CN107709531B - Cleaning agent composition for automatic cleaning machine - Google Patents
Cleaning agent composition for automatic cleaning machine Download PDFInfo
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- CN107709531B CN107709531B CN201680003793.XA CN201680003793A CN107709531B CN 107709531 B CN107709531 B CN 107709531B CN 201680003793 A CN201680003793 A CN 201680003793A CN 107709531 B CN107709531 B CN 107709531B
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
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Abstract
A detergent composition for an automatic cleaning machine, comprising: 0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a polyoxyalkylene monoalkyl ether represented by the general formula (2); and 0.1 to 10 mass% in total of (b) at least 1 surfactant selected from the group consisting of reverse pluronic block polymer, reverse quaternary ketone block polymer, pluronic block polymer and quaternary ketone block polymer (in the general formula (1), R is R1A residue obtained by removing all hydroxyl groups from a 3-to 8-membered C3-20 polyhydric alcohol, A1O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, n represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 1000, m represents an integer of 3 to 8, and m [ (O- (A)1O) n-H are optionally the same or different. In the general formula (2), R2Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, A2O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, and t represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 100. ).
Description
Technical Field
The present invention relates to a detergent composition for an automatic cleaning machine.
Background
In hotels, restaurants, and the like, automatic washing machines such as automatic dish washing machines are used for washing used dishes and kitchenware from the viewpoints of efficiency of work, hygiene management, and the like. In addition, automatic washing machines have rapidly become widespread in general households in recent years. As performance required for a cleaning agent composition used in an automatic cleaning machine, foaming is small (low foaming property) in addition to high cleaning power.
Patent document 1 discloses a liquid detergent composition for a low-foaming automatic dishwasher, which contains (a) 0.1 to 5% by mass of a nonionic surfactant and (b)0.1 to 10% by mass of polypropylene glycol, and has a total surfactant concentration of 10% by mass or less and a viscosity of 1000 to 4000mPa · s. Patent document 2 discloses a detergent composition for an automatic dishwasher, which contains 0.1 to 20% by weight of a total of a nonionic surfactant (a) having a specific structure and a polyoxypropylene (b) having an average degree of condensation of oxypropylene groups of 10 to 90, and the weight ratio (a)/(b) of (a) to (b) is 1/2 to 1/1. Patent document 3 discloses a detergent composition for automatic dish washing machines, which contains polyoxypropylene having an average degree of condensation of oxypropylene groups of 30 to 90.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5064045
Patent document 2: japanese patent No. 3413351
Patent document 3: japanese patent No. 2931571
Disclosure of Invention
Problems to be solved by the invention
Most automatic washing machines are of a type that sprays a high-temperature (e.g., 40 to 70 ℃) washing liquid to cause the dirt of dishes to fall off, but at the time of starting up (starting operation) of the automatic washing machine, the temperature of the washing liquid is often low, around room temperature. When the temperature of the cleaning liquid is low (low temperature), components such as a surfactant contained in the cleaning liquid composition for an automatic cleaning machine tend to foam. The foaming of the cleaning liquid is caused not only by components such as a surfactant contained in the cleaning liquid composition but also by substances taken in from dirt (food residue and the like) adhering to the dishes and the like. For example, foaming is easily caused by food-derived dirt such as oil dirt, protein dirt, and starch dirt. In particular, protein fouling is caused by severe foaming, and typical examples thereof include egg fouling. The detergent compositions for automatic dish washing machines of patent documents 1 to 3 have room for improvement in the effect of suppressing foaming at such a low temperature and foaming due to dirt.
In addition, in a professional automatic washing machine, washing is performed with a higher pressure water flow than in a general household automatic washing machine, and therefore, foaming is large, and higher foam suppression is required. When the detergent compositions for automatic dish washing machines of patent documents 1 to 3 are used in professional automatic washing machines, the foam inhibition performance is insufficient, and there is room for further improvement in the foam inhibition performance.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a detergent composition for an automatic cleaning machine, which can suppress foaming at low temperatures and foaming due to dirt, and can suppress foaming even when used in a professional automatic cleaning machine.
Means for solving the problems
The detergent composition for an automatic cleaning machine of the present invention is characterized by comprising: 0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2); and (b)0.1 to 10 mass% in total of at least 1 surfactant selected from the group consisting of reverse pluronic block polymers, reverse quaternary ketone block polymers, pluronic block polymers, and quaternary ketone block polymers.
