Detergent composition for washing machine

Abstract

To provide a detergent composition for a washing machine having detergency and excellent in sterilizing performance.SOLUTION: The detergent composition for washing machines comprises (a) a nonionic surface active agent represented by general formula (a1), (b) a cationic surface active agent and (c) a chelating agent. R1a-O - (EO) a (AO) b - H (a1) wherein R1a is a hydrocarbyl group having 8 or more and 18 or less carbon atoms, EO is an ethyleneoxy group, AO is a propyleneoxy group or a butyleneoxy group, EO and AO may be block-bonded or randomly added, and either EO or AO may be added first. A and b each represent an average number of moles added, and each independently represent a number of 1 or more and 50 or less. (I) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a detergent composition for a washing machine and a cleaning method using a washing machine, and further to a detergent composition for an industrial washing machine and a cleaning method using an industrial washing machine, and particularly to a detergent composition for an industrial washing machine for cleaning containers (e.g., food containers, trays, or baskets) or food processing utensils used in food processing factories, preferably plastic food containers, and a cleaning method for an industrial washing machine using the detergent composition. [Background technology]

[0002] Washing machines are known that automatically wash various items, such as commercial plastic containers and tableware, used in food processing factories. Because commercial washing machines require short washing times, the detergents used in these machines are required to have excellent cleaning power (e.g., Patent Documents 1 to 7). Commercial washing machines achieve high cleaning power and short washing times by increasing the temperature of the cleaning solution prepared by diluting the detergent with water, or by using steam as a heat source in some factories. However, increasing the temperature of the cleaning solution leads to the consumption of large amounts of fossil fuel resources, and since electricity is also generated from fossil fuels, increased power consumption leads to increased carbon dioxide emissions. Therefore, in recent years, with a view to achieving a sustainable society, there has been a demand for lowering the temperature of the cleaning solution and reducing power consumption.

[0003] Patent Document 1 discloses a liquid detergent composition having a pH of 11 or higher, which contains specific amounts of (A) a dioctyldimethylammonium salt, (B) a nonionic surfactant, (C) an amphoteric surfactant, (D) an alkaline agent, and (E) a chelating agent. Patent Document 2 discloses a self-emulsifying composition containing specific amounts of a) one or more polyolefins, b) one or more polymeric emulsifiers Px, c) one or more oils Ox, d) one or more surfactants Sx, e) one or more additives Ax, and f) water. Patent Document 3 discloses a detergent composition containing a surfactant system including a mixture of a specific isoprenoid surfactant and 5% to 97% of one or more non-isoprenoid surfactants, and one or more cleaning auxiliary additives. Patent Document 4 discloses a laundry detergent or cleaning composition containing a copolymer composition containing two specific copolymers. Patent Document 5 discloses a detergent composition for dishwashing machines, which comprises (a) at least one disinfecting component selected from cationic disinfectants and amphoteric disinfectants, and (b) at least one cleaning component selected from nonionic surfactants, anionic surfactants, and amphoteric surfactants. Patent Document 6 discloses a liquid detergent composition containing a surfactant-solubilized solution in which an anionic surfactant (b) and a cationic surfactant (c) are solubilized in a liquid (a) consisting of water or water and a water-soluble solvent, resulting in a transparent, homogeneous solution. Patent Document 7 discloses an aqueous liquid detergent containing specific amounts of (a) an alkaline agent, (b) a cationic disinfectant, (c) a metal chelating agent, (d) a low-foaming nonionic surfactant, (e) a specific fatty acid or a salt thereof, and (f) glycols. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent Publication No. 2021-95550 [Patent Document 2] Special Publication No. 2015-502994 [Patent Document 3] Special Publication No. 2014-534279 [Patent Document 4] Special Publication No. 2011-503285 [Patent Document 5] Japanese Patent Application Laid-Open No. 2004-263013 [Patent Document 6] Japanese Patent Application Laid-Open No. 2002-129189 [Patent Document 7] Japanese Patent Application Laid-Open No. 2000-96098 Summary of the Invention [Problem to be solved by the invention]

[0005] As a method for suppressing carbon dioxide emissions in a cleaning machine, it is possible to reduce power consumption and, in some factories, reduce dependence on steam obtained by directly burning fossil fuels. To achieve this, it is conceivable to shorten the cleaning time or lower the temperature of the cleaning solution. However, a decrease in the temperature of the cleaning solution directly affects the deterioration of cleaning power and sterilizing power. Therefore, in order to obtain cleaning power and sterilizing power equal to or greater than conventional cleaning power and sterilizing power even when the temperature of the cleaning solution in the cleaning machine is lowered, further improvements in cleaning power and sterilizing performance are required for the cleaning agent composition for the cleaning machine. The present invention provides a detergent composition for a washing machine having detergency and excellent sterilizing performance, and a cleaning method. [Means for solving the problem]

[0006] The present invention relates to a detergent composition for a washing machine, which contains (a) a nonionic surfactant represented by the following general formula (a1), (b) a cationic surfactant, and (c) a chelating agent: R 1a -O-(EO) a (AO) b -H (a1) [In the formula, R 1a is a hydrocarbon group having 8 to 18 carbon atoms, EO is an ethyleneoxy group, and AO is a propyleneoxy group or a butyleneoxy group, and EO and AO may be bonded in a block bond or added randomly, and either EO or AO may be added first. a and b are the average number of moles added, and are each independently a number of 1 to 50.

