JPH09176690A - Bleaching detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bleaching detergent compsn. which is appropriate for the removal of dye dirt attached to the hard surface of metal, glass, porcelain, or plastics, having a low-temp bleaching effect, a merit of no degradation of its bleaching effect by decomposition even after a long-term use and storage, a good bleaching effect even in the bleaching and washing esp. using a washing machine, and, moreover, a good stability of an enzyme. SOLUTION: This bleaching detergent compsn. contains 5-70wt.% water-soluble aminopolycarboxylate, esp. at least one member selected from among 0.5-10wt.% org. polyelectrolyte, 0.5-5wt.% surfactant, and 10-90wt.% detergent builder except water-soluble aminopolycarboxylate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a bleaching detergent composition having a suitable bleaching and detergency against dye stains adhering to hard surfaces such as metal, glass, ceramics and plastics. The present invention relates to the above bleaching detergent composition having a suitable bleaching washing effect in washing used tableware, cooking utensils and the like.

[0002]

2. Description of the Related Art As a cleaning agent for pigment stains adhering to hard surfaces such as metal, glass, ceramics and plastics,
Conventionally, a bleaching agent containing sodium hypochlorite as a main component has been widely used because of its high bleaching effect at low temperatures. However, when such a bleaching agent is used, for example, it causes rust in metals, and in glass, ceramics, plastics, etc., peeling, fading, and lowering of gloss of tableware, etc. There were problems such as burial. Further, in the case of such a bleaching agent, misuse accidents due to the combined use with an acidic substance may occur, and in recent years, environmental pollution such as water pollution has been feared. In addition, in recent years, JP-A-7-
As in Japanese Patent No. 278597, oxygen-based bleaching agents such as sodium percarbonate and sodium perborate, and bleaching agents containing a surfactant as a main component have been widely used. However, in the case of a bleaching agent containing an oxygen-based bleaching agent as a main component, there is a problem that a sufficient bleaching effect cannot be obtained unless the temperature of the cleaning solution at the time of use is about lukewarm water. Further, both the chlorine-based bleaching agent and the oxygen-based bleaching agent have a drawback that they tend to decompose over time during long-term use and storage, especially under hot and humid conditions.

On the other hand, in the field of dishwashing, due to changes in lifestyles and diversification of menus, oil stains, protein stains, and pigments tend to adhere significantly, resulting in high performance,
High-performance methods have been required. Therefore, in hotels, restaurants, catering companies, hospitals and company cafeterias, jet type automatic dishwashers have come to be widely used for washing used dishes, and in recent years, such automatic dishwashing machines have been widely used. The machine has become popular not only for commercial use but also for general households. As a cleaning agent used in such an automatic dishwasher, an oxygen-based bleaching agent is used, for example, JP-A-1-198698 discloses a hydroxy polycarboxylic acid (salt), a polymer chelating agent, An automatic dishwasher detergent containing an inorganic alkaline agent, an amylase and an oxygen-based bleaching agent in a specific ratio is disclosed in Japanese Patent Application Laid-Open No. HEI-1.
Japanese Unexamined Patent Publication (Kokai) -198700 discloses an automatic dishwashing detergent containing a peroxide, an organic precursor containing a quaternary ammonium group which is an activator thereof, a starch hydrolase and an inorganic alkaline agent. However, all of these are easily decomposed with time when stored for a long time under high temperature and high humidity conditions, and in use, sufficient effects cannot be exhibited unless a certain cleaning solution temperature is secured. there were. Further, as a cleaning agent for a dishwasher using a chlorine-based bleaching agent, a cleaning agent containing a chloroisocyanurate salt has been used as seen in JP-A-2-289700. However, the detergent containing chloroisocyanurate has a problem that when the enzyme is added at the same time, the enzyme is inactivated and a sufficient cleaning effect cannot be obtained for starch stains and protein stains. .