(in the formula, R1A residue obtained by removing all hydroxyl groups from a 3-to 8-membered C3-20 polyhydric alcohol, A1O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, n represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 1000, m represents an integer of 3 to 8, and m [ (O- (A)1O) n-H are optionally the same or different. )
(in the formula, R2Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, A2O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, and t represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 100. )
In the present specification, unless otherwise specified, the content (% by mass) of each component of the detergent composition is the net content of each component (in the detergent composition) relative to the content of the detergent composition.
The detergent composition for an automatic cleaning machine of the present invention (hereinafter, also simply referred to as the detergent composition of the present invention) comprises: 0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a polyoxyalkylene monoalkyl ether represented by the general formula (2) (hereinafter, also referred to as component (a)); and 0.1 to 10 mass% in total of (b) at least 1 surfactant selected from the group consisting of Reverse Pluronic block polymers, Reverse quaternary ketone block polymers, Pluronic block polymers, and Tetronic block polymers (hereinafter also referred to as component (b)). The detergent composition of the present invention can exhibit excellent foam inhibition and detergency by containing the components (a) and (b) in the above amounts. Therefore, excellent foam inhibition can be exhibited at low temperatures and in the presence of dirt such as food residues. In addition, even when the detergent composition is used in a professional automatic cleaning machine, foaming can be suppressed. In particular, by including the component (a) in the above amount, foaming at a low temperature can be suppressed, and foaming of the cleaning liquid can be suppressed even when the cleaning liquid is low temperature at the time of starting the washing machine, for example, in a temperature range from a low temperature to a cleaning temperature in the cleaning of tableware and the like by the automatic washing machine. Further, by containing the component (b) in the above amount, foaming due to fouling can be suppressed, and even in the case where fouling is present in a large amount, high foam inhibition can be exhibited. Further, the cleaning agent composition of the present invention contains the components (a) and (b) in the above amounts, and thus has a high cleaning power.
The cleaning liquid is an aqueous cleaning liquid solution prepared by diluting or dissolving a cleaning liquid composition for an automatic cleaning machine with water.
In the present invention, the low temperature is, for example, a case where the temperature of the cleaning liquid is lower than 40 ℃, preferably 10 to 30 ℃, more preferably 10 to 20 ℃. The detergent composition of the present invention can exhibit high foam inhibition at such a low temperature.
In the present invention, it is preferable that in the above general formula (2), R2Represents an alkyl group having 1 to 20 carbon atoms. When the polyoxyalkylene monoalkyl ether is such a polyoxyalkylene monoalkyl ether, the foam suppressing property at low temperature is further improved.
In the present invention, it is more preferable that in the above general formula (2), R2Represents an alkyl group having 3 to 15 carbon atoms, the above-mentioned A2O represents an oxypropylene group, and t is a number of 2 to 60.
When the polyoxyalkylene monoalkyl ether is such a polyoxyalkylene monoalkyl ether, the foam suppressing property at low temperature can be further improved.
The polyoxyalkylene monoalkyl ether represented by the above general formula (2) is more preferably polyoxypropylene tridecyl ether. When the polyoxypropylene tridecyl ether is contained, the foam suppressing property at low temperatures can be further improved.
In the above general formula (1), R is preferably1A represents a residue obtained by removing all hydroxyl groups from a 3-to 5-membered aliphatic alcohol having 3 to 5 carbon atoms1O represents an oxypropylene group, n is a number of 2 to 250, and m is 3.
When the alkylene oxide adduct of the polyhydric alcohol in the component (a) is a propylene oxide adduct of such a 3-membered aliphatic alcohol, the foam suppressing property at low temperatures is further improved.
In the present invention, the molar ratio (EO/PO) of oxyethylene (EO) groups to oxypropylene (PO) groups in the reverse pluronic block polymer is preferably 1/10 to 1/2. More preferably, the molar ratio (EO/PO) is 1/6 to 1/2.
If the molar ratio of oxyethylene (EO) to oxypropylene (PO) (EO/PO) in the reverse pluronic block polymer is in the above range, the suds suppression in the presence of soil is further improved.
The detergent composition of the present invention preferably further contains at least 1 selected from the group consisting of an alkaline agent, a chelating agent, a solubilizing agent, a bleaching agent, an anticorrosive agent, a bactericide and an enzyme.
