite, low temperature stability, stability of sequestering power, and detergency. In particular, it is excellent in anti-reattachment performance, finish, and scale generation suppression ability.

  In addition, compared to conventional cleaning compositions, it has excellent cleaning performance against various food stains even without a surfactant, has excellent anti-redeposition performance, and scale formation suppression capability, Even when a molecular electrolyte polymer is blended, the stability of the desired alkali metal hypochlorite can be ensured.

  Therefore, this cleaning composition is suitable for cleaning hard surfaces such as glass, ceramics, metals and plastics. Moreover, it can be used not only for tableware but also as an automatic washing machine for washing instruments and containers in various manufacturing factories, processing factories, and plastic containers used for distribution. In addition, it can also be preferably used for cleaning hard surfaces such as tiles and floors in food factories and food processing factories, cleaning containers such as glass bottles and beer bottles for beverages, and cleaning metal surfaces. In particular, it is suitable for use in automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias and the like.

  In addition, this cleaning composition is automatically used as a 0.15 to 0.5 mass% cleaning solution in consideration of the type of dirt, the amount (degree) of dirt, the quality of tap water used for cleaning, and the like. By supplying to the washing machine, an excellent finishing effect can be obtained particularly for tableware and cooking utensils.

  Next, examples will be described together with comparative examples.

[Examples 1 to 32, Comparative Examples 1 to 15]
A liquid detergent composition for an automatic washing machine having the composition shown in Table 1 to Table 12 below is prepared, and its pH, stability of sodium hypochlorite, low temperature stability, stability of sequestering power, washing power Evaluation was made on 8 items of anti-reattachment performance, finish, and ability to suppress scale formation. The results are also shown in Tables 1 to 12 below. In addition, the test method and evaluation method of each item are as shown below. “Water” in the table is the sum of water contained in the form of crystal water or aqueous solution derived from various components constituting the liquid detergent composition and water added from the outside, and the entire detergent composition Is shown as a balance so as to be 100% by mass.

  The details of various components used in Tables 1 to 12 below and their effective pure content (% by mass) are as follows, and the values in the table are shown in terms of 100% by mass effective net content. It is a thing.

Polymer electrolyte polymer 1 (F component):
Sodium polyacrylate (45% pure, average molecular weight 4,500)
Product name: Accusol 445N, manufactured by Rohm and Haas, polyelectrolyte polymer 2 (component F):
Sodium polyacrylate (45% pure, average molecular weight 8,000)
Product name: Socaran 30CL, manufactured by BASF, polyelectrolyte polymer 3 (component F):
Sodium polyacrylate (45% pure, average molecular weight 4,000)
Product name: Socaran 25CL, manufactured by BASF, polyelectrolyte polymer 4 (component F):
Sodium polyacrylate (43% pure, average molecular weight 2,000)
Product name: Aron A-210, manufactured by Toagosei Co., Ltd., polymer electrolyte polymer 5 (component F):
Sodium salt of acrylic acid maleic acid copolymer (pure content 35%, average molecular weight 40,000)
Product name: Accusol 505N, manufactured by Rohm and Haas, polyelectrolyte polymer 6 (component F):
Sodium poly-α-hydroxypolyacrylate (pure content 30%, average molecular weight 10,000 to 14,000)
Product name: Pale Black 1200, manufactured by Nippon Peroxide Co., Ltd. Polymer electrolyte polymer 7 (component F):
2-hydroxy-3-allyloxypropanesulfonic acid sodium acrylate (pure content 50%, average molecular weight 3,000)
Product name: Aquaric GL246, manufactured by Nippon Shokubai Co., Ltd./Polyelectrolyte polymer 8 (component F):
2-hydroxy-3-allyloxypropanesulfonic acid sodium acrylate (pure content 50%, average molecular weight 6,000)
Product name: Aquaric GL366, manufactured by Nippon Shokubai Co., Ltd.

[PH]
-Test method According to JIS Z-8802: 1984, pH at 25 degreeC of the aqueous solution of the detergent composition prepared to 0.2 mass% was measured, and the following evaluation criteria evaluated.

-Evaluation criteria (circle): pH is 11 or more.
X: pH is less than 11.

