JP2009242643A - Liquid detergent composition for automatic dishwasher - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent liquid detergent composition for an automatic dishwasher which does not contain a surfactant, is excellent in various performances such as stability of sodium hypochlorite and stability of metal ion sequestering capability, is specifically excellent in low-temperature stability and high-temperature stability, and also does not affect a glass surface. <P>SOLUTION: The liquid detergent composition for the automatic dishwasher contains, as active ingredients, sodium tripolyphosphate (A) of 2 to 13 mass%, sodium silicate (B) of 1 to 20 mass%, potassium hydroxide (C) of 0.1 to 20 mass%, a hypochlorous acid alkalimetal salt (D) of 0.2 to 3 mass% as an active chlorine amount and a polymer electrolyte polymer (E) of 0.1 to 5 mass%, and also contains water (F), wherein the total amount of the above active ingredient amounts is 10 to 50 mass% of the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition for an automatic dishwasher suitable for cleaning hard surfaces such as tableware, glass, ceramics, metal, and plastic.

  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.

Examples of the detergent composition for the automatic dishwashing machine and the automatic washing machine include, for example, 10 to 45% by weight of a mixture of 3 to 40% by weight of potassium tripolyphosphate and 0 to 17% by weight of sodium tripolyphosphate, SiO ₂ / K. ₂ O molar ratio of 1 to 20% by weight of 0.5-1 potassium silicate, KOH0～20 wt%, hypochlorous acid alkali salt aqueous solution containing available chlorine of from about 6-13% by weight available chlorine 0 A liquid detergent (see Patent Document 1) consisting of 50% by weight of a mixture of 2 to 3% by weight and water and less hydrolysis of alkali metal tripolyphosphate, or 10 to 25% by weight of NaOH or KOH , Composed of 1 to 5% by weight of polyacrylate, and the remainder of water with an electrical conductivity of 0.1 micro-dimens (20 ° C.) or less, no precipitation occurs during storage, and excellent detergency and scale adhesion prevention effect Automatic dishwashing liquid detergent composition (see Patent Document 2) are disclosed.

  Further, the starchy substance contains 1 to 30% by weight of a nonionic surfactant, 1 to 50% by weight of a Ca ion capture chelating agent, lipase and a predetermined pullulanase, and a 0.2% by weight aqueous solution has a pH of 7 to 10. In addition, a detergent composition for an automatic dishwashing machine having excellent cleaning power against complex dirt such as oil and fat and protein dirt has been disclosed (see Patent Documents 3 and 4).

  Furthermore, 0.5 to 30% by weight of an alkali agent such as potassium hydroxide and sodium hydroxide, 0.5 to 30% by weight of an acrylic acid and / or maleic acid polymer substance having a metal ion scavenging ability, Disclosed is a detergent composition for an automatic dishwasher that contains 0.1 to 10% by weight of a bleaching agent such as sodium chlorite and does not impair the appearance of dishware, and has an excellent cleaning effect and bleaching effect. (See Patent Document 5).

Also, as an active ingredient, potassium tripolyphosphate 0.1 to 40 wt%, of sodium tripolyphosphate 0.1 to 20 mass%, SiO ₂ and K ₂ O molar ratio (SiO ₂ / K ₂ O) is 0.5 1 to 20% by mass of potassium silicate, 0.2 to 3% by mass of an alkali metal hypochlorite salt as an effective chlorine content, and a water-containing cleaning composition. The pH of the 2% by weight aqueous solution is 11 or more, and the stability of the alkali metal hypochlorite, the stability at low temperature, the stability of the sequestering power, and the detergency are particularly excellent. A liquid detergent composition for an automatic washer that does not contain a surfactant and has an excellent ability to suppress scale formation, and a washing method using the same have been disclosed (see Patent Document 6).
JP-B-2-29720 JP-A-4-15299 Japanese Patent Publication No. 6-99714 Japanese Patent Publication No. 6-99715 JP-A-8-199194 JP 2006-199723 A

  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.