[0007] The present invention also relates to a cleaning method, which comprises using a cleaning machine to prepare a cleaning liquid by diluting a cleaning machine detergent composition containing (a) a nonionic surfactant represented by the above general formula (a1), (b) a cationic surfactant, and (c) a chelating agent with water, and then cleaning an object to be cleaned with the cleaning liquid. [Effects of the Invention]

[0008] According to the present invention, there are provided a cleaning agent composition for a washing machine having detergency and excellent sterilizing performance, and a cleaning method. DETAILED DESCRIPTION OF THE INVENTION

[0009] The cleaning liquid used in washing machines, particularly commercial washing machines, has conventionally been heated to about 60° C. The detergent composition for a washing machine of the present invention not only has excellent detergency and sterilizing performance at conventional use temperatures, but also maintains excellent detergency and sterilizing performance even when the cleaning liquid is at a relatively low temperature (for example, about 45° C.), thereby contributing to a sustainable society. Furthermore, this can further reduce the operating costs of the washing machine. Furthermore, the detergent composition for a washing machine of the present invention has excellent rinsing properties, which not only contributes to water saving but also is expected to shorten the time from the start of washing to finishing.

[0010] The mechanism by which the cleaning machine detergent composition of the present invention has excellent detergency and bactericidal performance, particularly the mechanism by which the cleaning machine detergent composition of the present invention has excellent detergency and bactericidal performance without increasing the temperature of the cleaning liquid containing the composition, is not clear, but is presumed to be as follows. Component (a) has high emulsifying power, and because component (a) is a surfactant with low foaming and anti-foaming properties, it maintains its cleaning power without causing a decrease in mechanical strength due to foaming, and component (b) has high bactericidal performance, so it is thought to achieve both high cleaning performance and improved bactericidal properties. The cleaning machine detergent composition and cleaning method of the present invention are not limited to the above-mentioned mechanism of action.

[0011] <Cleaning agent composition for cleaning machines> The cleaning machine detergent composition of the present invention contains (a) a nonionic surfactant represented by the following general formula (a1) [hereinafter referred to as component (a)], (b) a cationic surfactant [hereinafter referred to as component (b)], and (c) a chelating agent [hereinafter referred to as component (c)]. R 1a-O-(EO) a (AO) b -H (a1) [In the formula, R 1a is a hydrocarbon group having 8 to 18 carbon atoms, EO is an ethyleneoxy group, and AO is a propyleneoxy group or a butyleneoxy group, and EO and AO may be bonded in a block bond or added randomly, and either EO or AO may be added first. a and b are the average number of moles added, and are each independently a number of 1 to 50.

[0012] <Component (a)> The component (a) is a nonionic surfactant represented by the above general formula (a1). One or more types of component (a) can be used. In general formula (a1), R 1a R is a hydrocarbon group, preferably an alkyl group, having a molecular weight of 8 or more, preferably 10 or more, from the viewpoint of further improving the cleaning properties, and having a molecular weight of 18 or less, preferably 14 or less, from the viewpoint of further improving the foam suppressing properties and the blending stability. 1a R bonds to the oxygen atom of -O- 1a The carbon atom is preferably a primary carbon atom or a secondary carbon atom, more preferably a secondary carbon atom. In the general formula (a1), the bonding order of EO and AO is not particularly limited, but it is more preferable that the terminal is AO from the viewpoint of foam suppression. 1a A compound in which EO and AO are bonded to —O— in this order is preferred, where AO is a propyleneoxy group or a butyleneoxy group, and preferably a propyleneoxy group. In general formula (a1), a and b represent the average number of moles added, and from the viewpoint of further improving the cleaning ability, they are each independently 1 or more, preferably 3 or more, more preferably 5 or more, and from the viewpoint of further improving the foam-suppressing ability, they are 50 or less, preferably 30 or less, more preferably 10 or less. In general formula (a1), the sum of a and b (a+b) is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more, from the viewpoint of further improving cleansing ability, and is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and even more preferably 20 or less, from the viewpoint of further improving foam-suppressing ability.

[0013] More specifically, the component (a) is preferably one or more nonionic surfactants selected from the following (a1-1) and (a1-2), and more preferably one or more selected from (a1-2) in order to further enhance cleaning properties and anti-foaming properties.

[0014] (a1-1): In the general formula (a1), R 1a is a hydrocarbon group having 8 to 18 carbon atoms, and R 1a a nonionic surfactant having a propyleneoxy group and / or an ethyleneoxy group bonded to a primary carbon atom of the formula (a1-1), preferably a nonionic surfactant represented by the following general formula (a1-1): R 1a -O-(EO) g -(PO) h -(EO) i -H (a1-1) [In the formula, R 1a is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, and R 1a R bonds to the oxygen atom of -O- 1a is a primary carbon atom, EO is an ethyleneoxy group, PO is a propyleneoxy group, g, h, and i are the average number of moles added, g is 1 or more and 10 or less, preferably 2 or more and 10 or less, more preferably 3 or more and 8 or less, h is 1 or more and 6 or less, preferably 1 or more and 4.5 or less, more preferably 1 or more and 3 or less, i is 1 or more and 12 or less, preferably 2 or more and 10 or less, more preferably 3 or more and 8 or less, and the sum of g, h, and i (g+h+i) is 3 or more and 28 or less, preferably 3 or more and 20 or less, more preferably 4 or more and 15 or less.