[0004]

In consideration of the above conditions, the present inventors have no fear of environmental pollution, can obtain an effective bleaching effect even at low temperature, and can decompose it even during long-term use and storage. The bleaching effect does not decrease, and particularly in bleaching and washing using a washing machine, a good bleaching effect is exhibited, and further, the present invention has been completed in order to develop a bleaching detergent composition having good enzyme stability. It has come to do. That is, the present invention is a bleaching detergent composition suitable for removing pigment stains adhering to hard surfaces of metals, glass, ceramics, plastics, etc. without concern about environmental pollution. It develops and has the advantage of not deteriorating the bleaching effect due to decomposition even during long-term use and storage, and particularly in bleaching washing using a washing machine, it has a good bleaching washing effect, and also has good enzyme stability. The purpose of the present invention is to provide a bleaching detergent composition.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a bleaching detergent composition containing a specific amount of a water-soluble aminopolycarboxylate, particularly a bleaching composition containing a specific additive added thereto. The present invention has been completed by finding that the above-mentioned object of the present invention can be effectively achieved by the detergent composition. That is, the present invention provides (1) a bleaching detergent composition characterized by containing water-soluble aminopolycarboxylate in an amount of 5 to 70% by weight, (2) an organic electrolyte polymer 0.5 to 10 % By weight, surfactant 0.5-
5% by weight and at least one selected from 10 to 90% by weight of a washing builder other than the water-soluble aminopolycarboxylate, the bleaching detergent composition according to the above (1), (3) the water-soluble amino. 5 to 70% by weight of polycarboxylate and 0.5 to 3.0% by weight of chlorine bleach
A bleaching detergent composition containing (4)
Further, it contains at least one selected from 0.5 to 10% by weight of an organic electrolyte polymer, 0.5 to 5% by weight of a surfactant, and 10 to 90% by weight of a washing builder other than a water-soluble aminopolycarboxylate. The bleaching detergent composition according to the above (3), and the bleaching detergent composition according to any one of the above (1) to (4), which comprises (5) an enzyme for a detergent. And (6) above (1) to
A bleaching cleaning method using the bleaching detergent composition according to any one of (5), characterized in that the bleaching detergent using solution comprising the bleaching detergent composition has a pH of 6 to 11. A method for bleaching and washing is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The bleaching detergent composition of the present invention is characterized by containing 5 to 70% by weight of a water-soluble aminopolycarboxylate. As the water-soluble aminopolycarboxylate used here, preferably, respective salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, N- (2-hydroxyethyl) -nitrilodiacetic acid and the like are mentioned, and particularly, solubility and From the viewpoint of long-term storage stability, these sodium salts, potassium salts and the like can be preferably used. The water-soluble aminopolycarboxylate is contained in the bleaching detergent composition in an amount of 5 to 70% by weight. When the content is less than 5% by weight, the bleaching effect is poorly expressed, and when it exceeds 70% by weight, the content of other components contained in the bleaching detergent composition is restricted, and the compositional component is limited. However, it is not economical to use a larger amount because the effect tends to be saturated and the effect tends to be saturated. From this point of view, the content is further 20 to 70% by weight, particularly 20 to 70% by weight.
It is preferably 50% by weight. Further, in the present invention, the water-soluble aminopolycarboxylate may be used alone or in combination of two or more.