  In addition, even when the composition does not contain a surfactant, the storage stability of the composition is still particularly important when preparing a liquid detergent composition that has anti-redeposition performance, finish, and scale formation suppression performance. It is difficult to maintain the properties, and it is difficult to obtain a stable product in both a low temperature range and a high temperature range. Moreover, those containing no surfactant and containing an alkali metal hypochlorite also have a problem that they are easily affected by discoloration, damage, etc. on the glass surface.

  The present invention has been made in view of such circumstances, and although it does not contain a surfactant, the stability of sodium hypochlorite, the stability of the sequestering power, the cleaning performance, and the anti-redeposition prevention The objective is to provide an excellent liquid detergent composition for an automatic dishwasher that is excellent in performance, finish, and scale generation inhibiting ability, in particular, low temperature stability and high temperature stability, and has no effect on the glass surface. To do.

In order to achieve the above object, the present invention contains the following components (A) to (E) as active ingredients and (F) water, and the total amount of the active ingredients is in the whole composition. A liquid detergent composition for an automatic dishwasher that is 10 to 50% by mass is a first gist.
(A) Sodium tripolyphosphate 2 to 13% by mass
(B) Sodium silicate 1-20 mass%
(C) Potassium hydroxide 0.1-20 mass%
(D) 0.2-3 mass% with hypochlorite alkali metal salt as effective chlorine content
(E) 0.1-5% by mass of polymer electrolyte polymer

  In addition, the present invention provides a liquid detergent composition for an automatic dishwasher, in which (B ′) 0.1-20% by mass of potassium silicate is further contained as an active ingredient. In summary, for an automatic dishwashing machine further containing, as an active ingredient, at least one of (A ′) 0.1 to 20% by mass of potassium tripolyphosphate and (C ′) 0.1 to 5% by mass of sodium hydroxide The liquid detergent composition is a third aspect.

  Furthermore, the present invention has a pH of 0.2% by weight aqueous solution obtained by diluting the above-mentioned liquid detergent composition for automatic washing machine (JIS Z-8802: 1984 “pH measurement method”). A liquid detergent composition for an automatic dishwasher set to 11 or more at 25 ° C. is a fourth gist.

  That is, since the liquid detergent composition for automatic dishwashers of the present invention (hereinafter referred to as “the present detergent composition”) has the above-mentioned special composition, the stability of alkali metal hypochlorite, metal It has excellent properties in terms of stability of ion sequestering power, cleanability, anti-reattachment performance, finish, and scale generation suppression ability. Moreover, the conventional composition of a type not containing a surfactant has a problem that the glass surface is likely to be affected by discoloration, damage, etc., but the present invention has such a problem. It is also excellent in that no occurs.

  In addition, the cleaning composition has excellent storage stability at low temperatures, and even when stored at high temperatures, decomposition of sodium hypochlorite is minimized, and causes of scale and cleaning Since the ability to sequester metal ions contained in tap water, which causes a reduction in force, is stable over time, the same performance as immediately after production can be maintained over a long period of time. For this reason, even if the storage period and storage conditions are different, the detergency, finish of tableware, bleaching power, and scale suppression effect can always be exhibited.

  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 cleaning composition of the present invention comprises (A) sodium tripolyphosphate, (B) sodium silicate, (C) potassium hydroxide, (D) alkali metal hypochlorite, (E) high It contains a molecular electrolyte polymer and (F) water.

  Moreover, this cleaning composition can contain (B ') potassium silicate as an active ingredient with said (A)-(E) as needed. Alternatively, at least one of (A ′) potassium tripolyphosphate and (C ′) sodium hydroxide can be contained.

  The component (A) sodium tripolyphosphate is usually available as an anhydride or hydrate.

  And said (A) component is mix | blended in 2-13 mass% in this cleaning composition. If the amount is less than 2% by mass, the cleaning performance and the scale formation inhibiting performance are lacking. If the amount exceeds 13% by mass, separation and precipitation are likely to occur due to balance with other components, resulting in low-temperature stability. It will be scarce.

The sodium silicate as the component (B) is a sodium silicate aqueous solution having a molar ratio of SiO ₂ to Na ₂ O (SiO ₂ : Na ₂ O) of 1: _{2 to} 3.8: 1, or powdery , Granular and crystalline sodium metasilicate, sodium orthosilicate and other anhydrides and hydrates are available.