[0015] (a1-2): In the general formula (a1), R 1ais a hydrocarbon group having 8 to 18 carbon atoms, and R 1a a nonionic surfactant having a propyleneoxy group and / or an ethyleneoxy group bonded to a secondary carbon atom of the formula (a1-2), preferably a nonionic surfactant represented by the following general formula (a1-2): R 1a -O-(EO) j -(PO) k -H (a1-2) [In the formula, R 1a is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group having 10 to 14 carbon atoms, and R 1a R bonds to the oxygen atom of -O- 1a is a secondary carbon atom, EO is an ethyleneoxy group, PO is a propyleneoxy group, j and k are the average number of moles added, j is 1 or more and 15 or less, preferably 2 or more and 12 or less, more preferably 4 or more and 10 or less, and even more preferably 5 or more and 10 or less, k is 1 or more and 15 or less, preferably 2 or more and 12 or less, more preferably 4 or more and 10 or less, and even more preferably 6 or more and 10 or less, and the sum of j and k (j+k) is 2 or more and 30 or less, preferably 2 or more and 20 or less, more preferably 4 or more and 18 or less, and even more preferably 10 or more and 16 or less.

[0016] <(b) Component> Component (b) is a cationic surfactant. One or more types of component (b) can be used. From the viewpoint of bactericidal activity, component (b) is preferably one or more types selected from compounds represented by the following general formula (b1) and compounds represented by the following general formula (b2), and more preferably one or more types selected from compounds represented by general formula (b2).

[0017] [ka]

[0018] [In the formula, R 1b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 2bis a group selected from an aliphatic hydrocarbon group having from 8 to 18 carbon atoms, an alkyl group having from 1 to 3 carbon atoms, and a hydroxyalkyl group having from 1 to 3 carbon atoms, and R 3b and R 4b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, and X - is an anion.

[0019] [ka]

[0020] [In the formula, R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, and R 6b and R 7b are each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms, and X - is an anion.

[0021] In general formula (b1), R 1b From the viewpoint of further enhancing sterilizing and cleaning properties, the number of carbon atoms in R is preferably 9 or more, more preferably 10 or more, even more preferably 12 or more, and preferably 16 or less. 1b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group. In general formula (b1), R 2b is a group selected from aliphatic hydrocarbon groups having 8 to 18 carbon atoms, alkyl groups having 1 to 3 carbon atoms, and hydroxyalkyl groups having 1 to 3 carbon atoms. R 2b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms, R 2b From the viewpoint of further enhancing the bactericidal and cleaning properties, is preferably an alkyl or alkenyl group having 8 or more carbon atoms, and preferably 14 or less, more preferably 12 or less, and is preferably an alkyl group.

[0022] In general formula (b1), R 3b and R 4bare each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 3b and R 4b are preferably each independently a group selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0023] In general formula (b1), X - is an anion. Examples of anions include halide ions and alkyl sulfate ions having 1 to 3 carbon atoms. Examples of halide ions include chloride ions, bromide ions, and iodide ions. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0024] Preferred compounds represented by general formula (b1) include one or more selected from N-alkyl-N,N,N-trimethylammonium salts in which the alkyl group has 12 to 18 carbon atoms, N,N-dialkyl-N,N-dimethyl-ammonium salts in which the alkyl group has 8 to 16 carbon atoms, and N-alkyl-N,N-dimethyl-N-ethylammonium salts in which the alkyl group has 12 to 16 carbon atoms.

[0025] In general formula (b2), R 5b is an aliphatic hydrocarbon group having 8 to 18 carbon atoms. 5b From the viewpoint of further enhancing sterilizing and cleaning properties, the number of carbon atoms in R is 8 or more, and preferably 18 or less, and more preferably 16 or less. 5b is preferably an alkyl group or an alkenyl group, and is preferably an alkyl group.

[0026] In general formula (b2), R 6b and R 7bare each independently a group selected from an alkyl group having 1 to 3 carbon atoms and a hydroxyalkyl group having 1 to 3 carbon atoms. 6b and R 7b are preferably each independently a group selected from alkyl groups having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 3 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of hydroxyalkyl groups having 1 to 3 carbon atoms include a hydroxymethyl group, a hydroxyethyl group, and a hydroxypropyl group.

[0027] In general formula (b2), X - is an anion. Examples of anions include halide ions and alkyl sulfate ions having 1 to 3 carbon atoms. Examples of halide ions include chloride ions, bromide ions, and iodide ions. Examples of alkyl sulfate ions having 1 to 3 carbon atoms include methyl sulfate ions, ethyl sulfate ions, and propyl sulfate ions.

[0028] Examples of the compound represented by the general formula (b2) include N-dodecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tridecyl-N,N-dimethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-dimethyl-N-benzyl ammonium salt, N-pentadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-hexadecyl-N,N-dimethyl-N-benzyl ammonium salt, N-dodecyl-N,N-diethyl-N-benzyl ammonium salt, N-tridecyl-N,N-diethyl-N-benzyl ammonium salt, N-tetradecyl-N,N-diethyl-N-benzyl ammonium salt, and N-hexadecyl-N,N-diethyl-N-benzylammonium salt, N-dodecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tridecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-tetradecyl-N-methyl-N-ethyl-N-benzylammonium salt, N-pentadecyl-N-methyl-N-ethyl-N-benzylammonium salt, and N-hexadecyl-N-methyl-N-ethyl-N-benzylammonium salt.

