JP5788671B2 - Powder cleaning composition for automatic cleaning machine - Google Patents

Description

  The present invention relates to a powder cleaning composition used in an automatic cleaning machine for cleaning hard articles. More particularly, the present invention relates to a powder cleaning composition for an automatic cleaning machine used for cleaning hard articles such as kitchen utensils and plastic containers for food and beverage processing.

  Automatic washing machines are used for washing dishes such as dirty dishes, glasses and cooking utensils in kitchens such as homes, restaurants, and coffee shops, and washing plastic containers for foodstuffs and products used in food and beverage factories. . Main target soils include food-derived proteins, starches, oils and fats, and these soils are combined and adhered to dishes, glasses, tableware such as cooking utensils, and plastic containers. In addition, during cooking, these stains may be heat-denatured to become strong stains and be fixed. In particular, heat-denatured oil is a difficult-to-clean stain, and there is a need for a cleaning agent that removes this stain.

  Usually, the washing process by the automatic washing machine is performed in the order of washing and rinsing, but the time required for these processes is as short as about 40 to 60 seconds for the washing process and about 5 to 20 seconds for the rinsing process. It is.

  For this reason, alkali metal hydroxides, carbonates, and silicate alkali agents are used in powder detergent compositions for automatic washing machines in order to efficiently wash these strong stains in a short time. Has been. Among these alkali agents, alkali metal hydroxides are preferably used from the viewpoint of detergency. However, alkali metal hydroxides have deliquescent properties, so that handling properties are inferior, and when mixed with 5% or more, they are handled as deleterious substances, so there are restrictions on their use.

  In addition, tap water and well water containing hardness components such as Ca ions and Mg ions are often used for washing, and these hardness components and detergent-derived carbonate radicals, silicate radicals, and carbonates in the atmosphere are used. The gas reacts to form products such as calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate. Since this product is insoluble in water, it adheres to tableware, tanks of automatic washing machines, tank walls, etc., and forms a strong film called scale. As a result, it causes troubles such as a decrease in thermal efficiency of the heat exchange unit, blockage of the circulation pump, malfunction of the concentration sensor, and the like. In particular, while automatic dishwashers for general households are used only a few times a day, in commercial automatic washing machines used in kitchens such as restaurants and coffee shops, a day The continuous use is performed for several hours or more and several tens of times or more, and the adhesion of the scale is a big problem.

  In order to avoid troubles due to scale adhesion, phosphorus-type powder cleaners for automatic washing machines that contain tripolyphosphate, which is highly effective in suppressing scale adhesion, have been used. In view of environmental friendliness, it is a causative substance of nutrition, and development of a scale adhesion control technique equivalent to or higher than that of the phosphorus type is required in a phosphorus-free or very low amount of phosphate.

  In such a background, a detergent composition for an automatic dishwasher containing one or more alkali agents, a polymer substance having a metal ion scavenging ability, and a bleaching agent is disclosed (for example, Patent Document 1). ). However, this technology does not substantially use alkali metal hydroxides, that is, does not use alkali metal hydroxides at all, or does not impair physical properties and product stability due to deliquescence, etc. Therefore, it is not sufficient to achieve both high detergency and high scale adhesion inhibiting effect.

JP-A-8-199194

  An object of the present invention is to substantially eliminate alkali metal hydroxides in washing dishes such as dirty dishes, glasses and cooking utensils in kitchens, washing plastic containers for foods and products used in food and beverage factories, and the like. Powder cleaning composition for automatic washing machine for hard articles having high scale adhesion inhibiting effect and high detergency against heat-denatured oil even in a system containing no phosphorus or very little phosphate Is to provide.

  The present invention relates to a polymer selected from (a) polyacrylic acid or a salt thereof, and a copolymer of acrylic acid and maleic acid or a salt thereof (hereinafter referred to as component (a)) of 8% by mass or more, (b) metasilicic acid Containing 10 to 90% by mass of a silicate selected from a salt and an orthosilicate (hereinafter referred to as component (b)), and (c) a carbonate (hereinafter referred to as component (c)), and (b) a silicate (C) It is related with the powder detergent composition for automatic washing machines of a hard article whose total of carbonate is 35-92 mass%.

  In the present invention, the powder cleaning composition for an automatic cleaning machine for hard articles means a powder cleaning composition used for cleaning hard articles such as dishes, cooking utensils, and plastic containers with an automatic cleaning machine.