The cleaning agent composition preferably contains at least 1 of the above-mentioned components in addition to the components (a) and (b), because the cleaning power and the like are further improved.
The detergent composition for automatic cleaning machines of the present invention is suitable as a detergent composition for automatic dish cleaning machines or container cleaning machines.
An example of an embodiment of the present invention is described.
<1-1> a detergent composition for an automatic cleaning machine, characterized by comprising: 0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a polyoxyalkylene monoalkyl ether represented by the general formula (2); and 0.1 to 10 mass% of (b) a reverse pluronic block polymer.
<1-2>According to the above<1-1>The detergent composition for an automatic cleaning machine, wherein in the general formula (2), R2Represents an alkyl group having 1 to 20 carbon atoms.
<1-3>According to the above<1-1>Or<1-2>The detergent composition for an automatic cleaning machine, wherein in the general formula (2), R2Represents an alkyl group having 3 to 15 carbon atoms, the above-mentioned A2O represents oxypropyleneT is a number of 2 to 60.
<1-4> the detergent composition for an automatic cleaning machine according to any one of <1-1> to <1-3>, wherein the polyoxyalkylene monoalkyl ether represented by the general formula (2) is polyoxypropylene tridecyl ether.
<1-5>According to the above<1-1>～<1-4>The detergent composition for an automatic cleaning machine as described in any one of the above general formulae (1), wherein R is represented by the formula1A represents a residue obtained by removing all hydroxyl groups from a 3-to 5-membered aliphatic alcohol having 3 to 5 carbon atoms1O represents an oxypropylene group, n is a number of 2 to 250, and m is 3.
<1-6> the detergent composition for automatic cleaning machines according to any one of <1-1> to <1-5>, wherein the molar ratio (EO/PO) of oxyethylene (EO) to oxypropylene (PO) in the reverse pluronic block polymer is 1/10 to 1/2.
<1-7> the detergent composition for an automatic cleaning machine according to any one of <1-1> to <1-6>, which further comprises at least 1 selected from the group consisting of an alkaline agent, a chelating agent, a solubilizing agent, a bleaching agent, an anticorrosive agent, a bactericide and an enzyme.
<1-8> the detergent composition for automatic dishwashing machines according to any one of <1-1> to <1-7>, which is a detergent composition for automatic dishwashing machines.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a detergent composition for an automatic cleaning machine, which can suppress foaming at low temperatures and foaming due to fouling, and which can suppress foaming even when used in a service cleaning machine.
Detailed Description
The embodiments of the present invention will be specifically described below. However, the present invention is not limited to the following embodiments, and can be applied by appropriately changing the embodiments without changing the gist of the present invention.
The detergent composition for an automatic cleaning machine of the present invention is characterized by comprising: 0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2); and (b)0.1 to 10 mass% in total of at least 1 surfactant selected from the group consisting of reverse pluronic block polymers, reverse quaternary ketone block polymers, pluronic block polymers, and quaternary ketone block polymers.
(in the formula, R1A residue obtained by removing all hydroxyl groups from a 3-to 8-membered C3-20 polyhydric alcohol, A1O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, n represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 1000, m represents an integer of 3 to 8, and m [ (O- (A)1O) n-H are optionally the same or different. )
(in the formula, R2Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, A2O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, and t represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 100. )
The component (a) is at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2). As the component (a), only 1 kind of these compounds may be used, or 2 or more kinds may be used in combination.
By containing the component (a) in the above amount, excellent foam suppressing properties can be exhibited. In particular, the foam suppressing property at low temperatures is improved, and foaming at the start of the automatic cleaning machine can be suppressed. In addition, foaming can be suppressed even when the cleaning agent composition is used in a professional automatic cleaning machine.