[0029] <(c) component> Component (c) is a chelating agent. One or more types of component (c) can be used. From the viewpoint of further enhancing bactericidal properties, detergency, and scale inhibition, component (c) is preferably one or more types selected from (c1) a sequestering agent (hereinafter referred to as component (c1)) and (c2) a carboxylic acid polymer compound (hereinafter referred to as component (c2)), and more preferably one or more types selected from component (c1).

[0030] Examples of component (c1) include one or more selected from ethylenediaminetetraacetic acid (also known as EDTA), methylglycinediacetic acid (also known as MGDA), hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid (also known as NTA), L-glutamic acid diacetic acid (also known as GLDA), ethylene glycol bis(2-aminoethyl ether)tetraacetic acid, citric acid, gluconic acid, hydroxybenzyl iminoacetic acid, iminodiacetic acid, and salts thereof. Among these, one or more selected from ethylenediaminetetraacetic acid, methylglycinediacetic acid, citric acid, and salts thereof are preferred, and one or more selected from citric acid and salts thereof are more preferred.

[0031] Examples of salts of component (c1) include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as magnesium salts, ammonium salts, and organic amine salts such as monoethanolamine salts, diethanolamine salts, and triethanolamine salts, with alkali metal salts being preferred, and sodium salts being more preferred.

[0032] The component (c2) is a carboxylic acid polymer. The carboxylic acid polymer may be a polymer having structural units derived from a monomer having a carboxy group. Examples of the component (c2) include acrylic acid polymers and maleic acid polymers, and among these, one or more selected from poly(meth)acrylic acid, polymaleic acid, and acrylic acid-maleic acid copolymers are preferred. Some or all of these may be in the form of an alkali metal salt, ammonium salt, or alkanolamine salt. The salt of the component (c2) is preferably an alkali metal salt, more preferably a sodium salt or potassium salt, and even more preferably a sodium salt. The weight average molecular weight of the (c2) component is preferably from 2,000 to 20,000, and more preferably from 2,000 to 15,000. This weight average molecular weight is a value measured by gel permeation chromatography. The maleic acid-based polymer is, for example, a homopolymer of maleic acid, or a copolymer of maleic anhydride with other monomers copolymerizable therewith, or a salt thereof, and preferably has a structure represented by the following general formula (c2-1):

[0033] [ka]

[0034] [In the formula, R 1c , R 2c , R 3c , R 4c each independently represents a hydrogen atom, an alkyl group having from 1 to 5 carbon atoms, a phenyl group, an alkoxy group, or a carboxy group; each independently represents a hydrogen atom, an alkali metal, or an alkyl-substituted ammonium group; x and y are numbers such that the x / y (molar ratio) is from 1 / 10 to 10 / 1, and the weight-average molecular weight of the polymer is from 2,000 to 100,000.

[0035] In the general formula (c2-1), the molar ratio x / y is 1 / 10 or more and 10 / 1 or less, preferably 3 / 7 or more and 7 / 3 or less. The weight-average molecular weight of the maleic acid-based polymer represented by the general formula (c2-1) is 2,000 or more and 100,000 or less, preferably 2,000 or more and 80,000 or less, and more preferably 5,000 or more and 80,000 or less. This weight-average molecular weight is a value measured by gel permeation chromatography.

[0036] <Composition, optional ingredients, etc.> The washing machine detergent composition of the present invention contains component (a) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoint of further improving detergency and foam-suppressing properties, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of further improving economy.

[0037] The washing machine detergent composition of the present invention contains component (b) in an amount of preferably 0.2% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, in order to further enhance cleaning and disinfecting properties, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less, in order to further enhance economy and foam-suppressing properties. In the washing machine detergent composition of the present invention, when component (b) can be in the form of a salt, the mass of component (b) is specified as a value converted into chloride.

[0038] In the washing machine detergent composition of the present invention, the mass ratio of the content of component (b) to the content of component (a) [(b) / (a)] is preferably 0.1 or more, more preferably 0.15 or more, and even more preferably 0.2 or more, from the viewpoint of further enhancing the disinfecting property, and is preferably 10 or less, more preferably 8 or less, even more preferably 5 or less, and even more preferably 3 or less, from the viewpoint of further enhancing the cleaning property. The preferred range of the mass ratio [(b) / (a)] may be the preferred range when the machine detergent composition of the present invention contains the component (d) described below.

[0039] The washing machine detergent composition of the present invention contains component (c) in an amount of preferably 5% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more, in order to further enhance cleaning performance, bactericidal performance, and scale-inhibiting performance, and in an amount of preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 40% by mass or less, in order to further enhance economy. When the chelating agent having an amine structure, such as NTA, MGDA, or EDTA, of component (c1) is used in combination with an oxidizing agent, which will be described in detail later, the amount of the chelating agent in the composition is preferably 12% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, from the viewpoint of stability of the oxidizing agent. In the detergent composition for a washing machine of the present invention, the mass of component (c) is specified as a converted value assuming that it is a sodium salt.

[0040] In the washing machine detergent composition of the present invention, the mass ratio of the content of component (c) to the content of component (b) [(c) / (b)] is preferably 0.8 or more, more preferably 1.5 or more, even more preferably 2.0 or more, and still more preferably 3.0 or more, from the viewpoint of further enhancing cleaning performance, and is preferably 12 or less, more preferably 10 or less, even more preferably 9 or less, and still more preferably 8.5 or less, from the viewpoint of further enhancing bactericidal performance.