The bleaching detergent composition of the present invention comprises, in addition to the above-mentioned water-soluble aminopolycarboxylate, at least one selected from a washing builder other than an organic electrolyte polymer, a surfactant and a water-soluble aminopolycarboxylate. Those obtained by blending are preferably used. Examples of organic electrolyte polymer that can be used include poly (meth) acrylic acid, polyaconitic acid, polyitaconic acid,
Polycitraconic acid, polyfumaric acid, polymaleic acid,
Polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene Copolymers, ethylene maleic anhydride crosslink copolymers, maleic anhydride vinyl acetate copolymers, maleic anhydride acrylonitrile copolymers, maleic anhydride acrylic acid ester copolymers, maleic anhydride butadiene copolymers, anhydrous Maleic isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid ethylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid Acrylic acid copolymer, methyl malonate Examples of the copolymer include a ren copolymer, an itaconic acid fumaric acid copolymer, an ethylene glycol ethylene terephthalate copolymer, a vinylpyrrolidone vinyl acetate copolymer, and the like. In the present invention, from the viewpoint of solubility and cost, acrylic is preferable. Polymers or copolymers using one or two selected from acids, maleic acid, methacrylic acid, fumaric acid and itaconic acid can be used. The molecular weight of the organic electrolyte polymer is not particularly limited, but from the viewpoint of the effect of preventing soil redeposition, for example, a polymer of acrylic acid has a weight average molecular weight (Mw) of 4,0.
It is preferable to use a copolymer having an acrylic acid content and a maleic acid content in the range of 2,000 to 20,000, and a copolymer of acrylic acid and maleic acid in the range of 30,000 to 100,000.

The above organic electrolyte polymer is contained in the bleaching detergent composition in an amount of 0.5 to 10% by weight. Content is 0.5
When it is less than 10% by weight, the effect of the present invention is poorly expressed, and when it exceeds 10% by weight, it is not desirable in terms of cost. From such a point, the content is more preferably 1 to 5% by weight. Further, in the present invention, the above organic electrolyte polymer may be used alone or in combination of two or more.

As the surfactant, one or a combination of two or more selected from nonionic surfactants and anionic surfactants can be used. Examples of the nonionic surfactant include polyoxyethylene polyoxypropylene polymer, phosphoric acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester. , Polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, alkyl amine oxide, etc. can be used. Especially, among the above items, improvement of cleaning performance against oily stains Alternatively, a low-foaming nonionic surfactant is preferably used for the purpose of enhancing the effect of preventing stains and the adhesion of calcium-insoluble salts. As the anionic surfactant, alkyl or alkenyl ether sulfate, alkyl sulfate ester salt,
Examples thereof include olefin sulfonates, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, α-sulfo fatty acid salts or esters thereof. In the present invention, as the surfactant, a polyoxyethylene polyoxypropylene polymer is preferably used among the above compounds.

The above-mentioned surfactant is contained in the bleaching detergent composition in an amount of 0.
It is contained in an amount of 5 to 5% by weight. If the content is less than 0.5% by weight, sufficient cleaning effect and antifouling effect of dirt and calcium insoluble salt cannot be obtained, and if it exceeds 5% by weight, the effect tends to be saturated. It is not economical to use the above amount. From such a point, the above content is 1.0 to
More preferably, it is 3.0% by weight. Further, in the present invention, the above surfactants may be used alone, but may be used in combination of two or more kinds.

Examples of the washing builder other than the water-soluble aminopolycarboxylate used in the bleaching detergent composition of the present invention include carbonates, bicarbonates, silicates, sulfates, organic acid salts and phosphates. To be Here, as the carbonate, sodium carbonate, potassium carbonate, sodium sesquicarbonate or the like is used, as the bicarbonate, sodium bicarbonate or the like is used, and as the silicate, sodium metasilicate or sodium orthosilicate is used. , Sodium sesquisilicate, etc. are used. In addition, sodium sulfate or the like is used as the sulfate, and sodium citrate, sodium malate, sodium tartrate, sodium succinate, sodium gluconate, or the like is used as the organic acid salt. Sodium phosphate, sodium orthophosphate, etc. are used. In the present invention, sodium carbonate, sodium metasilicate or sodium succinate is preferably used among the above-mentioned cleaning builders from the viewpoints of improving cleaning performance and environmental protection.
The washing builder is contained in the bleaching detergent composition in an amount of 10 to 90% by weight. When the blending amount is within the above range, the detergency can be improved, and the bleaching effect can be further improved, and favorable results can be obtained.