[Stability of sodium hypochlorite]
Test Method: The test detergent composition is placed in a 250 ml polypropylene container, stored at 38 ° C. for 1 month, the remaining effective chlorine is measured by the following method, and the effective chlorine amount immediately after preparation is 100 (% ) As the residual ratio (%) of available chlorine, and the stability of sodium hypochlorite was evaluated according to the following evaluation criteria.

・ Available chlorine measurement method Take 3 g of the test sample in a 200 ml Erlenmeyer flask, add 15 ml of 10% by weight potassium iodide iodide solution and 10 ml of (1 + 1) sulfuric acid, and leave it in a cool dark place for 3 minutes to release iodine. The solution is titrated with 0.1N sodium thiosulfate normal solution until the yellow color of iodine disappears and calculated from the following formula.

Evaluation criteria A: Residual rate is 70% or more.
○: Residual rate is 50% or more and less than 70%.
Δ: Residual rate is 30% or more and less than 50%.
X: Residual rate is less than 30%.

[Low temperature stability]
・ Test method The test detergent composition is placed in a 250 ml polypropylene container, and the liquid temperature is cooled and heated so as to draw a cycle of + 5 ° C. to −5 ° C. in 24 hours. The presence or absence of crystal precipitation was examined, and the low-temperature stability was evaluated according to the following evaluation criteria.

Evaluation criteria A: No precipitation was observed even after 100 days.
○: Precipitation was observed between the 60th day and the 99th day.
Δ: Precipitation was observed between the 30th and 59th days.
X: Precipitation was recognized by the 29th day.

[Stability of sequestering power]
The test detergent composition was placed in a 250 ml polypropylene container, stored at 38 ° C. for 3 months, the remaining sequestering force was measured by the following method, and the sequestering force immediately after preparation was 100 (% ) As a residual ratio (%) of the sequestering force, and the stability was evaluated according to the following evaluation criteria.

・ Method for measuring sequestering force 60 g of a 0.15% solution of the test detergent composition was placed in a 100 ml beaker, 1 ml of pH buffer solution, Eriochrome Black T indicator and sodium thiosulfate were added. And automatically titrating with a calcium chloride solution having a known concentration, and calculating from the following equation.

Evaluation criteria A: Residual rate is 70% or more.
○: Residual rate is 50% or more and less than 70%.
Δ: Residual rate is 30% or more and less than 50%.
X: Residual rate is less than 30%.

[Detergency]
Test Method The prepared cleaning composition was charged into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. And the ceramic dish which is the following to-be-cleaned object was wash | cleaned as 1 set of 10 sheets, and the washing | cleaning performance was evaluated by the following evaluation criteria. In addition, beef tallow, fine powder, curry, egg yolk and tea astringent were prepared as dirt, and a detergency test was performed on each dirt.

* Operating condition Detergent concentration: 0.2% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70-80 mg / L (as CaCO ₃ )
Beef tallow dirt: Refined beef tallow was used.
Upper fresh powder stain: Water 75 was added to upper fresh powder 25 and boiled for 20 minutes while stirring in the middle to use a paste.
Curry stain: A commercially available retort curry (Bon Curry (registered trademark), manufactured by Otsuka Pharmaceutical Co., Ltd.) was used.
Egg stain: Only egg yolk was used, especially with good mixing.
Tea astringent stain: 50 g powdered tea in 1 L hot water and boiled for 1 hour was used.
Object to be cleaned: A ceramic dish having a diameter of 10 cm was attached with the above-mentioned dirt so as to be 4 g / sheet and dried at room temperature for 1 hour. As for the tea astringent stain, the surface of the ceramic dish was scratched with # 180 sandpaper, 10 g of the tea astringent stain was placed on the surface, put in a dryer at 100 ° C., and the moisture was completely removed.

・ Evaluation criteria A: Removal of dirt of 90% or more.
○: Dirt removal of 70% or more and less than 90%.
Δ: Dirt removal of 50% or more and less than 70%.
X: Dirt removal of less than 50%.

(Reattachment prevention performance)
·Test method
A washing rack in which 30 g of salad oil colored with oil red (Sudan IV) as dirt is put into a washing tank of a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and a clean melamine dish is placed. After setting in the automatic dishwasher and operating under the following operating conditions using the test detergent composition, visually check the degree of dirt adhered to a clean melamine dish, according to the following evaluation criteria: evaluated.