  ADVANTAGE OF THE INVENTION According to this invention, the powder cleaning composition for automatic washing machines of the hard article which has the high washing | cleaning property with respect to heat-denatured oil, and a high scale adhesion inhibitory effect substantially without using an alkali metal hydroxide is provided. Is done.

<(A) component>
The powder cleaning composition for an automatic cleaning machine of the present invention contains, as component (a), a polymer selected from polyacrylic acid or a salt thereof and a copolymer of acrylic acid and maleic acid or a salt thereof. Examples of polyacrylic acid or a salt thereof include polyacrylic acid, sodium polyacrylate, potassium polyacrylate, and the like. Sodium polyacrylate and potassium polyacrylate are preferred, and a copolymer of acrylic acid and maleic acid or a salt thereof. May include acrylic acid and maleic acid copolymer, sodium salt of acrylic acid and maleic acid copolymer, potassium salt of acrylic acid and maleic acid copolymer, sodium salt of acrylic acid and maleic acid copolymer, acrylic acid and The potassium salt of the maleic acid copolymer is preferred. The molar ratio of the copolymer of acrylic acid and maleic acid is preferably 99/1 to 1/99, more preferably 90/10 to 10/90, as the number of moles of acrylic acid / number of moles of maleic acid.

  The component (a) of the present invention is a monomer other than acrylic acid and maleic acid and can be copolymerized with acrylic acid and / or maleic acid as long as the effects of the present invention are not hindered. It may be a copolymer. Examples of monomers other than acrylic acid and maleic acid that can be copolymerized with acrylic acid and / or maleic acid include vinyl monomers, acrylic monomers, styrene monomers, and more specifically methacrylic monomers. Examples include acid, methyl acrylate, ethyl acrylate, methyl methacrylate, and styrene. The molar ratio in the component (a) of the monomer other than acrylic acid and maleic acid, which can be copolymerized with acrylic acid and / or maleic acid, is the property of the present invention such as water solubility or the like of the present invention. Although it will not be limited if it does not influence on expression of an effect, 0-5 mol% is preferable in (a) component, 0-3 mol% is more preferable, and it is most preferable that it is 0 mol%. Therefore, the polyacrylic acid of the present invention or a salt thereof, and a copolymer of acrylic acid and maleic acid or a salt thereof are monomers other than acrylic acid and maleic acid among all constituent monomers, and are acrylic acid and / or maleic acid. It may be a polymer or copolymer containing a monomer copolymerizable with 0 to 5 mol%.

  Usually, maleic anhydride is used in the copolymerization reaction for producing the component (a), and therefore, the above molar ratio may be a molar ratio based on maleic anhydride.

  In addition, the weight average molecular weight of the component (a) is preferably 1,000 to 100,000, more preferably 2,000 to 90,000, from the viewpoint of the scale adhesion inhibiting effect. This weight average molecular weight is a polyacrylic acid (for example, sigma), which is a commercially available polymer standard reagent having a molecular weight known by gel permeation chromatography using a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent. Aldrich molecular weight standard reagent) was obtained as a standard substance.

<(B) component>
The powder detergent composition for automatic washing machines of the present invention contains an inorganic silicate selected from metasilicates and orthosilicates as the component (b). Examples of the component (b) include alkali metal metasilicates and alkali metal orthosilicates, and further include sodium metasilicate, potassium metasilicate, sodium orthosilicate, potassium orthosilicate, and the like. Therefore, sodium orthosilicate and sodium metasilicate are preferred.

As the component (b) of the present invention, generally available alkali metal metasilicates and alkali metal orthosilicates can be used. The molar ratio of the constituent silicic acid and the alkali metal oxide is the mol of silicic acid. The number / mole number of the alkali metal oxide is preferably 0.3 to 1.2, and more preferably 0.5 to 1.0. Specifically, in the case of sodium orthosilicate and sodium metasilicate, the number of moles of SiO ₂ / number of moles of Na ₂ O is preferably 0.3 to 1.2, and more preferably 0.5 to 1. 0.