[0041] <(d) component> The washing machine detergent composition of the present invention may optionally contain (d) an alkaline agent (hereinafter referred to as component (d)). One or more types of component (d) may be used. Examples of component (d) include one or more selected from alkanolamines such as monoethanolamine, and hydroxides, carbonates, phosphates, and silicates of alkali metals. From the viewpoint of further improving detergency, component (d) is preferably one or more selected from carbonates, phosphates, and silicates, more preferably one or more selected from carbonates and silicates, even more preferably contains a silicate, and even more preferably the salt is a salt of these alkali metals. Examples of alkali metals include sodium and potassium, with sodium being preferred.

[0042] When the washing machine detergent composition of the present invention contains component (d), the washing machine detergent composition of the present invention contains component (d) in an amount of preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more in terms of further improving detergency, and preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less in terms of further improving economy. In the detergent composition for a washing machine of the present invention, the mass of component (d) is specified as a converted value assuming that it is a sodium salt.

[0043] The total content of carbonate and silicate in the alkaline agent, component (d), is preferably 20% by mass or more. When the composition is in the form of a solid, the total content of carbonate and silicate in the alkaline agent, component (d), is preferably 60% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 100% by mass or less, and particularly preferably substantially 100%. The total content of carbonate and silicate in the alkaline agent is preferably the total content when the content of component (d) in the washing machine detergent composition is 20 mass% or more.Moreover, the specification regarding the total content of carbonate and silicate in the alkaline agent is more preferably the total content when the carbonate and silicate are alkali metal salts.

[0044] In component (d), the mass ratio of alkali metal carbonate to alkali metal silicate is preferably 0 or more from the viewpoint of detergency, but from the viewpoint of further improving water solubility and storage stability in a solid state, it is more preferably 0.5 or more, and even more preferably 1 or more, and from the viewpoint of further improving detergency, it is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less. Furthermore, when component (d) is used in combination with an oxidizing agent, it is preferable that it be substantially free of alkanolamines.

[0045] <(e) component> The washing machine detergent composition of the present invention may optionally contain (e) an oxidizing agent (hereinafter referred to as component (e)). One or more types of component (e) may be used. From the viewpoint of further enhancing cleaning and disinfecting properties, component (e) is preferably one or more selected from hypochlorite, dichloroisocyanurate, and chlorite, and when used in a solid form, dichloroisocyanurate is more preferred. Examples of salts of component (e) include alkali metal salts, such as sodium hypochlorite, potassium hypochlorite, sodium chlorite, and sodium dichloroisocyanurate, with sodium dichloroisocyanurate being preferred.

[0046] When the washing machine detergent composition of the present invention contains component (e), the washing machine detergent composition of the present invention contains component (e) in an amount of preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, from the viewpoints of further enhancing cleaning performance, sterilizing properties, and foam-suppressing properties; and from the viewpoints of low substrate damage and low odor, the amount of component (e) in the composition is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less.

[0047] The cleaning machine detergent composition of the present invention may be in the form of a solid or liquid. The solid form of the washing machine detergent composition of the present invention may be, for example, a fine powder, powder, fine granules, or granules, with a powder being preferred from the viewpoint of improving handleability. The particle size and particle size distribution of the powder or the like are preferably designed for each composition in consideration of flowability, solubility, storage stability, and ease of use, and may also take into consideration the properties of the device. The washing machine detergent composition of the present invention can be produced by a known production method.

[0048] <Water> When the cleaning machine detergent composition of the present invention is in a liquid form, it may contain water. The water may be deionized water, tap water, distilled water, purified water, groundwater, well water, etc. Water may be used as the remainder of the composition in an amount such that the total composition amount is 100% by mass. When the washing machine detergent composition of the present invention is a liquid washing machine detergent composition containing water, the washing machine detergent composition of the present invention contains water in an amount of preferably 1% by mass or more, more preferably 5% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably less than 95% by mass, in terms of handleability.

[0049] The cleaning machine detergent composition of the present invention may optionally contain sodium sulfate, calcium carbonate, an enzyme, or an antifoaming agent. In the case of a powder, amorphous silicas commercially available under the trade names of Toxil NR, Fluorite, etc. may be optionally used as modifiers for the purposes of obtaining flowability and preventing solidification.

[0050] The cleaning agent composition for a cleaning machine of the present invention has a pH of a 0.1% by mass aqueous solution of the composition at 25°C, which is preferably 9 or higher, more preferably 9.5 or higher, still more preferably 10 or higher, from the viewpoint of enhancing detergency and bactericidal properties, and preferably 13 or lower, more preferably 12.5 or lower, still more preferably 12 or lower, from the viewpoint of enhancing economy. This pH is measured by the following method for measuring pH. This pH can be adjusted by the component (c) and / or the component (d). The same applies to the pH of the stock solution of the following composition.

[0051] When the cleaning agent composition for a cleaning machine of the present invention is a liquid, the liquid cleaning agent composition for a cleaning machine of the present invention has a pH of the stock solution of the composition at 25°C, which is preferably 13 or higher, more preferably 13.5 or higher, still more preferably 13.8 or higher, from the viewpoint of enhancing detergency and bactericidal properties, and the upper limit thereof is not particularly limited, but for example, it is 14 or lower, and from a chemical viewpoint, it is substantially 14 or lower. Although a value exceeding 14 may be displayed on the system of the measuring device, in the present invention, it is interpreted as substantially 14.