  The said (B) component is mix | blended in 1-20 mass% in this cleaning composition. If it is less than 1% by mass, the metal ion sequestering performance is poor from the balance with the component (A), and the cleaning performance is poor. Moreover, when it mix | blends exceeding 20 mass%, it will become easy to produce isolation | separation and precipitation, and low temperature stability and high temperature stability will fall.

  Moreover, the potassium hydroxide of the above component (C) is usually available as 48 mass% liquid, powder and granule, and liquid is preferably used from the viewpoint of workability.

  The said (C) component is mix | blended in the range of 0.1-20 mass% in this cleaning composition. If it is less than 0.1% by mass, the low-temperature stability, the cleaning performance, and the anti-reattachment performance of dirt will be poor, and in particular, the cleaning performance for protein (egg yolk) dirt will be poor. Moreover, when it mixes exceeding 20 mass%, while it becomes scarce in scale production | generation suppression ability, the influence with respect to a glass surface becomes strong and becomes unpreferable.

  As the alkali metal hypochlorite of the component (D), sodium hypochlorite is preferably used, and is usually supplied as an aqueous solution having an effective chlorine content of 6% by mass or 12% by mass. Can be used.

  The said (D) component is mix | blended in the range of 0.2-3 mass% as an effective chlorine amount in this cleaning composition. When the effective chlorine content is less than 0.2% by mass, the washing performance for protein stains (egg yolk) is poor and the bleaching power for tea astringency is lacking. Moreover, when mix | blending exceeding 3 mass%, while becoming low-temperature stability and the stability of a hypochlorite alkali metal salt, it becomes a thing with a strong chlorine smell, and is not practical.

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

  And the average molecular weight of the polymer electrolyte polymer which is said (E) component is 1,000-60,000 in the point of scale adhesion suppression performance, for example in polyacrylic acid or its alkali metal salt etc. 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 component (E) may be used alone or in combination of two or more. And this thing is mix | blended with 0.1-5 mass% with respect to this cleaning composition whole, Preferably it mix | blends in 0.5-3 mass%. If the blending amount is less than 0.1% by mass, the effect of improving the cleaning performance, finish performance and scale adhesion inhibiting ability of the object to be cleaned is insufficient, and if it exceeds 5% by mass, the balance with other components and economy From the point of sex, it is easy to produce a malfunction. 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.

The potassium silicate (B ′), which is an optional active ingredient that can be used together with the essential active ingredients (A) to (E), is a molar ratio of SiO ₂ to K ₂ O (SiO ₂ : K ₂ O) as an aqueous potassium silicate solution of 1: _{2 to} 3.7: 1, or as an anhydrous or hydrated powder, granular or crystalline potassium silicate, potassium metasilicate, or potassium orthosilicate It is available.

  The said (B ') component can be mix | blended in the range of 0.1-20 mass% in this cleaning composition. When it exceeds 20% by mass, the scale formation inhibiting ability and the stability of sodium hypochlorite are poor, and the influence on the glass surface increases, which is not preferable.

  Similarly, potassium tripolyphosphate (A ′), which is also an optional active ingredient, is usually available as an anhydride or hydrate.

  The component (A ′) can be blended in the range of 0.1 to 20% by mass in the present cleaning composition. When it exceeds 20% by mass, the high temperature stability and sodium hypochlorite stability are poor, and the low temperature stability is poor.

  Similarly, sodium hydroxide of (C ′), which is also an optional active ingredient, is usually available as 25% by mass or 48% by mass of liquid, powder, granule and flakes.

  The component (C ′) can be blended in the range of 0.1 to 5% by mass in the present cleaning composition. If it exceeds 5% by mass, it will have poor scale formation suppression performance and sodium hypochlorite stability, in particular, low temperature stability and high temperature stability, and further influence on the glass surface. Increases and becomes undesirable.

  The components (A) to (E), or the component (B ′) or at least one of the components (A ′) and (C ′), or (B ′), (A ′), (C ′) ) The total amount of the active ingredients added with the respective components must be set to 10 to 50% by mass with respect to the entire cleaning composition. That is, if it is less than 10% by mass, the cleaning composition is not compact, and not only a large storage space is required, but also the cleaning performance against various stains and the scale generation suppression performance are poor, which is not suitable. On the other hand, if it exceeds 50% by mass, hydrolysis of the phosphate is promoted and the low-temperature stability is poor, which is also unsuitable.