In the present invention, one or more selected from the above-mentioned organic electrolyte polymer, surfactant and washing builder other than water-soluble aminopolycarboxylate are appropriately combined with water-soluble aminopolycarboxylate. Although the bleaching detergent composition of the present invention can be prepared, it is particularly preferable that all of these are blended with a water-soluble aminopolycarboxylate in order to achieve the object of the present invention. As described above, the bleaching detergent composition of the present invention contains the above-mentioned respective components, and particularly in a system using a chlorine bleaching agent, more preferable effects can be obtained. Examples of the chlorine-based bleaching agent that can be used include chloroisocyanurate and the like, and preferably sodium dichloroisocyanurate can be used. The chlorine-based bleaching agent is contained in the bleaching detergent composition in an amount of 0.5 to 3.0% by weight. When the content is less than 0.5% by weight, the synergistic bleaching effect is poorly expressed, and when it exceeds 3.0% by weight, the chlorine odor becomes strong and peeling or fading of the decoration such as tableware is caused. ， In addition, it may reduce the gloss. From this point of view, the above content is more preferably 1.0 to 3.0% by weight. Further, in the present invention, the chlorine-based bleaching agent may be used alone or in combination of two or more kinds.

In the bleaching detergent composition of the present invention, a cleaning enzyme can be used, if necessary, in addition to the above components. As the washing enzyme, for example, one kind or two or more kinds selected from α-amylase, brotase, cellulase, revertase and the like can be used. The cleaning enzyme is contained in the bleaching detergent composition in an amount of 0.1 to 5.0% by weight. By using within the above range, a better effect of removing starch stains, protein stains, oil stains and the like can be exhibited. Furthermore, in the bleaching detergent composition of the present invention, known conventional components such as a dispersant, a silicone-based defoaming agent, a fragrance, a colorant, and a corrosion inhibitor may be added as necessary within the range that does not impair the object of the present invention. It can also be blended. The bleaching detergent composition of the present invention can be used after diluting it with water or the like, if desired, but the concentration thereof is not particularly limited and is generally 0.1.
It is convenient to use after diluting to a concentration of ˜2% by weight.
At this time, the pH of the liquid used is preferably in the range of 6 to 11, preferably 8 to 11, from the viewpoint of effective action conditions of the enzyme. If the pH value of the liquid used is within the above range, a better result can be obtained with favorable results.

[0014]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 15 and Comparative Examples 1 to 4 A bleaching detergent composition having a composition (% by weight) as shown in Table 1 was prepared, and each of them was subjected to a washing test by the following method. The results are shown in Table 1. Cleaning Test (1) Cleaning Test 1 Dish was immersed in an aqueous bleaching detergent solution under the following conditions for evaluation. <Immersion conditions> Detergent concentration: 0.5 wt% aqueous solution (pH = 10) Cleaning temperature: Hot water (30 ° C) Immersion time: 1 hour After immersion, rinse with tap water.

(2) Washing test 2 Evaluation was made by a dishwasher. <Washing conditions> Dishwasher: NP-720 manufactured by Matsushita Electric Co., Ltd. A dishwasher having a process of spraying a cleaning agent aqueous solution from a rotating nozzle to wash, rinse, and dry the dishes placed on the orbit thereof. Washing temperature: Gradually increase from tap water temperature (10 ° C) to about 60 ° C. Detergent concentration: 0.2 wt% aqueous solution (pH = 9) Washing time: 20 minutes of washing, 30 minutes of rinsing, 60 minutes of drying Washing liquid volume: 3300 ml

Preparation of Stain and Judgment Criteria (a) Stain 1: Tea Astringent Stain (Bleaching Power) A unglazed plate (10 cm × 10 cm) is boiled in green tea liquor for 15 minutes and dried 10 times to be subjected to the test. Judgment: The bleaching rate is calculated from the following formula. Bleaching rate (%) = (R2-R1) / (R0-R1) * 10
0 R0: reflectance of uncontaminated plate R1: reflectance of plate before washing (after contamination) R2: reflectance of plate after washing