[0052] <Method for Measuring pH> Connect a pH electrode (9615S-10D manufactured by Horiba, Ltd.) to a pH meter (pH / Ion Meter F-23 manufactured by Horiba, Ltd.), and turn on the power. The internal liquid of the pH electrode uses a saturated potassium chloride aqueous solution (3.33 mol / L). Next, fill 100 mL beakers with pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) respectively, and immerse them in a constant temperature bath at 25°C for 30 minutes. Immerse the pH measuring electrode in the standard solution adjusted to a constant temperature for 3 minutes, and perform calibration operations in the order of pH 6.86 → pH 9.18 → pH 4.01. Adjust the sample to be measured to 25°C, immerse the electrode of the above pH meter in the sample, and measure the pH after 3 minutes.

[0053] When the cleaning machine detergent composition of the present invention is a liquid, taking into consideration a usage pattern in which it is supplied by an automatic supply device via a tube, the viscosity of the cleaning machine detergent composition of the present invention at 25°C is preferably 50 mPa·s or less, more preferably 40 mPa·s or less, and even more preferably 30 mPa·s or less. This viscosity is measured using a Brookfield viscometer, using a rotor recommended for the viscosity to be measured from among rotors No. 1 to No. 3, at 60 r / min, and is the reading 1 minute after the start of measurement. The cleaning machine detergent composition is measured at a temperature adjusted to 25±1°C. If there are multiple rotors that satisfy the conditions, the value obtained using the rotor with the smaller number is used.

[0054] The washing machine detergent composition of the present invention can be applied to articles to be washed by a washing machine, particularly articles containing plastic, metal, or glass, and specific examples thereof include containers, pallets, vessels, and tableware. Containers and pallets used in beverage factories, food factories, etc. are suitable. The washing machine detergent composition of the present invention may be a detergent composition for articles to be washed by a washing machine. The cleaning machine detergent composition of the present invention may be a detergent composition for an industrial cleaning machine. In this specification, the industrial cleaning machine is, for example, an automatic cleaning machine for cleaning food containers (e.g., food containers, trays, baskets), mainly plastic food containers, used in food processing factories, and the cleaning machine detergent composition of the present invention may be a detergent composition for an industrial cleaning machine for cleaning such containers. The washing machine detergent composition of the present invention may be a detergent composition for an automatic washing machine used in food processing businesses. Automatic washing machines used in food processing businesses have larger objects to be cleaned than automatic dishwashers used in home or restaurant kitchens, and the washing machine detergent composition of the present invention can exhibit high detergency and excellent sterilizing performance even on such objects to be cleaned.

[0055] <Cleaning method> The present invention provides a cleaning method, which includes using a cleaning machine to prepare a cleaning liquid by diluting with water a cleaning agent composition for a cleaning machine, the cleaning liquid comprising (a) a nonionic surfactant represented by the following general formula (a1), (b) a cationic surfactant, and (c) a chelating agent, and then cleaning an object to be cleaned with the cleaning liquid. R 1a -O-(EO) a (AO) b -H (a1) [In the formula, R 1a is a hydrocarbon group having 8 to 18 carbon atoms, EO is an ethyleneoxy group, and AO is a propyleneoxy group or a butyleneoxy group, and EO and AO may be bonded in a block bond or added randomly, and either EO or AO may be added first. a and b are the average number of moles added, and are each independently a number of 1 to 50. The cleaning method of the present invention may be a cleaning method in which a cleaning liquid is prepared by diluting the cleaning agent composition for a cleaning machine of the present invention with water, and an object to be cleaned is washed with the cleaning liquid. The object to be cleaned in the cleaning method of the present invention may be any of the articles described above in connection with the cleaning agent composition for a cleaning machine of the present invention. In the cleaning method of the present invention, a cleaning machine is used to bring the cleaning solution into contact with the object to be cleaned, thereby cleaning the object.

[0056] In the cleaning method of the present invention, the components (a) to (c) and optional components contained in the machine detergent composition, and preferred embodiments of the machine detergent composition are the same as those described for the machine detergent composition of the present invention. The water used for dilution is not particularly limited, and examples thereof include tap water and groundwater.

[0057] The cleaning solution contains the component (a) in an amount of preferably 2.5 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more, from the viewpoint of further improving cleaning ability and foam-suppressing property, and preferably 400 ppm or less, more preferably 300 ppm or less, and even more preferably 200 ppm or less, from the viewpoint of further improving economic efficiency.

[0058] The cleaning solution contains component (b) in an amount of preferably 2 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more, from the viewpoint of further enhancing bactericidal properties and cleaning performance, and preferably 600 ppm or less, more preferably 400 ppm or less, and even more preferably 200 ppm or less, from the viewpoint of further enhancing economy and foam suppression.

[0059] The cleaning solution contains the component (c) in an amount of preferably 25 ppm or more, more preferably 50 ppm or more, and even more preferably 75 ppm or more, from the viewpoint of further enhancing the bactericidal, cleaning, and scale-inhibiting properties, and preferably 800 ppm or less, more preferably 780 ppm or less, and even more preferably 750 ppm or less, from the viewpoint of further enhancing the economic efficiency.

[0060] When the cleaning liquid contains the component (d), the cleaning liquid contains the component (d) in an amount of preferably 25 ppm or more, more preferably 50 ppm or more, and even more preferably 75 ppm or more in order to further improve cleaning properties, and preferably 1000 ppm or less, more preferably 800 ppm or less, and even more preferably 700 ppm or less in order to further improve economic efficiency.