R in the above general formula (1)13 to 8 carbon atoms of 3 to 20 carbon atomsThe residue of all hydroxyl groups in the polyhydric alcohol is removed. Examples of the 3 to 8-membered polyhydric alcohol having 3 to 20 carbon atoms include: 3-membered alcohols such as glycerol (glycerin), 1,2, 3-butanetriol, 1,2, 4-butanetriol, 1,2, 3-pentanetriol, 1,2, 4-pentanetriol, 2-methyl-1, 2, 3-propanetriol, 2-methyl-2, 3, 4-butanetriol, 2-ethyl-1, 2, 3-butanetriol, 2,3, 4-pentanetriol, 3-methylpentane-1, 3, 5-triol, 2, 4-dimethyl-2, 3, 4-pentanetriol, 2,3, 4-hexanetriol, 4-propyl-3, 4, 5-heptanetriol, 1,3, 5-cyclohexanetriol, pentamethylglycerol, trimethylolethane, trimethylolpropane, etc.; 4-membered alcohols such as tetramethylolmethane (pentaerythritol) and diethylene glycol; 5-membered alcohols such as arabitol, galactose, xylitol, glucose, fructose, mannose, allose, gulose, idose, and talose; 6-membered alcohols such as dipentaerythritol, sorbitol, mannitol, iditol and inositol; mannitol, a 7-membered alcohol; and polyhydric aliphatic alcohols such as 8-membered alcohols such as sucrose, maltose, and lactose. Among them, a 3 to 6-membered polyhydric alcohol having 3 to 20 carbon atoms is preferable, a 3 to 6-membered polyhydric alcohol having 3 to 10 carbon atoms is more preferable, and for example, glycerin, sorbitol, pentaerythritol, and trimethylolpropane are further preferable. Among them, a 3-membered aliphatic alcohol having 3 to 5 carbon atoms is particularly preferable, and glycerol is most preferable.
A1The oxyalkylene group having 3 or 4 carbon atoms represented by O is oxypropylene or oxybutylene. A. the1O preferably contains oxypropylene groups, and the ratio of the oxypropylene groups in the entire oxyalkylene groups is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 95 mol% or more. It is particularly preferred that A1O is oxypropylene.
Having oxypropylene and oxybutylene radicals as A1When O is used, the addition form may be random or block.
In the general formula (1), n is preferably 2 to 250, more preferably 2 to 200, more preferably 2 to 100, further preferably 10 to 100, particularly preferably 15 to 100, and most preferably 15 to 70.
m is preferably 3 to 6, more preferably 3 to 5, and further preferably 3.
In addition, the average molar number (n × m) of oxyalkylene groups added is preferably 10 to 300, more preferably 40 to 150, on average to the alkylene oxide adduct of the polyhydric alcohol represented by the general formula (1).
The mass average molecular weight of the alkylene oxide adduct of the polyol represented by the general formula (1) is preferably 250 to 40000, more preferably 500 to 10000.
The mass average molecular weight was determined by gel permeation chromatography using N, N-Dimethylformamide (DMF) as a developing solvent and polyethylene glycol (PEG) as a standard substance.
An example of a preferred form of the alkylene oxide adduct of the polyol in component (a) is: in the general formula (1), R1A residue obtained by removing all hydroxyl groups from a 3-to 5-membered aliphatic alcohol having 3 to 5 carbon atoms, A1O represents an oxypropylene group, n is a number of 2 to 250, and m is 3. The alkylene oxide adduct of the polyol is more preferably: in the general formula (1), R1Denotes a residue obtained by removing all hydroxyl groups from glycerol, A1O represents an oxypropylene group, n is a number of 10 to 200 (preferably 15 to 100), and m represents 3. 3 [ -O- (A)1O) n-H are optionally the same or different.
Further, as the alkylene oxide adduct of the polyhydric alcohol, also preferred are: in the general formula (1), R1A represents a residue obtained by removing all hydroxyl groups from trimethylolpropane, pentaerythritol or sorbitol1O represents an oxypropylene group, n is a number of 5 to 50 (preferably 8 to 30), and m represents 3,4 or 6. In this case, m [ (O- (A) s)1O) n-H are optionally the same or different.
When such a compound is contained as an alkylene oxide adduct of a polyol, the foam suppressing property at low temperatures can be further improved. Therefore, foaming at the time of starting the automatic washing machine can be more sufficiently suppressed.
The component (a) in the present invention is preferably a polyoxyalkylene monoalkyl ether represented by the general formula (2).
R in the above general formula (2)2Represents an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, A2O's are the same or different and each represents an oxyalkylene group having 3 or 4 carbon atoms, and t represents an average molar number of addition of the oxyalkylene group and is a number of 2 to 100.
