TWI470077B - A detergent detergent composition for automatic washing machine - Google Patents

Description

Powder cleaner composition for automatic washing machine

The present invention relates to a powder detergent composition for use in a washing machine for hard articles. More specifically, the present invention relates to a powder detergent composition for an automatic washing machine for washing hard objects such as kitchen utensils or plastic containers for food and beverage processing.

The automatic washing machine is used for washing dishes such as dirty dishes, glassware, cooking utensils, etc. in kitchens such as homes, restaurants, cafes, etc., and washing of plastic containers for foods and products used in food and beverage factories. . As a main target stain, there are proteins, starches, fats and the like derived from foods, and these stains are composited and adhered to dishes and plastic containers such as dishes, glassware, and cooking utensils. Further, in the case of heating and cooking, the stains are thermally denatured and become stubborn stains and fixed.

Usually, the washing step of the automatic washing machine is carried out in the order of washing-washing, and the time required for the steps is very short, that is, the washing step is about 40 to 60 seconds, and the washing step is 5~. 20 seconds or so.

Therefore, in the powder detergent composition for an automatic cleaner, an alkali agent such as an alkali metal hydroxide is prepared in order to efficiently wash the stubborn stains in a short time.

In addition, tap water, well water, and the like containing a hardness component such as Ca or Mg ions are often used for washing, and the hardness components in the water are reacted with carbonate, citrate, and carbon dioxide in the atmosphere from the lotion to form calcium carbonate. Products such as magnesium carbonate, calcium citrate, magnesium citrate. Since the product is insoluble in water, it adheres to the dish, the tank of the automatic washing machine, the groove wall, etc., and forms a stubborn film called scale. As a result, the thermal efficiency of the heat exchange unit is lowered, the clogging of the circulation pump, and the malfunction of the concentration sensor are caused.

In order to avoid the failure caused by the adhesion of scale, a powder detergent for a phosphorus type automatic washing machine equipped with a tripolyphosphate having a high inhibitory effect on scaling adhesion is used, but the tripolyphosphate system causes water superiority. Because of the environmentally friendly nature, we are seeking to develop technologies that do not use them.

In the above-mentioned background, there is disclosed a detergent composition for an automatic dishwashing machine containing one or more kinds of alkali chemicals, a polymer material having metal ion trapping energy, and a bleaching agent (for example, Japanese Patent Laid-Open No. Hei 8-199194) ). Japanese Laid-Open Patent Publication No. 2002-12627 discloses a water-soluble polymer and its use for washing. Japanese Laid-Open Patent Publication No. 2003-27095 describes a lotion containing sodium metasilicate, anhydrous sodium carbonate and a chelating agent. Japanese Patent No. 4038271 B describes the prevention of scale adhesion by polyacrylic acid, polyacrylate, polyacrylic acid copolymer or the like. Japanese Laid-Open Patent Publication No. 2009-500487 describes a lotion containing a polyacrylate, a carbonate, a phosphate or the like.

The present invention relates to a powder detergent composition for an automatic cleaning machine for a hard article, which comprises (a) polyacrylic acid or a salt thereof (hereinafter referred to as component (a)), (b) copolymerization of acrylic acid and maleic acid And a salt or a salt thereof (hereinafter referred to as component (b)), and (c) one or more alkali chemicals (hereinafter referred to as component (c)) selected from the group consisting of carbonates and citrates, which are 35 wt% or more And (d) an organic chelating agent, and the total amount of (a) and (b) is 6% by weight or more, and (a) / (b) (weight ratio) is 1 or more.

Japanese Patent Laid-Open No. Hei 8-199194 is insufficient in terms of both high detergency and high scale adhesion inhibiting effect.

In the present invention, the powder detergent composition for an automatic cleaner of a hard article refers to a powder detergent composition used when a hard article such as a tableware, a cooking utensil, or a plastic container is washed by an automatic washing machine.

The present invention provides a powder detergent composition for an automatic cleaning machine for a hard article, which is used for washing dishes such as dishes, glassware, and cooking utensils in a kitchen, and for foods and beverages used in food and beverage factories. Washing of plastic containers, etc., has high scale adhesion inhibition effect and high detergency.