  And this cleaning composition is prepared as a liquid with the water which is (F) component. 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 viewpoints 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 dyes, fragrances, pH adjusters, metal corrosion inhibitors, bactericides, deodorants, and antistatic agents.

  According to JISZ-8802: 1984, the present cleaning composition obtained using each of the above components has a pH of 11 or more at 25 ° C. of an aqueous solution of the cleaning composition prepared to 0.2% by mass. Preferably, in the liquid property having a pH of 11 or more, it has an effect of being particularly excellent in cleaning performance of oily and fat soils and protein soils, and being excellent in stability of alkali metal hypochlorite.

  Thus, since this cleaning composition has the above-mentioned special composition, the stability of the alkali metal hypochlorite, the stability of the sequestering power, the cleaning performance, the anti-redeposition performance, and the finishing performance. In addition, it has excellent characteristics in terms of both scale generation suppression performance. In addition, there is an advantage that it can be used safely with little or no influence on the glass surface, which has been a problem in the past.

  In addition, the cleaning composition has excellent storage stability at low temperatures, and even when stored at high temperatures, decomposition of sodium hypochlorite is minimized, and causes of scale and cleaning Since the ability to sequester metal ions contained in tap water, which causes a reduction in force, is stable over time, the same performance as that immediately after production can be maintained over a long period of time. For this reason, even if the storage period and storage conditions are different, the detergency, finish of tableware, bleaching power, and scale suppression effect can always be exhibited.

  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 can be suitably used for 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 0.1 to 0.5 mass% cleaning solution in consideration of the type of soil, the amount (degree) of soil, the quality of tap water used for cleaning, and the like. By supplying it to the dishwasher, an excellent finishing effect can be obtained particularly for tableware and cooking utensils.

  Next, examples will be described together with comparative examples. The present invention is not limited to the following examples.

  Liquid detergent composition for automatic dishwashers (hereinafter referred to as “test cleaning”) of the compositions of Examples 1 to 47 and Comparative Examples 1 to 22 shown in Tables 1 to 18 below (units of numerical values in each table are% by mass) The pH, sequestering stability, scale formation suppression performance, low temperature stability, high temperature stability, cleaning performance, anti-redeposition performance, finish after cleaning, glass surface The following 10 methods were tested and evaluated according to the following methods. However, about pH, it measured only about Examples 1-47.

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

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

[Stability of sequestering power]
200 ml of each prepared cleaning composition for test was placed in a 250 ml polypropylene container and stored at 38 ° C. for 3 months, and then the remaining sequestering force was measured by the following method. And the ratio with respect to the metal ion sequestration force before storage was calculated | required as metal ion sequestration force residual rate (%), and stability was evaluated according to the following criteria.

Metal ion sequestration force measuring method 60 g of 0.15 mass% solution of the prepared 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 auto titration was performed. Using an apparatus (model: TS-980, manufactured by Hiranuma Sangyo Co., Ltd.), titration is automatically performed with a calcium chloride solution having a known concentration, and the following formula is calculated.

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% ×: Residual rate is less than 30%

[Scale generation suppression performance]
Test method Using artificial hard water (total hardness: 250 mg / L), the test detergent composition was diluted to 0.05% by mass, 50 ml was poured into a colorimetric tube having a capacity of 100 ml, and the atmosphere at 60 ° C. with an incubator After being placed for 24 hours, the amount of scale produced was visually determined according to the following criteria.

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

[Low temperature stability]
Test Method The adjusted test detergent composition is put in a 250 ml polypropylene container, and the temperature of the liquid is cooled and heated so as to draw a cycle of + 5 ° C. to −5 ° C. in 24 hours. It was carried out continuously for days, and 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 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.

[High temperature stability]
Test Method 200 ml of the prepared test detergent composition was placed in a 250 ml polypropylene container, placed in an atmosphere at 38 ° C. by an incubator and stored for 100 days. The presence or absence of crystal precipitation or discoloration was examined, and the high temperature stability was evaluated according to the following evaluation criteria.