In the general formula (2), R2Preferably an alkyl group having 1 to 20 carbon atoms. The polyoxyalkylene monoalkyl ether in the invention is preferably represented by the general formula (2) wherein R is2A polyoxyalkylene monoalkyl ether which represents an alkyl group having 1 to 20 carbon atoms.
Examples of the alkyl group having 1 to 20 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, sec-hexyl, tert-hexyl, isohexyl, n-heptyl, sec-heptyl, tert-heptyl, isoheptyl, n-octyl, sec-octyl, tert-octyl, isooctyl, 2-ethylhexyl, 3-ethylhexyl, n-nonyl, sec-nonyl, tert-nonyl, isononyl, n-decyl, sec-decyl, tert-decyl, isodecyl, n-undecyl, sec-undecyl, tert-undecyl, isoundecyl, n-dodecyl, sec-dodecyl, tert-dodecyl, isododecyl, n-tridecyl, sec-tridecyl, iso-tridecyl, n-tetradecyl, tert-tetradecyl, iso-tetradecyl, n-pentadecyl, sec-pentadecyl, tert-pentadecyl, iso-pentadecyl, n-hexadecyl, iso-tetradecyl, tert-decyl, iso-tetradecyl, iso-, Straight-chain or branched alkyl groups such as secondary hexadecyl, tertiary hexadecyl, isohexadecyl, n-heptadecyl, secondary heptadecyl, tertiary heptadecyl, isoheptadecyl, n-octadecyl, secondary octadecyl, tertiary octadecyl, and isooctadecyl. Among them, an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 4 to 15 carbon atoms is more preferable, an alkyl group having 12 to 15 carbon atoms is further preferable, and an alkyl group having 13 carbon atoms is particularly preferable. In addition, the alkyl group is preferably a branched alkyl group.
Examples of the alkenyl group having 2 to 20 carbon atoms include: a straight-chain or branched alkenyl group such as a vinyl group, a 1-propenyl group, a 2-butenyl group, a 3-pentenyl group, a 4-pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, and an octadecenyl group. Among them, an alkenyl group having 4 to 15 carbon atoms is preferable, and for example, 2-butenyl, 3-butenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl and pentadecenyl are preferable, an alkenyl group having 5 to 15 carbon atoms is more preferable, and a tridecenyl group is particularly preferable.
A2The oxyalkylene group having 3 or 4 carbon atoms represented by O is oxypropylene or oxybutylene. A. the2O preferably contains oxypropylene groups, and the ratio of the oxypropylene groups in the entire oxyalkylene groups is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 95 mol% or more. It is particularly preferred that A2O is oxypropylene.
Having oxypropylene and oxybutylene radicals as A2When O is used, the addition form may be random or block.
t is preferably 2 to 60, more preferably 2 to 55, and further preferably 2 to 10.
The polyoxyalkylene monoalkyl ether represented by the general formula (2) preferably has a mass average molecular weight of 150 to 5000, more preferably 250 to 4000.
The mass average molecular weight was determined by gel permeation chromatography using DMF as a developing solvent and PEG as a standard substance.
An example of a preferred embodiment of the general formula (2) is R2Represents an alkyl group having 3 to 15 carbon atoms, A2O represents oxypropylene group, and t is a number of 2 to 60. More preferably, in the general formula (2), R2Represents an alkyl group having 4 to 15 carbon atoms (more preferably 12 to 15 carbon atoms), A2O represents oxypropylene group, and t is a number of 2 to 60. When the polyoxyalkylene monoalkyl ether is such a compound, the foam suppressing property at low temperature can be further improved.
In the present invention, the polyoxyalkylene monoalkyl ether represented by the above general formula (2) is preferably R2A polyoxypropylene monoalkyl ether having an alkyl group of 12 to 15 carbon atoms, particularly preferably a polyoxypropylene tridecyl ether. The polyoxypropylene tridecyl ether is preferably contained because the foam suppressing property at low temperature is particularly good. R2The average molar number (t) of oxypropylene groups added to a polyoxypropylene monoalkyl ether (preferably polyoxypropylene tridecyl ether) having an alkyl group with 12 to 15 carbon atoms is preferably 2 to 50 (more preferably 2 to 10, even more preferably 2 to 8).