According to the present invention, it is possible to provide a powder detergent composition for an automatic cleaner having a high-detergency and a high scale adhesion-preventing effect.

<(a) component>

The powder detergent composition for an automatic cleaner of the present invention contains polyacrylic acid or a salt thereof as the component (a). The polyacrylic acid or a salt thereof includes a homopolymer of acrylic acid or a salt thereof. Examples of the component (a) include polyacrylic acid, sodium polyacrylate, and potassium polyacrylate. Preferred are sodium polyacrylate and potassium polyacrylate. The component (a) of the present invention may be a copolymer containing a monomer other than acrylic acid and being a monomer copolymerizable with acrylic acid (excluding maleic acid) as long as it does not impair the performance of the effect of the present invention. . Examples of the monomer other than acrylic acid and which are copolymerizable with acrylic acid (excluding maleic acid) include a vinyl monomer, an acrylic monomer, a styrene monomer, and the like, and more specifically Examples include methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene, and the like. A monomer other than acrylic acid and a monomer copolymerizable with acrylic acid (excluding maleic acid) may be used as long as the component (a) does not adversely affect the physical properties such as water solubility or the effect of the present invention. The molar ratio in the a) component is not limited, and is preferably 0 to 5 mol%, more preferably 0 to 3 mol%, and most preferably 0 mol%, in the component (a). Therefore, the polyacrylic acid or a salt thereof of the present invention may further comprise a monomer other than acrylic acid in a range of 0 to 5 mol% in all constituent monomers and is a monomer copolymerizable with acrylic acid (including maleic acid) Except for polymers or copolymers.

Further, the weight average molecular weight of the component (a) is preferably from 1,000 to 20,000, more preferably from 2,000 to 15,000, from the viewpoint of the effect of suppressing scale adhesion. The weight average molecular weight is a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent, and is subjected to gel permeation chromatography, and is a commercially available and commercially available polyacrylic acid having a known molecular weight as a polymer standard reagent. For example, a molecular weight standard reagent manufactured by Sigma-Aldrich is obtained as a standard substance.

<(b) component>

The powder detergent composition for an automatic cleaner of the present invention contains a copolymer of acrylic acid and maleic acid or a salt thereof as the component (b). Examples of the component (b) include a copolymer of acrylic acid and maleic acid, a sodium salt of a copolymer of acrylic acid and maleic acid, a potassium salt of a copolymer of acrylic acid and maleic acid, and the like, and acrylic acid and maleic acid are preferred. a sodium salt of a copolymer, a potassium salt of a copolymer of acrylic acid and maleic acid. Further, from the viewpoint of the effect of suppressing scale adhesion in the component (b), the molar ratio of the acrylic acid/maleic acid is preferably 0.25 to 4, more preferably 0.4 to 2.5. The component (b) of the present invention may be a monomer containing a monomer other than acrylic acid and maleic acid and copolymerizable with acrylic acid and/or maleic acid as long as it does not impair the performance of the effect of the present invention. Copolymer. Examples of the monomer other than acrylic acid and maleic acid and copolymerizable with acrylic acid and/or maleic acid include a vinyl monomer, an acrylic monomer, a styrene monomer, etc., more specifically Examples thereof include methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene. The monomer other than acrylic acid and maleic acid is a single copolymerizable with acrylic acid and/or maleic acid as long as the component (b) does not adversely affect the physical properties such as water solubility or the effect of the present invention. The molar ratio in the component (b) is not limited, and is preferably 0 to 5 mol%, more preferably 0 to 3 mol%, and most preferably 0 mol%, in the component (b). Therefore, the copolymer of acrylic acid and maleic acid of the present invention or a salt thereof may comprise a monomer other than acrylic acid and maleic acid in a range of 0 to 5 mol% in all constituent monomers and is compatible with acrylic acid and / or a copolymer of maleic acid copolymerized monomers.

Generally, maleic acid is used in the copolymerization reaction in the case of producing the component (a), and thus the above molar ratio can be a molar ratio based on maleic anhydride.

Further, from the viewpoint of the effect of suppressing scale adhesion, the weight average molecular weight of the component (b) is preferably from 1,000 to 100,000, more preferably from 2,000 to 90,000. The weight average molecular weight is a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent, and is subjected to gel permeation chromatography, and is a commercially available and commercially available polyacrylic acid having a known molecular weight as a polymer standard reagent. For example, a molecular weight standard reagent manufactured by Sigma-Aldrich is obtained as a standard substance.