[0061] When the cleaning liquid contains component (e), the cleaning liquid contains component (e) in an amount of preferably 2.5 ppm or more, more preferably 5 ppm or more, and even more preferably 10 ppm or more, from the viewpoints of further enhancing cleaning performance, sterilizing properties, and foam-inhibiting properties, and preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 120 ppm or less, from the viewpoints of low substrate damage and low odor.

[0062] In the cleaning method of the present invention, the liquid detergent composition for a cleaning machine of the present invention is diluted with water so that the content of the composition in the cleaning liquid is preferably 0.05 mass% or more, more preferably 0.07 mass% or more, and even more preferably 0.1 mass% or more, from the viewpoint of further enhancing cleaning and disinfecting properties, and preferably 0.3 mass% or less, more preferably 0.2 mass% or less, even more preferably 0.18 mass% or less, and even more preferably 0.15 mass% or less, from the viewpoint of further enhancing foam-suppressing properties and economy, and cleaning is carried out, for example, in an automatic cleaning machine equipped with a conveyor.

[0063] The cleaning time is preferably 1 second or more, more preferably 2 seconds or more, and even more preferably 3 seconds or more, from the viewpoint of further improving cleaning and disinfecting properties, and is preferably 80 seconds or less, more preferably 70 seconds or less, and even more preferably 60 seconds or less, from the viewpoint of further improving work efficiency. The temperature of the cleaning liquid obtained by diluting the cleaning machine detergent composition of the present invention with water is preferably 25°C or higher, more preferably 30°C or higher, and even more preferably 35°C or higher, from the viewpoint of further enhancing cleaning and sterilizing properties, and is preferably 60°C or lower, more preferably 57°C or lower, and even more preferably 55°C or lower, from the viewpoint of enhancing sustainability and economic efficiency. The washing machine detergent composition of the present invention can exhibit high detergency and sterilizing properties even when washing is carried out at a relatively low temperature when the diluted solution of the composition is used as described above.

[0064] In the cleaning method of the present invention, rinsing may be performed after the cleaning object has been cleaned. In the cleaning method of the present invention, the rinsing time is preferably 1 second or longer, more preferably 2 seconds or longer, and even more preferably 3 seconds or longer, from the viewpoint of further improving rinsing performance, and is preferably 30 seconds or shorter, more preferably 25 seconds or shorter, and even more preferably 20 seconds or shorter, from the viewpoint of further improving economy and work efficiency. The temperature of the water used for rinsing is preferably 25°C or higher, more preferably 30°C or higher, and even more preferably 35°C or higher, from the viewpoint of further enhancing cleaning and sterilizing properties, and is preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of improving economy. [Example]

[0065] The following components (a) to (e) were used to prepare cleaning machine detergent compositions of Examples and Comparative Examples shown in Tables 1 and 2, and the cleaning and disinfecting properties of the compositions were evaluated. The mass % of the components in the tables is all based on the pure content.

[0066] <Component (a)> (a-1): Polyoxyethylene polyoxypropylene alkyl ether having a secondary alkyl group having 12 to 14 carbon atoms, an average number of moles of ethyleneoxy groups (EO) added being 7, and an average number of moles of propyleneoxy groups (PO) added being 8.5; Softanol EP7085, manufactured by Nippon Shokubai Co., Ltd.; in the general formula (a1), R 1a is a secondary alkyl group having 12 to 14 carbon atoms, AO is a propyleneoxy group, a is 7, b is 8.5, and EO and AO are R 1a This compound is a compound in which EO and AO are blocked in the order of O bonded to the O bonded to the (a-2): Polyoxyethylene polyoxypropylene alkyl ether having a secondary alkyl group having 12 to 14 carbon atoms, an average number of moles of ethyleneoxy groups (EO) added being 7, and an average number of moles of propyleneoxy groups (PO) added being 4.5; Softanol EP7045, manufactured by Nippon Shokubai Co., Ltd.; in the general formula (a1), R 1a is a secondary alkyl group having 12 to 14 carbon atoms, AO is a propyleneoxy group, a is 7, b is 4.5, and EO and AO are R 1a This compound is a compound in which EO and AO are blocked in the order of O bonded to the O bonded to the (a-3): Polyoxyethylene polyoxybutylene alkyl ether having a secondary alkyl group having 12 to 15 carbon atoms, an average number of moles of ethyleneoxy groups (EO) added being 4.8, and an average number of moles of butyleneoxy groups (BO) added being 1.7, PlurafacLF224, manufactured by BASF Japan Ltd.; 1a is a secondary alkyl group having 12 to 15 carbon atoms, AO is a butyleneoxy group, a is 4.8, b is 1.7, and EO and AO are R 1a This compound is a compound in which EO and AO are blocked in the order of O bonded to the O bonded to the

[0067] <(b) Component> (b-1): Benzalkonium chloride, Sanizol B-50, manufactured by Kao Corporation, general formula (b2), R 5b is an alkyl group having 8 to 18 carbon atoms, R 6b and R 7b is a methyl group, X - is a compound of chloride ion. (b-2): Dodecyltrimethylammonium chloride, Kotamine 20W, manufactured by Kao Corporation, general formula (b1), R 1b is a dodecyl group, R 2b , R 3b and R 4b is a methyl group, X - is a compound of chloride ion. (b-3): Didecyldimethylammonium chloride, Kotamin D10E, manufactured by Kao Corporation, general formula (b1), R 1b and R 2b is a decyl group, R 3b and R 4b is a methyl group, X - is a compound of chloride ion.