<(C) component>
The powder cleaning composition for an automatic cleaning machine of the present invention contains a carbonate as the component (c). Examples of the component (c) include alkali metal carbonates, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. From the viewpoint of detergency, sodium carbonate and potassium carbonate are preferable, especially scale. From the viewpoints of adhesion suppression effect, detergency, solubility, and cost, the combined use of sodium carbonate and potassium carbonate is more preferable. The mass ratio of sodium carbonate to potassium carbonate is not particularly limited, but is preferably 1 to 10 and more preferably 2 to 5 as the mass of sodium carbonate / the mass of potassium carbonate.

<(D) component>
The powder cleaning composition for an automatic cleaning machine of the present invention preferably contains an organic chelating agent as the component (d) from the viewpoints of detergency and scale adhesion inhibiting effect. As the component (d), (d1) aminocarboxylates such as tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, tetrasodium L-glutamate diacetate, (d2) trisodium citrate, disodium malate, Examples thereof include hydroxycarboxylates such as sodium tartrate, and preferably at least one selected from the group consisting of tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, tetrasodium L-glutamate diacetate, and trisodium citrate. .

<Powder cleaning composition for automatic cleaning machine>
The powder cleaning composition for an automatic cleaning machine of the present invention contains the above components (a) to (c) and, if necessary, the component (d), and may further contain other components.

  The content of the component (a) in the powder cleaning composition for an automatic cleaning machine of the present invention is 8% by mass or more, 10% by mass or more, and further 20% by mass from the viewpoints of detergency and scale adhesion inhibiting effect. The above is preferable. Although an upper limit is not specifically limited, 40 mass% or less is preferable from a viewpoint of a scale adhesion inhibitory effect and cost, and 30 mass% or less is more preferable.

  Moreover, content of (b) component in the powder cleaning composition for automatic washing machines of this invention is 10-90 mass%. From the viewpoint of detergency, the lower limit is 10% by mass or more, preferably 12% by mass or more, and more preferably 25% by mass or more. The upper limit is 90% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less, from the viewpoint of the scale adhesion inhibiting effect.

    Further, the content of the component (c) in the powder cleaning composition for an automatic cleaning machine of the present invention is preferably 5% by mass or more from the viewpoint of detergency. Although an upper limit is not specifically limited, From a viewpoint of the scale adhesion inhibitory effect, 50 mass% or less is preferable and 40 mass% or less is more preferable.

  In addition, the total amount of the component (b) and the component (c) in the powder cleaning composition for an automatic cleaning machine of the present invention is 35 to 92% by mass from the viewpoint of detergency, and is 35 to 90%. % By mass is preferable, 35 to 80% by mass is more preferable, and 40 to 80% by mass is still more preferable.

  In addition, the mass ratio of the component (b) to the component (c) in the powder cleaning composition for an automatic cleaning machine of the present invention is the mass of the component (b) / (c ) The mass of the component is preferably 0.6 to 45, more preferably 0.6 to 7, and still more preferably 1 to 3.

  Further, in the powder cleaning composition for an automatic cleaning machine of the present invention, the ratio of the mass of the component (b) and the total mass of the component (c) to the mass of the component (a) is the detergency and scale adhesion suppression. From the viewpoint of the effect, [mass of component (b) + mass of ingredient (c)] / mass of ingredient (a) is preferably 0.5 to 7, more preferably 1 to 6, and further preferably 2 to 5. .

  The content of the component (d) in the powder cleaning composition for an automatic cleaning machine of the present invention is preferably 1 to 50% by mass and more preferably 10 to 40% by mass from the viewpoints of detergency and scale adhesion inhibiting effect. .

  In addition to the components (a) to (d), the powder cleaning composition for an automatic cleaning machine of the present invention includes, as necessary, mirabilite, surfactant, bleach, enzyme, antifoaming agent, preservative, Rusts, bactericides, antibacterial agents, pigments, fragrances, hydrotropes and the like can be blended.

  As the surfactant blended in the powder cleaning composition for an automatic cleaning machine of the present invention, a nonionic surfactant, an anionic surfactant, a cationic surfactant, or an amphoteric surfactant may be used depending on the purpose. However, a nonionic surfactant is preferable from the viewpoint of detergency.