<(c) component>

The powder detergent composition for an automatic cleaner of the present invention contains one or more alkali agents selected from the group consisting of carbonates and citrates as the component (c). Examples of the component (c) include sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, sodium citrate No. 1, potassium citrate No. 1, sodium carbonate, potassium carbonate, and sodium hydrogencarbonate. Potassium hydrogencarbonate or the like is preferably sodium carbonate, potassium carbonate, sodium metasilicate or potassium metasilicate. From the viewpoints of detergency and storage stability, sodium carbonate and sodium metasilicate are preferred. From the viewpoint of the scale adhesion inhibiting effect, sodium metasilicate is preferred. Therefore, in the present invention, it is preferred to contain a decanoate as the component (c).

<(d) component>

The powder detergent composition for an automatic cleaner of the present invention contains an organic chelating agent as the component (d) from the viewpoint of excellent scale inhibition effect. Examples of the component (d) include (d1) an aminocarboxylic acid salt such as tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, and tetrasodium L-glutamic acid diacetate, and (d2) lemon. a hydroxycarboxylic acid salt such as trisodium acid, disodium malate or sodium tartrate; preferably selected from the group consisting of tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, and tetrasodium L-glutamic acid diacetate. And at least one of the group consisting of trisodium citrate.

<Powder detergent composition for automatic washing machine>

The powder detergent composition for an automatic cleaner according to the present invention contains the above components (a) to (d), and may further contain other components.

The content of the component (a) in the powder detergent composition for an automatic cleaner of the present invention is preferably 5% by weight or more, and more preferably 6% by weight or more, from the viewpoint of the effect of inhibiting the scale adhesion. The upper limit is not particularly limited, and is preferably 40% by weight or less, more preferably 30% by weight or less, and still more preferably 15% by weight or less from the viewpoint of effect and cost. From the above viewpoints, the content of the component (a) is preferably from 5 to 40% by weight, more preferably from 6 to 30% by weight, still more preferably from 6 to 15% by weight.

Further, the content of the component (b) in the powder detergent composition for an automatic cleaner of the present invention is preferably from 0.5 to 10% by weight, more preferably from 1 to 5, from the viewpoint of the effect of inhibiting scale adhesion. weight%. It is preferably 0.5% by weight or more, more preferably 1% by weight or more. The upper limit is not particularly limited, and is preferably 10% by weight or less, and more preferably 5% by weight or less from the viewpoint of effect and cost. From the above viewpoints, the content of the component (b) is preferably from 0.5 to 10% by weight, more preferably from 1 to 5% by weight.

In addition, the content of the component (c) in the powder detergent composition for an automatic cleaner of the present invention is preferably 35 wt% or more from the viewpoint of imparting a detergency component and having excellent detergency. From the viewpoint of the detergency and scale adhesion inhibiting effect, it is preferably 40 to 90% by weight, more preferably 45 to 85% by weight, still more preferably 40 to 55% by weight. Further, the ratio of the citrate in the component (c) is preferably 20% by weight or more, more preferably 25 to 100% by weight, still more preferably 30%, from the viewpoints of the detergency and the scale adhesion inhibiting effect. 100% by weight.

The content of the component (d) in the powder detergent composition for an automatic cleaner of the present invention is preferably from 1 to 50% by weight, more preferably from 10 to 40% by weight, from the viewpoint of the effect of inhibiting scale adhesion. .

In addition, the total amount of the component (a) and the component (b) in the powder detergent composition for an automatic cleaner according to the present invention is preferably 6% by weight or more, preferably 7 to 60% by weight, more preferably 8 to 40% by weight, still more preferably 8 to 20% by weight.

Further, the weight ratio of the component (a) to the component (b) in the powder detergent composition for an automatic cleaner of the present invention is (a)/(b) from the viewpoint of the effect of inhibiting the scale adhesion. It is 1 or more, preferably 2 or more, and more preferably 3 or more. The upper limit is not particularly limited, but is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, still more preferably 15 or less from the viewpoint of effect and cost. From the above viewpoints, (a)/(b) is preferably from 1 to 50, more preferably from 2 to 40, still more preferably from 3 to 30, still more preferably from 3 to 15.