[0068] <(c) component> (c-1): Trisodium citrate (c-2): Sodium polyacrylate, molecular weight 4,000, Sokalan PA25CL (100% pure), manufactured by BASF Japan Ltd. (c-3): Polyacrylic acid-maleic acid copolymer sodium salt, molecular weight 70,000, Sokalan CP5, manufactured by BASF Japan Ltd. (c-4): NTA, sodium nitrilotriacetate, Triron A92R, manufactured by BASF Japan Ltd. (c-5): EDTA, sodium ethylenediaminetetraacetate monohydrate, Crabion TS, manufactured by Tozai Petrochemical Co., Ltd. <(d) component> (d-1): Anhydrous sodium metasilicate (d-2): Dense ash (sodium carbonate) (d-3): Potassium carbonate <(e) component> (e-1): Oxidizing agent, sodium dichloroisocyanurate, Neochlor 60MG, manufactured by Shikoku Chemicals Corporation <Other ingredients> Glauber's Salt: Neutral anhydrous mirabilite

[0069] <How to evaluate cleaning performance> The stain was applied with a brush to a 12.5cm x 23cm area of ​​the 53.5cm x 33.5cm surface of a plastic container with internal dimensions of 53.5cm x 33.5cm x 3.0cm, and then allowed to dry for one hour. 2g of Nisshin Seifun Welna meat sauce was applied as the stain. A washing machine (conveyor type model UA-1310, manufactured by Creo Co., Ltd.) was used, and the washing temperature was 45°C, the rinsing temperature was 45°C, and the conveyor speed was 12 cm / s. A cleaning solution was prepared by mixing a cleaning agent composition for a washing machine shown in Table 1 or 2 with water so that the concentration of the composition was 0.1% by mass. This cleaning solution was stored in a washing tank, and washing and rinsing were carried out. The cleaning performance of plastic containers was evaluated using adenosine triphosphate (ATP) wipe test (A3 method) using adenosine triphosphate as a soiling indicator. Specifically, the entire 10 cm × 10 cm area of ​​the soiled surface of the cleaned plastic container was wiped with a dry cotton swab, and ATP was extracted from the wiped dry cotton swab and reacted with the luminescent enzyme. This series of operations was performed using a Lucipack A3 Surface (Kikkoman Biochemifa Corporation). The light generated by the reaction between ATP and the luminescent enzyme was measured using a luminescence photometer (Lumitester Smart, Kikkoman Biochemifa Corporation). The lower this value (RLU), the higher the cleaning performance of the cleaning agent composition for a cleaning machine. A cleaning agent composition for a cleaning machine with a luminescence unit (RLU) of 100,000 or less can be said to have preferable cleaning performance.

[0070] <Bactericidal evaluation> A cleaning liquid was prepared by mixing the cleaning agent compositions for a cleaning machine shown in Tables 1 and 2 with water so that the concentration of the composition was 0.1% by mass. This washing solution was heated to 45°C, and the target bacteria (E. coli NBRC3972) was added to the washing solution at an initial count of 10 6 After 1 minute, the mixture was diluted 10-fold with Millipore D / E Neutralizing Broth to stop the reaction. To this mixture, a 30-fold volume of standard agar medium "Daigo" manufactured by Shioya MS Co., Ltd. was added, and the mixture was cultured at 37°C for 24 hours. The number of colonies was counted to determine the number of viable bacteria. This measurement value is designated as A. Further, a test was conducted by replacing the washing machine detergent composition with water using the above procedure, and the viable cell count was measured. This viable cell count was designated as B. The 1-minute bactericidal activity was then calculated according to the following formula (1). A lower viable cell count in the mixed solution containing the washing machine detergent composition indicates higher bactericidal activity. In other words, the larger the value of the 1-minute bactericidal activity (Δlog), the higher the bactericidal activity of the washing machine detergent composition. A washing machine detergent composition with a Δlog of 1 or more can be said to have preferable bactericidal activity. 1 minute sterilization (Δlog)=logB-logA (1)

[0071] [Table 1]

[0072] [Table 2]

Claims

1. A cleaning agent composition for a washing machine, comprising: (a) a nonionic surfactant represented by the following general formula (a1); (b) a cationic surfactant; and (c) a chelating agent: 2 １ａ --(EO) ａ (29) ｂ -2 (11) [In the formula, R １ａ is a hydrocarbon group having from 8 to 18 carbon atoms, EO is an ethyleneoxy group, and AO is a propyleneoxy group or a butyleneoxy group, and EO and AO may be bonded in a block bond or added randomly, and either EO or AO may be added first. a and b are the average number of moles added, and are each independently a number of from 1 to 50.

2. The machine detergent composition according to claim 1, further comprising (e) an oxidizing agent.

3. A cleaning method comprising: preparing a cleaning liquid by diluting a cleaning machine detergent composition containing (a) a nonionic surfactant represented by the following general formula (a1), (b) a cationic surfactant, and (c) a chelating agent with water, using a cleaning machine; and cleaning an object to be cleaned with the cleaning liquid. 2 １ａ --(EO) ａ (29) ｂ -2 (11) [In the formula, R １ａ is a hydrocarbon group having from 8 to 18 carbon atoms, EO is an ethyleneoxy group, and AO is a propyleneoxy group or a butyleneoxy group, and EO and AO may be bonded in a block bond or added randomly, and either EO or AO may be added first. a and b are the average number of moles added, and are each independently a number of from 1 to 50.

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