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

[Cleaning performance]
Test Method The prepared test detergent composition was put 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 10 sheets 1 set, and the washing | cleaning performance was evaluated by the evaluation criteria of a postscript. In addition, beef tallow, top fresh powder, curry, egg yolk and tea astringent were prepared as dirt, and cleaning evaluation 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: 75 g of water was added to 25 g of upper fresh powder, and the mixture was boiled for 20 minutes while stirring and used as a paste.
Curry dirt: A commercially available retort curry (bon curry) was used.
Egg yolk 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 adhered to the soil 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 thereon, put into a dryer at 100 ° C., and the water was completely removed.

・ Evaluation criteria ◎ ... 90% or more of soil removal ○ ... 70% or more and less than 90% soil removal Δ ... 50% or more and less than 70% soil removal × ... 50% or less of soil removal

(Reattachment prevention performance)
·Test method
30 g of salad oil colored with oil red (Zudan IV, manufactured by Wako Pure Chemical Industries, Ltd.) together with the prepared test detergent composition was charged into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) The operation was performed under the following operating conditions, and the degree of dirt adhered to the melamine clean dish was visually determined according to the following 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)
Tap water hardness: 70-80 mg / L (as CaCO ₃ )

・ Evaluation criteria ◎: No dirt adhered to the clean dish.
○: There was almost no dirt on the clean dish.
Δ: Dirt adhered to the clean dish.
X: Dirt adhered to the clean dish.

[Finishability after washing]
Test Method The prepared test detergent composition was put 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 below was wash | cleaned as 1 set, and the finished performance after washing | cleaning was evaluated by the evaluation criteria of a postscript.

・ 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 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 spot is seen.
○: 1 to 2 water spots are seen.
Δ: 3 to 5 water spots are seen.
X: Six or more water spots are seen.

[Influence on glass surface]
Test Method A commercially available normal tumbler glass (manufactured by soda glass) was immersed in the prepared test detergent composition under the following conditions. And the state of the tumbler glass after immersion was observed visually, and the following evaluation criteria evaluated.

・ Immersion condition detergent concentration: 0.2% by mass
Immersion temperature: 60 ° C
Immersion time: 2 weeks

-Evaluation criteria A: No discoloration or corrosion is observed on the surface of the tumbler glass.
○: The tumbler glass surface is slightly discolored.
Δ: Large discoloration on the surface of the tumbler glass.
X: Corrosion on the surface of the tumbler glass is large.

[Stability of sodium hypochlorite]
・ Test method The prepared test detergent composition was placed in a 250 ml polypropylene container and stored at 38 ° C. for 1 month. Then, the remaining effective chlorine was measured by the following method, and the effective chlorine before storage was measured. The ratio was determined as the effective chlorine residual rate (%), and the stability was evaluated according to the following criteria.

-Effective chlorine measurement method 3 g of a sample is placed in a 200 ml Erlenmeyer flask, 15 ml of a 10% by mass potassium iodide solution and 10 ml of (1 + 1) sulfuric acid are added thereto, and left in a cool dark place for 3 minutes to release iodine. Titrate with 1N sodium thiosulfate normal solution until the yellow color of iodine disappears, and calculate 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% ×: Residual rate is less than 30%

  Further, in Tables 1 to 18 below, details of each component constituting the test detergent composition and its effective pure content (mass%) are as follows, and the numerical values in the table below are effective. It is shown in terms of a pure content of 100% by mass. “Water” in the table is the sum of water contained in the form of crystal water or aqueous solution derived from each component constituting the test detergent composition and water added from the outside, and the test detergent It is shown as a balance so that the entire composition is 100% by mass.

[Component A]
-Sodium tripolyphosphate trade name: Wandet B, manufactured by Nippon Chemical Industry Co., Ltd. [A 'component]
-Potassium tripolyphosphate (50% pure)
Product name: KTP, manufactured by Nippon Chemical Industry Co., Ltd.