(B) Stains 2: Starch Stains (detergency) 3 g of freshly cooked rice is spread evenly on a ceramic dish having a diameter of 18 cm, and air-dried at room temperature for 1 hour for the test. Judgment: A potassium iodide iodide solution (indicator) is evenly dropped on the washed tableware, and the area where stains are removed and the color is not purple is visually judged. A: Almost removed B: 80% removed C: 50% removed D: 25% removed E: Almost not removed

(C) Dirt 3: Protein stain (detergency) 2 g of raw eggs (whole eggs) are evenly spread over a ceramic dish having a diameter of 18 cm and air-dried at room temperature for 1 hour for the test. Judgment: A ninhydrin solution (indicator) was evenly dropped onto the washed tableware, and the area where stains were removed and the color was not purple was visually judged. A: Almost removed B: 80% removed C: 50% removed D: 25% removed E: Almost not removed

(D) Dirt 4: Oil stain (detergency) 2 g of the refined beef tallow manufactured by Nippon Oil & Fat Co., Ltd., which was heated and dissolved, was evenly applied to a ceramic dish having a diameter of 18 cm,
Air-dry at room temperature for 1 hour and use for the test. Judgment: After the Sudan IV solution (indicator) was evenly dropped on the tableware after washing, it was visually rinsed with an area that was not rinsed with cold water to remove stains and showed no red color. A: Almost removed B: 80% removed C: 50% removed D: 25% removed E: Almost not removed

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

* 1 Organic electrolyte polymer: Acrylic acid polymer (Mw = 6,000) * 2 Surfactant: Polyoxyethylene polyoxypropylene polymer As is clear from Table 1, the bleaching cleaning of the present invention The agent composition exerts an excellent bleaching / cleaning effect on various stains adhering to the hard surface, and effectively exhibits the effect even when a cleaning machine is used. Further, each of the bleaching detergent compositions prepared in Examples 2, 6 and 10 was subjected to the same washing test as above after being stored at room temperature for 12 months, and as a result, both the bleaching rate and the detergency were before storage. There was almost no difference between the results and the ones.

[0024]

The bleaching detergent composition of the present invention is a bleaching detergent composition suitable for removing pigment stains adhering to hard surfaces of metals, glass, ceramics, plastics and the like. The effect is exhibited, and even in long-term use and storage, it has the advantage of not deteriorating the bleaching effect due to decomposition, etc. Especially, it exhibits a good bleaching effect even in the bleaching and washing using a washing machine, and the stability of the enzyme It is a good one. Further, the cleaning composition of the present invention is used for bleaching and cleaning bleaching of pigment stains adhering to hard surfaces of metals, glass, ceramics, plastics, etc., as well as preliminary cleaning of tableware and cooking utensils used in kitchens and kitchens. It is also suitable as a bleaching detergent for a dishwasher.

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Claims (6)

[Claims] 1. A water-soluble aminopolycarboxylate is added to 5
A bleaching detergent composition containing 70 to 70% by weight. 2. An organic electrolyte high molecular polymer 0.5 to 1
The bleaching wash according to claim 1, containing at least one selected from 0% by weight, 0.5 to 5% by weight of a surfactant and 10 to 90% by weight of a washing builder other than the water-soluble aminopolycarboxylate. Agent composition. 3. Water-soluble amino polycarboxylate 5
A bleaching detergent composition containing 70 to 70% by weight and a chlorine-based bleaching agent of 0.5 to 3.0% by weight. 4. An organic electrolyte high molecular polymer 0.5 to 1
4. Bleaching cleaning according to claim 3, containing at least one selected from 0% by weight, 0.5 to 5% by weight of a surfactant and 10 to 90% by weight of a washing builder other than the water-soluble aminopolycarboxylate. Agent composition. 5. The bleaching detergent composition according to any one of claims 1 to 4, which contains a detergent enzyme. 6. A bleaching cleaning method using the bleaching detergent composition according to any one of claims 1 to 5, wherein the bleaching detergent use liquid comprising the bleaching detergent composition has a pH of 6 to 11 A bleaching and cleaning method characterized by being used as.