In addition, the total amount of the component (a) and the component (b) in the powder detergent composition for an automatic cleaner according to the present invention is the same as the effect of suppressing the adhesion and scaling adhesion. The weight ratio of the components is preferably from 0.5 to 10, more preferably from 1 to 8, more preferably from 2 to 5, in terms of (c) / [(a) + (b)].

In the powder detergent composition for automatic washing machine of the present invention, in addition to the components (a) to (d), Glauber's salt, a surfactant, a bleaching agent, an enzyme, an antifoaming agent, a preservative, and the like may be optionally provided. Rust inhibitors, fungicides, antibacterial agents, pigments, perfumes, dissolution aids, etc.

The powder detergent composition for an automatic cleaner of the present invention is used in an automatic cleaning machine for hard articles. Here, the hard article includes a member including a member having a hard surface as a main body, and an article having a size, a shape, and a material suitable for washing by an automatic washing machine. In addition, soft components are also partially included. As a specific hard article, a tableware, a cooking utensil, a plastic container, etc. are mentioned. Further, the automatic washing machine can suitably use a device suitable for automatic washing of such hard articles. Moreover, as an automatic washing machine for hard articles of this invention, the automatic dish washing machine and the washing machine for plastic containers are mentioned, for example, and it is preferable to apply to the automatic dish washing machine.

Further, the powder detergent composition for an automatic cleaner of the present invention does not contain a phosphorus-containing compound and can be used as a so-called phosphorus-free composition.

The powder detergent composition for an automatic cleaner of the present invention preferably has a pH of from 10 to 13 at 25 ° C from the viewpoint of detergency and substrate damage, more preferably 11~12.

Example

The following examples illustrate the practice of the invention. The examples are illustrative of the invention and are not intended to limit the invention.

The powder detergent composition for an automatic washing machine having the composition shown in Table 1 was prepared, and the scale adhesion inhibiting ability and the detergency were evaluated by the following methods. The results are shown in Table 1.

[1] Evaluation of scale inhibition ability <Test conditions>

Use washing machine: Sanyo Electric Co., Ltd. Automatic tableware washing machine (SANYO DR53)

Washing temperature: 60 ° C

Washing time: 40 seconds

Washing temperature: 70 ° C

Washing time: 5 seconds

Washing concentration: 0.10% by weight

Use water: 6°dH hard water (adjusted with calcium chloride)

<Evaluation method>

Five samples of SUS304 (100 mm × 130 mm) were placed in a specific position of the washing rack, and after washing, washing, and air drying at room temperature for 1,000 times under the above test conditions, based on the following evaluation criteria The appearance of the sample was visually judged. Table 1 shows the average of 5 (back).

<Evaluation criteria>

6: Compared with before the test, there is no difference, shiny

5: slightly discolored but not attached to scale, shiny

4: discolored but not attached to scale, shiny

3: Part of the attached scale, shiny

2: The whole is covered by scale, matt

1: the whole is covered by scale, matt and rough surface

In addition, as the evaluation of the scale inhibiting ability of the present invention, it is preferable to determine that the scale is not adhered and the gloss is 4 or more.

[2] Evaluation of detergency <Production of model dirt>

In the center of the magnetic plate of 20 cm in diameter of the new product, 2 g of egg yolk was uniformly coated into a circular shape having a diameter of about 10 cm by a brush, and placed in an electric dryer set at 80 °C. After 30 minutes, the magnet plate coated with egg yolk was taken out and naturally cooled, and used as model soil for evaluation of detergency.

<Evaluation method>

In the washing tank (38 L) of the automatic dishwashing machine (SANYO DR53) manufactured by Sanyo Electric Co., Ltd., 38 g of the powder detergent composition for the automatic washing machine of Table 1 was used, and the warm water of 60 ° C was used. Let it dissolve. Four magnetic plate-making plates coated with model dirt were placed on a dedicated tray, and washed with a washing solution at 60 ° C for 40 seconds, and then washed with washing water at 70 ° C for 5 seconds. The magnetic plate was taken out from the dedicated tray, and the color was colored using a 1% by weight aqueous solution of erythrosine red, and the detergency was evaluated by visual judgment based on the criteria shown below.