  Nonionic surfactants that can be used in the present invention are not particularly limited. For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene dialkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene Alkylene alkyl phenyl ether, pluronic block polymer, tetronic block polymer, reverse pluronic block polymer, reverse tetronic block polymer, sucrose fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester , Propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, coconut fatty acid die Nolamide, lauric acid diethanolamide, lauric acid mytilinic acid diethanolamide, myristylic acid diethanolamide, oleic acid diethanolamide, palm kernel fatty acid diethanolamide, alkyl glucosides, amine oxides, etc. Polyoxyethylene polyoxypropylene alkyl ethers, pluronic block polymers, tetronic block polymers, reverse pluronic block polymers, and reverse tetronic block polymers are preferred. These nonionic surfactants may be used alone or in combination of two or more.

  The content of the nonionic surfactant is 0.1 to 10% by mass, and 0.5 to 5% by mass is more preferable from the viewpoint of the balance between detergency and other components and economic efficiency.

  The powder cleaning composition for an automatic cleaning machine of the present invention is used in an automatic cleaning machine for hard articles. Here, the hard article is an article mainly including a member having a hard surface, and includes an article having a size, shape, and material suitable for cleaning by an automatic washing machine. Moreover, the soft member may be partially contained. Specific examples of the hard article include tableware, cooking utensils, and plastic containers. Moreover, the automatic washing machine can use suitably the apparatus suitable for the automatic washing | cleaning of these hard articles. Moreover, the automatic washing machine can use suitably the apparatus suitable for the automatic washing | cleaning of these hard articles.

  Moreover, the powder cleaning composition for automatic washing machines of this invention can be made into what is called a phosphorus-free type composition which does not contain the compound containing phosphorus.

  From the viewpoint of detergency and substrate damage, the powder detergent composition for an automatic washing machine of the present invention has a pH of 10 to 13 and further 11 to 12 at 25 ° C. of a 0.1% by mass aqueous solution. preferable.

  A powder cleaning composition for an automatic cleaning machine having the composition shown in Tables 1 and 2 was prepared, and the scale adhesion inhibiting ability and cleaning performance were evaluated by the following methods. The results are shown in Tables 1 and 2.

[1] Evaluation of scale inhibition ability <Test conditions>
Washing machine used: Automatic dishwashing machine (SANIJET SD113EA6) manufactured by Nippon Washing Machine Co., Ltd.
Washing temperature: 65 ° C
Cleaning time: 45 seconds Rinsing temperature: 85 ° C
Rinsing time: 10 seconds Cleaning concentration: 0.10% by mass
Water used: 6 ° dH hard water (adjusted with calcium chloride)

<Evaluation method>
10 test pieces (100 mm x 130 mm) of SUS304 were installed at a predetermined position of the cleaning rack, and after the above test conditions, washing, rinsing, and air drying at room temperature were repeated 1000 times, the appearance of the test piece was Visual determination was made according to the following evaluation criteria. Tables 1 and 2 show the average value of 10 sheets.

<Evaluation criteria>
6: Glossy with no difference compared to before test 5: Slightly discolored but no scale attached, glossy 4: Discolored but no scale adhered, glossy 3: Part of the scale is attached, but glossy 2: The whole is covered with scale, and there is no gloss 1: The whole is covered with scale, and there is no gloss and the surface is rough. Is preferably 3 points or more that are judged to be glossy.

[2] Evaluation of detergency <Preparation of heat-denatured oil>
500 g of rapeseed oil was placed in a 1 L four-necked flask, and the mixture was stirred and mixed at 180 ° C. for 15 hours while blowing air at a flow rate of 2 L / min. To this heat-denatured oil, 0.1% of Sudan IV was added and colored red.

<Production of model dirt>
The above-mentioned colored heat-denatured oil (5 g) was uniformly applied in a circular shape having a diameter of about 10 cm with a brush to the center of a new 20 cm diameter polypropylene dish, and used as a model soil for evaluation of the cleaning property.

<Evaluation method>
62 g of the powder cleaning composition for automatic washing machines shown in Tables 1 and 2 was put into a washing tank (62 L) of an automatic dishwashing machine (SANIJET SD113EA6) manufactured by Nippon Washing Machine Co., Ltd., and dissolved in hot water at 65 ° C. . Four polypropylene dishes coated with model dirt were set on a dedicated rack, washed with a cleaning solution at 65 ° C. for 45 seconds, and then rinsed with 85 ° C. rinsing water for 10 seconds. The polypropylene dish was taken out from the dedicated rack, and the washability was visually judged by 10 researchers according to the following criteria, and the score was averaged to give an evaluation score.

<Criteria for cleaning performance>
7: No staining marks are observed on any of the four polypropylene dishes, and the dirt is removed. 6: Most stains are observed only on one of the four polypropylene dishes. 5; Most of the stains are removed to the extent that a slight coloring mark is observed on two of the four polypropylene dishes. 4; A slight coloring mark is shown on three of the four polypropylene dishes. Most of the dirt has been removed 3); almost all the dirt has been removed to the extent that slight staining marks are observed on all four polypropylene dishes 2; all four polypropylene dishes have been removed Color marks are observed, and about half of the dirt remains; all four polypropylene dishes have color marks, and most of the dirt remains. If the score is 3 or more Good.

・ A-1: Sodium salt of polyacrylic acid [weight average molecular weight 4,000, Socaran PA25CL Granules (manufactured by BASF Japan Ltd.): raw material information from the product catalog of BASF Japan Ltd.]
・ A-2: Sodium salt of acrylic acid / maleic acid copolymer (weight average molecular weight 70,000, acrylic acid / maleic acid copolymer ratio = 70/30, Socaran CP5 Granules (manufactured by BASF Japan Ltd.): (From the product catalog of BASF Japan)
Nonionic surfactant: propylene oxide / ethylene oxide / propylene oxide / block polymer [weight average molecular weight 3,100, propylene oxide / ethylene oxide ratio = 80/20, Pluronic RPE 2520 (manufactured by BASF Japan Ltd.): raw material information is BASF (From the Japan product catalog)

* 1: Sodium salt of olefin / maleic acid copolymer (weight average molecular weight 12,000, Socaran CP9 Granules (manufactured by BASF Japan Ltd.): raw material information from the product catalog of BASF Japan Ltd.)
* 2: Sodium salt of methacrylic acid homopolymer [weight average molecular weight 6,000, prepared according to the method described in JP-A-6-122894, and then used in terms of effective fraction. ]
* 3: Salt of acrylic acid / sulfonic acid monomer copolymer (weight average molecular weight 5,000, Aqualic GL386 (manufactured by Nippon Shokubai Co., Ltd.): Raw material information is from Nippon Shokubai Co., Ltd. product catalog)
* 4: Sodium salt of styrene / acrylic acid copolymer: [weight average molecular weight 30,000, prepared in accordance with the method described in JP-A-3-292400, and then used in terms of effective amount. ]

Claims (9)

(A) 8% by mass or more of a polymer selected from polyacrylic acid or a salt thereof and a copolymer of acrylic acid and maleic acid or a salt thereof, (b) a silicate 10 to 90 selected from a metasilicate and an orthosilicate Containing, by weight, and (c) carbonate,
(B) The total of silicate and (c) carbonate is 35 to 92% by mass,
(C) includes potassium carbonate;
A powder cleaning composition for an automatic cleaning machine for hard articles.   The ratio of the sum of the mass of (b) and the mass of (c) to the mass of (a) is 0.5 to 7 in terms of [mass of (b) + mass of (c)] / (a). The powder cleaning composition for automatic washing machines for hard articles according to claim 1.   The powder cleaning composition for automatic washing machines for hard articles according to claim 1 or 2, wherein the mass ratio (b) / (c) of (b) silicate to (c) carbonate is 0.6 to 45.   (D) The powder cleaning agent composition for automatic washing machines of hard articles given in any 1 paragraph of Claims 1-3 containing 1-50 mass% of organic chelating agents.   The powder cleaning composition for automatic washing machines for hard articles according to any one of claims 1 to 4, wherein (c) is potassium carbonate and sodium carbonate.   The powder cleaning composition for automatic washing machines for hard articles according to claim 5, wherein the mass ratio of sodium carbonate to potassium carbonate is 1 to 10 in terms of mass of sodium carbonate / mass of potassium carbonate. The hard article according to claim 4 , wherein the component (d) is one or more compounds selected from tetrasodium ethylenediaminetetraacetate, trisodium methylglycine diacetate, tetrasodium L-glutamate diacetate, and hydroxycarboxylate. Powder cleaning composition for automatic cleaning machines.   The powder detergent composition for automatic washing machines for hard articles according to any one of claims 1 to 7, wherein the pH of the 0.1 mass% aqueous solution is 10 to 13.   The powder cleaning composition for automatic washing machines for hard articles according to any one of claims 1 to 8, wherein the content of the component (a) is 40% by mass or less.