[B component]
Sodium silicate (pure content 39%, molar ratio Si ₂ O: Na ₂ O = 3: 1)
Product name: JIS No. 3 sodium silicate, manufactured by Guangei Chemical Co., Ltd.
Potassium silicate (pure content 40%, molar ratio Si ₂ O: K ₂ O = 3: 1)
Product name: Potassium Silicate, manufactured by Nippon Chemical Industry Co., Ltd.

[C component]
・ Potassium hydroxide (48% pure)
Product name: Caustic potash 48%, manufactured by Toagosei Co., Ltd. [C 'component]
・ Sodium hydroxide (25% pure)
Product name: Caustic soda 25%, manufactured by Shin-Etsu Chemical Co., Ltd.

[D component]
・ Sodium hypochlorite (12% pure)
Product name: Aron Clean, manufactured by Toagosei Co., Ltd.

[E component]
・ Polyelectrolyte polymer 1
Polyacrylic acid (48% pure, average molecular weight 4,500)
Product name: Primary LMW-45, manufactured by ROHM & HAAS, polyelectrolyte polymer 2
Sodium polyacrylate (45% pure, average molecular weight 4,500)
Product name: Acusol 445N, manufactured by ROHM & HAAS, polyelectrolyte polymer 3
Sodium polyacrylate (45% pure, average molecular weight 8,000)
Product name: Sokalan 30CL, manufactured by BASF, polyelectrolyte polymer 4
Sodium polyacrylate (45% pure, average molecular weight 4,000)
Product name: Sokalan 25CL, manufactured by BASF, polyelectrolyte polymer 5
Sodium polyacrylate (43% pure, average molecular weight 2,000)
Product name: Alon A-210, manufactured by Toagosei Co., Ltd., polyelectrolyte polymer 6
Sodium salt of acrylic acid-maleic acid copolymer (pure content 35%, average molecular weight 40,000)
Product name: Acusol 505N, manufactured by ROHM & HAAS, polyelectrolyte polymer 7
Sodium poly-α-hydroxypolyacrylate (pure content 30%, average molecular weight 10,000 to 14,000)
Product name: Pale Plaque 1200, manufactured by Nippon Peroxide Co., Ltd./polyelectrolyte polymer 8
2-hydroxy-3-allyloxypropanesulfonic acid sodium acrylate (pure content 50%, average molecular weight 3,000)
Product name: Aqualic GL246, manufactured by Nippon Shokubai Co., Ltd.

[Other ingredients]
・ Trisodium citrate ・ dihydrate Product name: Trisodium citrate crystal, manufactured by Iwata Chemical Industry Co., Ltd. ・ Trisodium triacetate ・ monohydrate Product name: Trilon A92R, manufactured by BASF

  The present cleaning compositions of Examples 1 to 47 have the stability of sequestering power, scale formation suppression performance, low temperature stability, high temperature stability, cleaning performance, anti-redeposition performance, finish after cleaning, glass It can be seen that good results have been obtained in all aspects of surface impact and sodium hypochlorite stability.

Claims (4)

It contains the following components (A) to (E) as active ingredients, (F) contains water, and the total amount of the active ingredients is 10 to 50% by mass with respect to the whole composition. Liquid detergent composition for automatic dishwashers.
(A) Sodium tripolyphosphate 2 to 13% by mass
(B) Sodium silicate 1-20 mass%
(C) Potassium hydroxide 0.1-20 mass%
(D) 0.2-3 mass% with hypochlorite alkali metal salt as effective chlorine content
(E) 0.1-5% by mass of polymer electrolyte polymer   The liquid detergent composition for an automatic dishwasher according to claim 1, further comprising 0.1 to 20% by mass of (B ') potassium silicate as an active ingredient.   The automatic component according to claim 1 or 2, further comprising at least one of (A ') 0.1 to 20% by mass of potassium tripolyphosphate and (C') 0.1 to 5% by mass of sodium hydroxide as an active ingredient. Liquid detergent composition for dishwashers.   The pH (JIS Z-8802: 1984 "pH measurement method") of a 0.2 mass% aqueous solution obtained by diluting the liquid detergent composition for automatic washing machines is set to 11 or more at 25 ° C. The liquid detergent composition for automatic dishwashers as described in any one of 1-3.