<Criteria for determination of detergency>

5: None of the 4 magnet plates were completely stained, and the stains were removed.

4: Any one of the four magnet plates sees a slight coloring, and most of the stains are removed.

3: 4 magnetic plates all saw slight traces of color, most of the stains were removed

2: All of the four magnetic plates are seen with colored marks, and about half of the stain remains.

1:4 magnets all see stains, most of the stains remain

In addition, as the evaluation of the detergency of the present invention, it is preferable to determine that the stain is removed by three or more.

‧a-1: sodium salt of polyacrylic acid [weight average molecular weight is 4,000, Sokalan PA25CL Granules (manufactured by BASF JAPAN): raw material information from BASF JAPAN products catalogue]

‧b-1: sodium salt of acrylic acid/maleic acid copolymer [weight average molecular weight is 70,000, acrylic acid/maleic acid copolymer ratio = 70/30, Sokalan CP5 Granules (manufactured by BASF JAPAN): raw material information comes from BASF JAPAN (stock) product catalogue]

‧b-2: Acrylic/maleic acid copolymer salt [weight average molecular weight 5,000, Aqualic TL37 (made by Nippon Shokubai Co., Ltd.): Raw material information from Japan Catalysts)

‧Nonionic surfactant: propylene oxide ‧ ethylene oxide ‧ propylene oxide ‧ block polymer [weight average molecular weight of 3,100, propylene oxide / ethylene oxide ratio = 80 / 20, Pluronic RPE2520 (BASF JAPAN (Stock) Manufacturing): Raw material information from BASF JAPAN (stock) product catalogue]

Claims (11)

A powder detergent composition for an automatic cleaning machine for a hard article, comprising (a) polyacrylic acid or a salt thereof, (b) a copolymer of acrylic acid and maleic acid or a salt thereof, (c) selected from the group consisting of carbonates and The amount of the component (a) is 5 to 40% by weight, and the content of the component (b) is 0.5% by weight of one or more alkali chemicals in the group consisting of citrate and (d) the organic chelating agent. 10% by weight, the content of the component (d) is 1 to 50% by weight, and the total amount of (a) and (b) is 6% by weight or more, and (a)/(b) (weight ratio) is 1 or more. The powder detergent composition for an automatic cleaner according to claim 1, wherein the ratio of the citrate in (c) is 20% by weight or more. The powder detergent composition for an automatic cleaner according to claim 1, wherein the ratio of the total amount of the component (a) to the component (b) to the component (c) is (c) / [(a) + (b) ] is 0.5~10. The powder detergent composition for an automatic cleaner according to claim 2, wherein the ratio of the total amount of the component (a) to the component (b) to the component (c) is (c) / [(a) + (b) ] is 0.5~10. The powder detergent composition for an automatic cleaner according to any one of claims 1 to 4, wherein (a) the polyacrylic acid or a salt thereof is a homopolymer of acrylic acid or a salt thereof. The powder cleaner composition for an automatic cleaner according to any one of claims 1 to 4, wherein (d) the organic chelating agent is selected from the group consisting of tetrasodium ethylenediaminetetraacetate and trisodium methylglycine diacetate At least one of the group consisting of L-glutamic acid tetrasodium acetate and trisodium citrate. The powder detergent composition for an automatic cleaner according to claim 5, wherein (d) the organic chelating agent is selected from the group consisting of tetrasodium ethylenediaminetetraacetate and methylglycine At least one of the group consisting of trisodium acetate, tetrasodium L-glutamic acid diacetate, and trisodium citrate. The powder detergent composition for an automatic cleaner according to any one of claims 1 to 4, wherein the hard article is one or more selected from the group consisting of a tableware, a cooking utensil, and a plastic container. The powder detergent composition for an automatic cleaner according to claim 5, wherein the hard article is one or more selected from the group consisting of tableware, cooking utensils, and plastic containers. The powder detergent composition for an automatic cleaner according to claim 6, wherein the hard article is one or more selected from the group consisting of tableware, cooking utensils, and plastic containers. The powder detergent composition for an automatic cleaner according to claim 7, wherein the hard article is one or more selected from the group consisting of tableware, cooking utensils, and plastic containers.