* Operating condition Detergent concentration: 0.2% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70-80 mg / L (as CaCO ₃ )

・ Evaluation criteria A: No dirt adhered to clean dishes.
○: Dirt is hardly adhered to a clean dish.
Δ: Dirt adheres to a clean dish.
X: Dirt adheres considerably to a clean dish.

[Finishability]
Test Method The prepared cleaning composition was charged into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following conditions. And the glass cup which is a to-be-cleaned object shown later was wash | cleaned as 1 set, and the finished performance after washing | cleaning was evaluated by the following evaluation criteria.

* Operating condition Detergent concentration: 0.2% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing 15 seconds)
Of use water hardness (as CaCO ₃₎ 70~80mg / L
Object to be washed: Milk was poured into an 8 ounce (225 ml) glass cup (manufactured by Sasaki Glass Co., Ltd.) and left for 5 minutes. Next, after discarding the milk, it was air-dried for 30 minutes without rinsing with water.

・ Evaluation criteria A: No water spots are seen.
○: 1 to 2 water spots are seen.
Δ: 3 to 5 water spots are seen.
X: Six or more water spots are seen.

[Scale generation suppression ability]
Test method Using artificial hard water (total hardness: 250 mg / L as CaCO ₃ ), the cleaning composition is diluted to 0.05% by mass, and 50 ml is poured into a colorimetric tube having a capacity of 100 ml, and then at 60 ° C. for 24 hours. After being held, the amount of scale produced was visually evaluated according to the following evaluation criteria.

Evaluation criteria A: No scale was generated.
○: There was almost no scale generation.
Δ: Scale was generated.
X: Scale adhesion was remarkable.

  From the above results, it can be seen that all of the example products exhibit excellent characteristics in all the evaluation items.

  The appearance (color change) of the test detergent composition placed in a 250 ml polypropylene container and placed at a constant temperature of 37 ° C. for 3 months was observed. In the products 1, 4, 5 and 6, no color change occurred, but in the other products, a slight color change was observed.

  Further, regarding the stability of the sodium hypochlorite, the stability after 3 months was confirmed, and among the test detergent compositions, those of Examples 1, 4, 5 and 6 were stable. However, a slight decrease in stability was observed in the other cases.

  In other words, when the blending amount of potassium tripolyphosphate is used in a small range of less than 3% by mass, the appearance (change in color) and the stability of sodium hypochlorite are particularly excellent during storage. I found out that

Claims (5)

A cleaning composition containing the following components (A) to (D) as active ingredients and water: 0.2 mass of the cleaning composition prepared according to JIS Z-8802: 1984 A liquid detergent composition for an automatic washing machine, wherein the pH of a 25% aqueous solution is 11 or more at 25 ° C.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount. A cleaning composition containing the following components (A) to (E) as active ingredients and water: 0.2 mass of the cleaning composition prepared according to JIS Z-8802: 1984 A liquid detergent composition for an automatic washing machine, wherein the pH of a 25% aqueous solution is 11 or more at 25 ° C.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount.
(E) 1-20 mass% of potassium hydroxide. A cleaning composition containing the following components (A) to (F) as active ingredients and water: 0.2 mass of the cleaning composition prepared according to JIS Z-8802: 1984 A liquid detergent composition for an automatic washing machine, wherein the pH of a 25% aqueous solution is 11 or more at 25 ° C.
(A) 0.1 to 40% by mass of potassium tripolyphosphate.
(B) Sodium tripolyphosphate 0.1 to 20% by mass.
(C) Potassium silicate having a molar ratio of SiO ₂ to K ₂ O (SiO ₂ / K ₂ O) of 0.5 to 1 is 1 to 20% by mass.
(D) 0.2-3 mass% with an alkali metal hypochlorite as an effective chlorine amount.
(E) 1-20 mass% of potassium hydroxide.
(F) 0.1-5 mass% of polymer electrolyte polymer.   4. The liquid cleaning composition for an automatic cleaning machine according to claim 1, wherein the total amount of the active ingredients is 10 to 50% by mass.   The liquid cleaning composition for an automatic cleaning machine according to any one of claims 1 to 4 is used as an aqueous cleaning agent solution of 0.1 to 0.5 mass%, and an object to be cleaned is cleaned in the automatic cleaning machine. A cleaning method comprising: