JP5207162B2 - Neutral liquid detergent composition for automatic dishwashers - Google Patents

Neutral liquid detergent composition for automatic dishwashers Download PDF

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JP5207162B2
JP5207162B2 JP2006315418A JP2006315418A JP5207162B2 JP 5207162 B2 JP5207162 B2 JP 5207162B2 JP 2006315418 A JP2006315418 A JP 2006315418A JP 2006315418 A JP2006315418 A JP 2006315418A JP 5207162 B2 JP5207162 B2 JP 5207162B2
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清隆 比気
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ディバーシー株式会社
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Description

  The present invention relates to a neutral liquid detergent composition for an automatic dishwashing machine having neutral liquidity, excellent environmental safety and work safety, and having excellent washing performance and storage stability comparable to an alkaline detergent.

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

  As cleaning agents used in these automatic cleaning machines, there are a powder input type, a cartridge type, a solid type and a liquid type. Among these, the powder input type, cartridge type, and solid type have complicated installation of the apparatus for supplying the cleaning agent, and the installation location is limited, while the liquid type has a small supply apparatus. Easy to install. And there are few restrictions on the installation location of the apparatus. Therefore, the use of a liquid detergent is preferred in small stores and kitchens where the space around the automatic washing machine is not sufficient.

  However, the liquid detergent usually contains 10 to 50% by mass (hereinafter referred to as “%”) of an alkali metal hydroxide salt such as sodium hydroxide or potassium hydroxide for the purpose of removing strong oil stains. The detergent containing about 5% of the alkali metal hydroxide salt is “external medicinal product”. For this reason, liquid detergents require not only special knowledge and attention from the point of view of safety, but also the alkali metal hydroxide salt erodes the surface of glass tableware and uses aluminum tableware and cooking utensils. There is a problem that there is a risk of blackening, and when it is scattered and adheres to the skin, it gives strong irritation. Furthermore, considering such safety, the plastic container is housed in a thick and sturdy plastic container, so that there is a problem that the cost is increased.

  Therefore, recently, in place of the alkali metal hydroxide salt, use of a milder alkali agent and blending of various surfactants having high cleaning performance against fat and oil stains are required. The surfactants are often foamed and are not suitable for nozzle-jet mechanical cleaning via a pump, or are easily decomposed by alkali or the like of the cleaning composition. On the other hand, those using a surfactant that does not foam or decompose have a problem that the cleaning composition is separated and precipitated, and it is difficult to obtain a homogeneous liquid cleaning composition at the time of use.

  On the other hand, for example, a two-component detergent and a detergent supply device in which a cleaning agent as a main component and a surfactant as an auxiliary cleaning component are separated have been proposed (see Patent Document 1). This product is weakly alkaline and is safer than conventional ones, but because the detergent is separated into two or more types, each component is not consumed at an equal rate and remains irregular. When trouble occurs in the operation of the dedicated detergent supply device, there is a problem that the mixing ratio of each component is disturbed and a uniform washing cannot be obtained.

  In addition, low foam nonionic surfactant, cleaning builder, specific aliphatic carboxylic acid are essential components, and the whole is homogeneous despite the relatively low amount of low foam nonionic surfactant. And a stable detergent for automatic dishwashers has been proposed (see Patent Document 2), but this has problems such as insufficient cleaning power against starch stains.

  On the other hand, for dirt such as starch, it has been proposed to add an enzyme such as amylase to the formulation (see Patent Documents 3 to 8). However, blending an enzyme into a liquid detergent has a problem of deactivation of enzyme activity during storage, and is not sufficient in terms of enzyme activity stability.

Also, a method has been proposed in which the enzyme and other components are divided into two liquids and the two liquids are charged separately so as not to impair the deterioration of the enzyme (see Patent Documents 9 and 10). Although there is little deterioration, there are problems that two supply devices are required and the merit peculiar to liquid detergents such as simplification of installation is lost.
Japanese Patent No. 2921791 Japanese Patent No. 2937635 JP 63-161092 A JP-A 63-245500 Japanese Patent Laid-Open No. 03-56600 JP-A-63-186800 Japanese National Patent Publication No. 7-505669 JP-T-2004-525219 Japanese Patent No. 3342702 Japanese National Patent Publication No. 10-509990

  Therefore, it is excellent in work safety and environmental safety, eliminating the complication of using two or more separate detergents, and a new composition that combines cleaning performance and storage stability equivalent to or better than conventional one solution. Development of a detergent composition is strongly desired. And the neutral detergent for automatic dishwashers which has the outstanding washing | cleaning performance with respect to starch stain | pollution | contamination and protein stain | pollution | contamination as well as fat and oil stains is desired.

  The present invention has been made in view of such circumstances, and is excellent in work safety and environmental safety, and has excellent cleaning performance and storage stability comparable to an alkaline cleaner, and can be used in one liquid. An objective of the present invention is to provide a neutral liquid detergent composition for automatic dishwashers.

In order to achieve the above object, the present invention contains the following components (A) to (D) at the following ratio with respect to the entire composition, and also includes the following components (E) to (G). The neutral liquid washing for automatic dishwashers characterized in that the pH of the composition at 25 ° C. (JIS-Z-8802: 1984 “pH measurement method”) is set to 6.0 to 8.0. The agent composition is the first gist.
(A) Nonionic surfactant, 1 to 15% by mass
(B) At least one organic acid selected from organic acids and water-soluble salts thereof (excluding xylene sulfonate and cumene sulfonate) , 2.5 to 15% by mass
(C) an enzyme, 1-5 wt%
(D) Water-soluble solvent, 15 to 35 % by mass
(E) Solubilizer comprising at least one of xylene sulfonate and cumene sulfonate (F) calcium additive (G) water

  In addition, among the above, the nonionic surfactant of the component (A) is preferably a polyoxyalkylene alkyl ether, a pluronic block polymer, a reverse pluronic block polymer, a polyhydric alcohol ethylene oxide propylene oxide. The neutral liquid detergent composition for automatic dishwashers which is at least 1 sort (s) chosen from the adduct and the ethylene oxide propylene oxide adduct of glycerol is made into the 2nd summary.

  Further, among these, the organic acid in the component (B) is citric acid, gluconic acid, malic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, maleic acid, methylglycine diacetic acid, Neutral liquid detergent for automatic dishwashers which is L-glutamic acid diacetic acid, glycolic acid, L-aspartic acid-N, N-diacetic acid, hydroxyethyliminodiacetic acid, 3-hydroxy-2,2'-iminodisuccinic acid The composition is a third gist, and the neutral liquid detergent composition for an automatic dishwasher in which the enzyme of the component (C) is α-amylase is the fourth gist.

And among these, in particular, the water-soluble solvent of the component (D) is ethyl alcohol, propylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethylene glycol, polyethylene glycol, an automatic dishwasher neutral liquid detergent composition is at least one selected from glycerin shall be the fifth aspect.

  The neutral liquid detergent composition for an automatic dishwasher according to the present invention is neutral in detergent stock, excellent in environmental safety and work safety, and excellent in cleaning performance comparable to an alkaline detergent. And achieve storage stability. And not only on the surface of glass tableware, aluminum tableware / cooking utensils, but also on the objects to be cleaned with gold wire, silver wire and patterns on the surface of tableware. Excellent finish.

Moreover, while the conventional cleaning composition is an alkaline cleaning composition mainly composed of an alkaline agent, the present invention is a nonionic surfactant (component A), organic acids (component B), Since it is a neutral detergent composition mainly composed of an enzyme (C component), a water-soluble solvent (D component), a specific solubilizer (E component), and a calcium additive (F component), Even if it adheres, its irritation is much lower than before. Moreover, since the activity of the enzyme used as one of the main ingredients is stably maintained over a long period of time, it has excellent cleaning properties derived from the enzyme.

  Furthermore, since it can be accommodated in a thin plastic container or a bag such as a pouch without being limited to being accommodated in a conventional thick plastic container, it is advantageous in terms of handling and cost. In addition, the load on the environment is small. And, in the conventional alkaline cleaning agent, it was necessary to neutralize the cleaning waste liquid with acid according to the waste water treatment facility, etc., but the neutral liquid cleaning composition for automatic dishwashing machine of the present invention. Then, there is an advantage that such neutralization work is not required.

  Therefore, the neutral liquid detergent composition for automatic dishwashers of the present invention is used for cleaning hard surfaces such as tableware, glass, ceramics, metals, plastics, and not only in tableware, but also in various manufacturing factories, processing factories, etc. It can also be used as an automatic washing machine for washing instruments, containers, plastic containers used for distribution, and the like. Besides, it can be widely used for washing hard surfaces such as tiles and floors in food factories and food processing factories, washing containers such as glass bottles and beer bottles for beverages, and washing 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. And since the liquid property is neutral, it can be effectively used not only for the main washing of the automatic dishwashing machine and its preliminary washing (immersion), but also for washing dishes by hand.

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

First, the neutral liquid detergent composition for automatic dishwashers of the present invention (hereinafter abbreviated as “detergent composition”) has (A) a nonionic surfactant and (B) organic acids as its main components. (C) an enzyme, (D) a water-soluble solvent, (E) a specific solubilizer, (F) a calcium additive, and (G) water.

  As the nonionic surfactant of the component (A), polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide propylene oxide adduct And ethylene oxide propylene oxide adduct of glycerin, glycerin fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and propylene glycol fatty acid ester.

  Among these, at least one of polyoxyalkylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide propylene oxide adduct, and glycerin ethylene oxide propylene oxide adduct is preferable.

  When these nonionic surfactants are described in more detail, as polyoxyethylene polyoxypropylene alkyl ether, 1 to 40 mol of ethylene oxide (EO) is added to a linear or branched alcohol having 6 to 24 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether added with 1 to 50 mol of propylene oxide (PO), 1 to 20 mol of EO and 1 to 20 mol of PO in a linear or branched alcohol having 6 to 18 carbon atoms And polyoxyethylene polyoxypropylene alkyl ether having a weight ratio of EO / PO in the range of 0.5 to 5, 1 to 15 mol of EO in a linear or branched alcohol having 6 to 18 carbon atoms Polyoxyethylene in which 1 to 50 mol of PO is added and the weight ratio of EO / PO is in the range of 0.05 to 1 Polyoxypropylene alkyl ether and the like.

  The pluronic block polymer has an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 4.0. The pluronic block polymer has an average molecular weight of 500 to 10. A pluronic block polymer having an EO content in the range of 5% to 80% of the total average molecular weight, an average molecular weight in the range of 500 to 10,000, and an EO / PO weight ratio of 0.00. Examples include pluronic block polymers in the range of 05-1.

  The reverse pluronic block polymer includes a reverse pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 1.

  Furthermore, as the EO / PO adduct of polyhydric alcohol, trimethylolpropane added with 3-45 mol of EO and 15-120 mol of PO can be mentioned. As the EO / PO adduct of glycerin, Examples include glycerin added with 3 to 45 mol of EO and 15 to 120 mol of PO.

  The nonionic surfactants are formulated for the purpose of improving detergency, oil re-adhesion preventing property and anti-foaming property, and may be used alone or in combination of two or more. May be used. In particular, the combination as described below is preferable in terms of improvement in detergency, prevention of re-adhesion of oil to the object to be washed, and foam suppression.

(1) Polyoxy having 1 to 20 mol of EO and 1 to 20 mol of PO added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO being in the range of 2 to 5 1-20 mol of EO and 1-20 mol of PO are added to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is EO of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2, polyhydric alcohol obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane -Three kinds of combinations consisting of PO adduct (b).

(2) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a straight or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO is in the range of 2 to 5. 1-20 mol of EO and 1-20 mol of PO are added to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is EO / PO adduct of glycerin in which polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and 3-45 mol of EO and 15-120 mol of PO are added to glycerin (C) 3 types of combinations.

(3) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO being in the range of 2 to 5 EO / PO weight ratio by adding 1 to 20 mol of EO and 1 to 20 mol of PO to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms Of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and linear or branched alcohol having 6 to 18 carbon atoms and 1 to 15 mol of EO and 1 to 50 of PO. And polyoxyethylene polyoxypropylene alkyl ether (a-3) having a weight ratio of EO / PO in the range of 0.05 to 0.5, 3 to 45 mol of EO in trimethylolpropane, and PO. Four combinations consisting 15 to 120 EO · PO adduct of a polyhydric alcohol obtained by adding a molar and (b).

(4) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO being in the range of 2 to 5 EO / PO weight ratio by adding 1 to 20 mol of EO and 1 to 20 mol of PO to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms Of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and linear or branched alcohol having 6 to 18 carbon atoms and 1 to 15 mol of EO and 1 to 50 of PO. And polyoxyethylene polyoxypropylene alkyl ether (a-3) having a weight ratio of EO / PO in the range of 0.05 to 0.5, 3 to 45 mol of EO and glycerin and PO 15 to 120 Four combinations consisting EO · PO adduct of glycerin was added and Le and (c).

(5) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. A polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5, and trimethylolpropane added with 3 to 45 mol of EO and 15 to 120 mol of PO. Three kinds of combinations consisting of an EO / PO adduct (b) of a monohydric alcohol.

(6) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5, and glycerol EO obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerol -3 types of combinations consisting of PO adduct (c).

(7) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. Polyoxyethylene polyoxypropylene alkyl ether (a-2), EO / PO adduct of polyhydric alcohol (b) or glycerin obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane Two kinds of combinations consisting of EO and PO adducts (c) of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to the above.

(8) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. A polyoxyethylene polyoxypropylene alkyl ether (a-2) and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 0.5 ( d-1) or a reverse pluronic block polymer (e-1) having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 0.5, and trimethylolpropane EO / PO adduct (b) of polyhydric alcohol obtained by adding 3 to 45 moles of EO and 15 to 120 moles of PO or 3 to 45 moles of EO and 15 to 12 parts of glycerin Three combinations consisting EO · PO adduct of glycerin was added and molar and (c).

(9) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. A polyoxyethylene polyoxypropylene alkyl ether (a-2) and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.5 to 4.0 ( d-2) or a reverse pluronic block polymer (e-2) having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.5 to 1.0, and trimethylolpropane EO / PO adduct (b) of polyhydric alcohol obtained by adding 3 to 45 moles of EO and 15 to 120 moles of PO, or 3 to 45 moles of EO and 15 to 120 moles of PO in glycerin. Three combinations consisting preparative EO · PO adduct of glycerin was added and (c).

(10) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. Polyoxyethylene polyoxypropylene alkyl ether (a-2), EO · PO adduct (b) of polyhydric alcohol obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane, Three combinations consisting of EO and PO adduct (c) of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerin.

(11) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. Two combinations comprising polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5.

  In particular, the combination of any of the above (5), (6), (7), (8), (10) and (11) is particularly suitable from the viewpoint of cleaning performance and foam suppression.

  The compounding quantity of the nonionic surfactant which is such (A) component is set in the range of 1 to 15% with respect to the whole cleaning composition. That is, when the blending amount is less than 1%, the desired cleaning performance is poor. On the other hand, when it exceeds 15%, the stability of the cleaning agent system is deteriorated from the overall balance, and a synergistic effect with other components is further obtained. Because it is not possible. In particular, setting in the range of 3 to 10% is preferable in terms of cleaning performance, stability of the cleaning agent system, and cost.

The organic acids (B) used in the present invention are blended for the purpose of improving the cleaning performance. Specifically, citric acid, gluconic acid, malic acid, succinic acid, tartaric acid, fumaric acid Lactic acid, maleic acid, methylglycine diacetic acid, L-glutamic acid diacetic acid, glycolic acid, L-aspartic acid-N, N-diacetic acid, hydroxyethyliminodiacetic acid, 3-hydroxy-2, '2-iminodisuccinic acid, Organic consisting of hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, dihydroxyethylglycine, 1,3-diaminopropanetetraacetic acid, 2-hydroxy-1,3-diaminopropanetetraacetic acid, dihydroxyethylethylenediaminediacetic acid, triethylenetetraminehexaacetic acid Examples thereof include acids or water-soluble salts thereof. However, xylene sulfonate and cumene sulfonate which are solubilizers of the component (E) described later are excluded.

  These organic acids may be used singly or in combination of two or more. Among them, citric acid, gluconic acid, malic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, maleic acid, methylglycine Organic acid consisting of diacetic acid, L-glutamic acid diacetic acid, glycolic acid, L-aspartic acid-N, N-diacetic acid, hydroxyethyliminodiacetic acid, 3-hydroxy-2,2'-iminodisuccinic acid or water-soluble salt thereof Are preferably used alone or in combination of two or more from the viewpoint of enzyme stability, stability of the detergent system, washing performance, and cost.

  In particular, from the viewpoint of cleaning performance and solubility of the cleaning composition, at least a part of the organic acids is at least one of sodium salt, potassium salt, ammonium salt, magnesium salt, amine salt, and ethanolamine salt. Preferably there is.

  The blending amount of the organic acids is set in a range of 2.5 to 15% with respect to the entire cleaning composition. That is, when the blending amount is less than 2.5%, it is difficult to obtain sufficient cleaning performance. On the other hand, when the blending amount exceeds 15%, the stability of the cleaning agent system is deteriorated from the overall balance. Especially, it is preferable to set to 4 to 12% from the point of washing | cleaning performance and stability of a cleaning agent system.

  Furthermore, examples of the enzyme of component (C) used in the present invention include amylase, protease, lipase, cellulase, glucanase, etc. Among them, amylase, protease, and lipase are preferably used from the viewpoint of washing performance and cost. It is done. These enzymes are used to obtain a specific cleaning effect that is difficult to supplement with other detergent components by the enzyme activity. From the viewpoint of the effect and cost, it is particularly preferable to use α-amylase. is there.

These enzymes may be used alone or in combination of two or more, and the blending amount thereof is set in the range of 1 to 5% with respect to the entire cleaning composition. That is, when the blending amount is less than 0.5%, the improvement in cleaning performance is poor due to the balance with other components. On the other hand, when the blending amount exceeds 5%, the synergistic effect with other components cannot be obtained any more, and the cost is low. This is also disadvantageous. Especially, it is preferable to set to the range of 1-3% from the point of washing | cleaning performance and a cost surface.

Examples of the water-soluble solvent of component (D) used in the present invention include alcohol solvents and glycol ether solvents. Examples of alcohol solvents include ethyl alcohol, isopropanol, 3-methoxybutanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and 1,3-butylene glycol. 1,4-butanediol, 1,5-pentanediol, hexylene glycol, glycerin and the like.

  Examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol. Dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, polyethylene glycol mono Chirueteru, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol and the like.

  These water-soluble solvents are used to keep the system stable, and may be used alone or in combination of two or more. Among them, it is possible to use enzyme alone or in combination of two or more of ethyl alcohol, propylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethylene glycol, polyethylene glycol and glycerin. From the viewpoint of stability and stability of the detergent system.

The blending amount of the water-soluble solvent is set within a range of 15 to 35 % with respect to the entire cleaning composition. That is, when the blending amount is less than 10%, it is difficult to obtain sufficient enzyme stability. On the other hand, when the blending amount exceeds 40%, further improvement in enzyme stability cannot be obtained, and the stability of the detergent system from the overall balance. Because it gets worse. And it is preferable to set it to the range of 15 to 35% from the point of the improvement of enzyme stability and a cost aspect, and it is further more preferable to set to the range of 20 to 30%.

Furthermore, the solubilizer of the component (E) used in the present invention can stably mix the nonionic surfactant as the component (A) and the organic acid as the component (B) in the cleaning composition. that is solubilized is blended for the purpose, in particular, xylene sulfonate, cumene sulfonate and the like. These may be used alone or in combination of two or more.

  In addition, the calcium additive of component (F) used in the present invention is blended in the detergent composition for the purpose of stably maintaining the activity of the enzyme that is component (C). Specifically, calcium chloride, calcium formate, calcium acetate, calcium lactate, calcium phosphate, calcium citrate, calcium gluconate, calcium sulfate, calcium hydroxide and the like can be mentioned. These may be used alone or in combination of two or more, but calcium chloride is preferably used from the viewpoint of solubility in a detergent system.

  And as water of (G) component used for this invention, a tap water, soft water, ion-exchange water, a pure water, purified water etc. are mention | raise | lifted, Preferably a soft water, ion-exchange water, and a pure water are used. These may be used alone or in combination of two or more. The “water” is the total of water contained in the form of crystal water or aqueous solution derived from each component constituting the liquid detergent composition and water added from the outside, and the entire detergent composition is 100. %.

  In the cleaning composition of the present invention, pH adjusters, polymer chelating agents, dyes, fragrances, metal corrosion inhibitors, bactericides, deodorants, antistatic agents, and the like can be used as optional components. .

  Among these, examples of the pH adjuster include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, silicates such as sodium silicate and potassium silicate, and carbonates such as sodium carbonate and potassium carbonate. . Of these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferably used from the viewpoint of storage stability and cost of the detergent system. In order to adjust the pH of the liquid detergent composition of the present invention, the pH of the detergent stock solution (JIS-Z-8802 “pH measurement method”, hereinafter the same) is 25 ° C., 6.0 to 8. An appropriate amount is added as appropriate so that it becomes zero.

  Examples of the polymer chelating agent include acrylic acid polymer and salts thereof, maleic acid polymer and salts thereof, acrylic acid-maleic acid copolymer and salts thereof, poly-α-hydroxyacrylic acid and salts thereof, acrylic Examples include acid-maleic acid-polyethylene glycol copolymers and salts thereof, olefin-maleic acid copolymers and salts thereof, and acrylic acid-sulfonic acid copolymers and salts thereof. Examples of these salts include sodium salts, potassium salts, ammonium salts, and ethanolamine salts. These are formulated for the purpose of improving the sequestering ability, threshold effect, water-insoluble substance dispersion performance, anti-redeposition property, and cleaning performance. They can be used alone or in combination of two or more. It is done.

  The cleaning composition of the present invention is obtained using the essential components (A) to (G) and the optional components added as necessary, and is excellent in environmental safety and work safety. Excellent cleaning performance and appearance comparable to alkaline detergents, and excellent enzyme activity stability, storage stability, and finish after rinsing.

  And while the conventional cleaning composition was an alkaline cleaning composition mainly composed of an alkaline agent, the present invention combines the above-mentioned specific essential components (A) to (G). In addition, since it is a neutral detergent composition, even if it may adhere to the skin, its irritation is much lower than before. Even if it adheres to the skin, its irritation is much lower than before. Moreover, since the activity of the enzyme used as one of the main ingredients is stably maintained over a long period of time, it has excellent cleaning properties derived from the enzyme.

  And, since it can be accommodated in a thin plastic container or a bag such as a pouch without being restricted in conventional thick plastic containers, it is advantageous in terms of handling and cost. In addition, the load on the environment is small. And, in the conventional alkaline cleaning agent, it was necessary to neutralize the cleaning waste liquid with acid according to the wastewater treatment facility, etc., but in the cleaning composition of the present invention, such neutralization operation is also necessary. It has the advantage of not.

  Therefore, the cleaning composition of the present invention is used for cleaning hard surfaces such as tableware, glass, ceramics, metals, plastics, and not only for tableware, but also for appliances, containers, and distribution in various manufacturing factories and processing factories. It can also be used as an automatic washing machine for washing plastic containers. Besides, it can be widely used for washing hard surfaces such as tiles and floors in food factories and food processing factories, washing containers such as glass bottles and beer bottles for beverages, and washing 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. And since the liquid property is neutral, it can be effectively used not only for the main washing of the automatic dishwashing machine and its preliminary washing (immersion), but also for washing dishes by hand.

Next, examples will be described together with reference examples and comparative examples. However, the present invention is not limited to these.

[Examples 1 36 Reference Examples 1-3, Comparative Examples 1-10]
49 types of cleaning compositions of Examples 1 to 36, Reference Examples 1 to 3 and Comparative Examples 1 to 10 shown in Tables 1 to 9 below were prepared. And while measuring and evaluating the pH, seven items, storage stability, enzyme-activity stability, foam suppression property, washing | cleaning performance, the finishing property after washing | cleaning, the influence with respect to glass, and scale formation suppression ability, were evaluated. The results are also shown in Tables 1 to 9 below.

  In addition, the components used in Tables 1 to 9 below and their effective pure content (% by mass) are as follows, and the numerical values in the table are shown as they are. Further, “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 liquid detergent composition and water added from the outside, and the entire detergent composition Is shown as a balance to be 100%. The number of moles of EO added to the surfactant is indicated by “p”, and the number of moles of PO added is indicated by “q”.

[Component A]
・ Nonionic surfactant 1:
Polyoxyethylene (p = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14, 15) ether EO / PO weight ratio = 1.26
Prototype / Nonionic Surfactant 2:
Polyoxyethylene (p = 8) Polyoxypropylene (q = 6) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 1.01 Cloud point = 31 ° C.
Product name: Pepol AS-054C (manufactured by Toho Chemical Industry Co., Ltd.)
Nonionic surfactant 3:
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.11 Average molecular weight = 2,000 Cloud point 24 ° C.
Product name: Pluronic PE6100 (manufactured by BASF)
Nonionic surfactant 4:
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
Average molecular weight = 2,800 EO / PO weight ratio = 0.11
Product name: Pluronic RPE2510 (manufactured by BASF)
Nonionic surfactant 5:
Trimethylolpropane EO / PO adduct represented by the following chemical formula (1) Average molecular weight = 4,500 EO / PO weight ratio = 0.21
Prototype

Nonionic surfactant 6:
Glycerin EO / PO adduct represented by the following chemical formula (2)

[B component]
·citric acid:
Product name: Citric acid (crystal) (manufactured by Iwata Chemical Industry Co., Ltd.)
・ Sodium citrate:
Product name: Trisodium citrate (crystal, manufactured by Iwata Chemical Industry Co., Ltd.)
・ Potassium citrate:
Product name: Tripotassium citrate (manufactured by Showa Kako)
・ Sodium gluconate:
Product name: Sodium Gluconate (Fujisawa Pharmaceutical Co., Ltd.)
・ Sodium malate:
Product name: Sodium malate (manufactured by Fuso Chemical Industries)
・ Sodium lactate:
Product name: Sodium lactate (50%, manufactured by Fuso Chemical Industry Co., Ltd.)
Content: 50.0%
・ Hydroxyethyliminodiacetic acid disodium:
Product name: Clewat Bi-HDS (manufactured by Nagase ChemteX Corporation)
Content: 26.0%
L-aspartic acid-N, N-diacetic acid tetrasodium salt:
Product name: Clewat Bi-ADS (manufactured by Nagase ChemteX Corporation)
Content: 45.1%
・ Methyldiglycine diacetate sodium:
Product Name: Torriron M (BASF)

[C component]
・ Amylase 1:
Product name: Termamyl Ultra 300L (Novozyme)
Amylase 2:
Product name: Puraster ST15000L (Genencore Kyowa)
Amylase 3:
Product name: Puraster HPAm5000L (Genencore Kyowa)
Amylase 4:
Product Name: Stainzyme 12L (Novozyme)
・ Protease 1:
Product name: Sabinase Ultra 16L (Novozyme)
・ Protease 2:
Product name: Purefect 4000L (Genencor Kyowa)
・ Lipase:
Product name: Lipolase 100L (Novozyme)

[D component]
·Propylene glycol:
Product name: Propylene glycol (Mitsui Takeda Chemical)
·ethylene glycol:
Product name: Ethylene glycol (Nippon Shokubai Co., Ltd.)
・ Polyethylene glycol:
Product name: PEG200 (Daiichi Kogyo Seiyaku Co., Ltd.)
·ethanol:
Product name: General 95 degree synthetic unmodified alcohol (manufactured by Nippon Alcohol Sales Co., Ltd.)
・ Glycerin:
Product name: Purified glycerin (Sakamoto Pharmaceutical Co., Ltd.)
・ Ethylene glycol monoethyl ether Product name: Seafosol MG (Nippon Shokubai Co., Ltd.)
・ Diethylene glycol monoethyl ether Product name: Seafosol DG (manufactured by Nippon Shokubai Co., Ltd.)
・ Dipropylene glycol monomethyl ether Product name: Methyl propylene diglycol (manufactured by Nippon Emulsifier Co., Ltd.)

[E component]
-Sodium xylene sulfonate Product name: Eltesol SX-93 (manufactured by Huntsman)
-Sodium cumene sulfonate Product name: Eltesol SC-93 (manufactured by Huntsman)

[F component]
・ Calcium chloride:
Product name: Calcium chloride [granular] (manufactured by Central Glass Co., Ltd.)
Content: 74.3% as anhydride

[G component]
Water: Ion exchange water

The test method and evaluation method for each item are as shown below.
[PH measurement]
Measurement Method Using a pH meter (pH METER F-12, manufactured by HORIBA, Ltd.), the pH value at 25 ° C. of the stock solution of the prepared cleaning composition was measured according to JIS Z-8802: 1984.
A: 6.0 or more and 6.0 or less. X: Less than 6.0 or more than 8.0.

[Storage stability]
Test method The prepared cleaning composition is placed in a 100 ml glass bottle and placed in a constant temperature bath (SLI-4S, manufactured by Sunaka Rika Kogyo Co., Ltd.) in an atmosphere of 40 ° C., and an incubator (MTH-2400, manufactured by SANYO). ) Under a program-controlled atmosphere from -5 ° C to 5 ° C and stored in that state for one month. And the external appearance was observed visually and evaluated by the following evaluation criteria.
・ Evaluation criteria ◎: After 1 month, there was no change in appearance such as separation / precipitation.
○: After one month, slight changes in appearance such as separation / precipitation were observed.
Δ: After 2 weeks, slight changes in appearance such as separation or precipitation were observed.
×: Immediately after blending, there was a change in appearance such as separation or precipitation.

[Enzyme activity stability]
Test method In the above storage stability evaluation test, the enzyme activity value of α-amylase in the detergent composition after 2 weeks at 40 ° C. was determined, and the residual rate was calculated from the enzyme activity values before and after storage. It was evaluated as follows. However, the enzyme activity value was determined as follows.
-Determination of enzyme activity value A tablet (Fadebas tablet) containing an indicator that develops color by the decomposition of starch and starch was put into the detergent aqueous solution, and the concentration of the dye after a predetermined time was measured.
-Evaluation criteria A: Residual rate is 70% or more.
○: Residual rate is 50% or more and less than 70%.
Δ: Residual rate is 25% or more and less than 50%.
X: Remaining rate is less than 25%.

[Foam suppression]
・ Test method Using tap water, dilute the detergent composition to 0.20%, pour 50 ml into a colorimetric tube with a capacity of 100 ml, cap it, and keep it warm at 45 ° C. for 1 hour. Held at 0C. The height of the bubble immediately after the colorimetric tube was shaken up and down 30 times (reciprocating) at a rate of 3 times per second (reciprocating) was measured and judged according to the following criteria.
Evaluation criteria A: Bubble height is less than 6 mm.
○: The height of the foam is 6 mm or more and less than 11 mm.
(Triangle | delta): The height of a bubble is 11 mm or more and less than 16 mm.
X: The bubble height is 16 mm or more.

[Cleaning performance]
Test Method The prepared cleaning composition was put into a commercial automatic dishwasher (DW-DR61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. Then, the following objects to be cleaned were washed as a set of 10 porcelain dishes or teacups, and the cleaning performance was evaluated according to the evaluation criteria described later. In addition, three types of dirt, beef tallow dirt, egg yolk dirt, and porridge dirt were prepared, and cleaning evaluation was performed on each dirt.
* Operating condition Detergent concentration: 0.20%
Washing temperature: 45 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 30 seconds, rinsing: 8 seconds)
Of use water hardness (as CaCO 3) 50~60ppm
Beef tallow dirt: A porcelain dish having a diameter of 25 cm and purified beef tallow attached to 4 g / sheet was used.
Egg stain: Egg yolk of chicken egg was attached to a porcelain dish having a diameter of 25 cm so as to be 4 g / sheet, dried at normal temperature for 1 hour, and immersed at 40 ° C. for 30 minutes immediately before washing.
Porridge: Put 40 g of cooked rice in 400 g of hot water and boil it for 20 minutes at 90-100 ° C., then attach the supernatant to the tea bowl at 0.6 g / piece and dry it at room temperature for 30 minutes. What was immersed in 40 degreeC for 10 minutes just before washing | cleaning was used.
・ Evaluation criteria For beef tallow dirt, apply oil red liquid to the washed porcelain dish. For pork dirt, apply iodine solution to the washed tea bowl. The degree of dirt removal was judged.
A: 90% or more of dirt is removed.
○: Dirt removal of 70% or more and less than 90%.
Δ: Dirt removal of 50% or more and less than 70%.
X: Dirt removal of less than 50%.

[Finishability after washing]
Test Method The prepared cleaning composition was charged into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following conditions. And the glass cup which is a to-be-cleaned object shown below was wash | cleaned as 1 set, and the finishing performance after washing | cleaning was evaluated by the evaluation criteria of a postscript.
* Operating condition Detergent concentration: 0.20%
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) 50~60ppm
Object to be washed: Milk was poured into a glass cup (manufactured by Sasaki Glass Co., Ltd.) of 227 g (= 8 ounces) and left for 5 minutes. Then, after discarding the milk, it was air-dried for 30 minutes without rinsing with water.
・ Evaluation criteria A: No water spots are seen.
○: 1 to 2 water spots are seen.
Δ: 3 to 5 water spots are seen.
X: Six or more water spots are seen.

[Influence on glass surface]
Test Method A commercially available 227 g (= 8 ounce) tumbler glass (manufactured by HOYA) was immersed in the prepared cleaning composition under the following conditions. And the state of the tumbler glass after immersion was observed visually, and the following evaluation criteria evaluated.
* Soaking conditions Detergent concentration: 0.20%
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.

[Scale generation suppression performance]
Test method The detergent composition was diluted to 0.20% using artificial hard water (total hardness: 250 mg / L), 50 ml was poured into a colorimetric tube having a capacity of 100 ml, and kept at 60 ° C. for 4 hours. The production amount of 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.

  From the above results, it can be seen that all of the example products show excellent characteristics in all the evaluation items. On the other hand, the comparative example product does not contain the essential components of the present invention, or even if blended, the ratio is out of the scope of the present invention. You can see that

Claims (5)

  1. The following components (A) to (D) are contained in the following proportion with respect to the entire composition, and the following components (E) to (G) are contained. -8802: 1984 "pH measurement method") is set to 6.0 to 8.0, a neutral liquid detergent composition for an automatic dishwasher.
    (A) Nonionic surfactant, 1 to 15% by mass
    (B) At least one organic acid selected from organic acids and water-soluble salts thereof (excluding xylene sulfonate and cumene sulfonate) , 2.5 to 15% by mass
    (C) an enzyme, 1-5 wt%
    (D) Water-soluble solvent, 15 to 35 % by mass
    (E) Solubilizer comprising at least one of xylene sulfonate and cumene sulfonate (F) calcium additive (G) water
  2.   The nonionic surfactant of the component (A) is a polyoxyalkylene alkyl ether, a pluronic block polymer, a reverse pluronic block polymer, an ethylene oxide propylene oxide adduct of polyhydric alcohol, or an ethylene oxide propylene oxide adduct of glycerin. The neutral liquid detergent composition for an automatic dishwasher according to claim 1, which is at least one selected.
  3.   The organic acid in the component (B) is citric acid, gluconic acid, malic acid, succinic acid, tartaric acid, fumaric acid, lactic acid, maleic acid, methylglycine diacetic acid, L-glutamic acid diacetic acid, glycolic acid, L-aspartic acid. The neutral liquid detergent composition for an automatic dishwasher according to claim 1 or 2, which is -N, N-diacetic acid, hydroxyethyliminodiacetic acid, or 3-hydroxy-2,2'-iminodisuccinic acid.
  4. The neutral liquid detergent composition for an automatic dishwasher according to any one of claims 1 to 3, wherein the enzyme of the component (C) is α-amylase.
  5.   The water-soluble solvent of the component (D) is at least one selected from ethyl alcohol, propylene glycol, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethylene glycol, polyethylene glycol, and glycerin. Item 5. A neutral liquid detergent composition for an automatic dishwasher according to any one of Items 1 to 4.
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JP5148410B2 (en) * 2008-08-25 2013-02-20 花王株式会社 Liquid detergent composition for dishwashers
JP5324207B2 (en) * 2008-12-19 2013-10-23 ディバーシー株式会社 Process for producing solid detergent for automatic dishwasher and solid detergent for automatic dishwasher obtained thereby
GB0917740D0 (en) 2009-10-09 2009-11-25 Reckitt Benckiser Nv Detergent composition
WO2011110593A1 (en) * 2010-03-12 2011-09-15 Purac Biochem Bv Stabilised enzyme-containing liquid detergent composition
TR201810936T4 (en) * 2010-04-23 2018-08-27 Procter & Gamble Detergent composition.
DE102010029348A1 (en) * 2010-05-27 2011-12-08 Henkel Ag & Co. Kgaa Dishwasher detergent
JP5634761B2 (en) * 2010-06-18 2014-12-03 花王株式会社 Liquid detergent composition for automatic dishwashers
GB201016001D0 (en) * 2010-09-23 2010-11-10 Innospec Ltd Composition and method
JP5579593B2 (en) * 2010-12-22 2014-08-27 ニュートリー株式会社 Jelly cleaning composition
DE102012107728A1 (en) * 2012-08-22 2014-02-27 Witty-Chemie Gmbh & Co. Kg Cleaning agent useful for dishwashing device, comprises enzyme, phosphorus-free complexing agent, nonionic surfactant, propylene glycol, and remaining amount of water, enzyme stabilizer, solubilizer and optionally dye and/or reducing agent
JP6321354B2 (en) 2012-12-05 2018-05-09 花王株式会社 Steel sheet cleaner
ES2539732B1 (en) * 2013-06-28 2016-02-05 Kao Corporation, S.A. liquid detergent composition
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JP6188239B2 (en) * 2014-07-08 2017-08-30 ライオン株式会社 Liquid cleaning agent
JP6581785B2 (en) * 2015-03-17 2019-09-25 シーバイエス株式会社 Liquid detergent composition for hard surface, dishwashing method using the same, and medical instrument washing method
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