The cleaning agent composition of the present invention contains 0.01 to 10% by mass of the component (a). When the content of the component (a) is in the above range, the foam inhibition property at low temperature is good. If the component (a) exceeds 10 mass%, the cleaning action may be reduced. The content of the component (a) is preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass, from the viewpoint of more satisfactory foam suppression at low temperatures. When the component (a) contains 2 or more compounds, the content is defined as the total of them.
The component (b) in the present invention is at least 1 surfactant selected from the group consisting of reverse pluronic type block polymers, reverse quaternary ketone type block polymers, pluronic type block polymers, and quaternary ketone type block polymers. These surfactants may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among them, the component (b) preferably contains at least 1 surfactant selected from the group consisting of reverse pluronic-type block polymers and reverse quaternary ketone-type block polymers, and the component (b) preferably contains at least 1 surfactant selected from the group consisting of reverse pluronic-type block polymers and reverse quaternary ketone-type block polymers. Component (b) is also preferably a reverse pluronic-type block polymer or a reverse quaternary ketone-type block polymer. These may be used alone in 1 kind, or 2 or more kinds may be used in combination. Among these, as the component (b), a reverse pluronic type block polymer is particularly preferable.
The mass average molecular weight of the reverse pluronic block polymer is preferably 1000 to 6000, more preferably 2000 to 5000.
The mass average molecular weight of the reverse quaternary ketone block polymer is preferably 1000 to 6000, and more preferably 3000 to 5000.
The mass average molecular weight of the pluronic block polymer is preferably 1000 to 6000, more preferably 1000 to 4000.
The quaternary ketone block polymer preferably has a mass average molecular weight of 1000 to 6000, more preferably 1500 to 4000.
When the mass average molecular weight is within the above range, the foam suppressing property in the presence of dirt is further improved.
The mass average molecular weight was determined by gel permeation chromatography using DMF as a developing solvent and PEG as a standard substance.
The molar ratio (EO/PO) of oxyethylene (EO) groups to oxypropylene (PO) groups in the reverse pluronic block polymer is preferably 1/10 to 1/2, more preferably 1/6 to 1/2.
The molar ratio (EO/PO) of oxyethylene (EO) groups to oxypropylene (PO) groups in the reverse quaternary ketone block polymer is preferably 1/0.5 to 1/10, more preferably 1/0.5 to 1/5, and still more preferably 1/1 to 1/3.
The molar ratio of EO to PO (EO/PO) in the pluronic block polymer is preferably 1/0.5 to 1/15, more preferably 1/2 to 1/12, and still more preferably 1/4 to 1/9. The molar ratio of EO to PO (EO/PO) in the quaternary ketone block polymer is preferably 1/0.5 to 1/15, more preferably 1/2 to 1/12, and still more preferably 1/4 to 1/9.
It is preferable that the component (b) contains 1 or 2 or more of the reverse pluronic block polymer, the reverse quaternary ketone block polymer, the pluronic block polymer, and the quaternary ketone block polymer in which the molar ratio of EO to PO is the above ratio, because the foam suppressing property in the presence of soil is further improved.
The cleaning agent composition of the present invention contains 0.1 to 10% by mass of the component (b). By containing the component (b) in the above amount, excellent foam suppressing properties can be exhibited. In particular, the foam suppressing property in the presence of the dirt is improved, and foaming can be suppressed even when the dirt is present in a large amount in the cleaning liquid. In addition, foaming can be suppressed even when the cleaning agent composition is used in a professional automatic cleaning machine. Further, by containing the component (b) in the above amount, high detergency can be exhibited. The content of the component (b) is preferably 0.5 to 10% by mass, more preferably 1 to 10% by mass, and further preferably 1 to 8% by mass. When the component (b) contains 2 or more compounds, the content is defined as the total of them.
The cleaning agent composition of the present invention may contain components other than the component (a) and the component (b) as long as the effects of the present invention are not impaired.
For example, the cleaning agent composition of the present invention preferably further contains at least 1 selected from the group consisting of an alkaline agent, a chelating agent, a solubilizing agent, a bleaching agent, an anticorrosive agent, a bactericide and an enzyme. These may be used alone in 1 kind, or 2 or more kinds may be used in combination.
The detergent composition preferably contains an alkaline agent because the detergency is improved.
The alkali agent may be a water-soluble alkali agent, and for example, an alkali metal salt or an alkaline earth metal salt may be used. The alkali metal salt is preferably at least 1 compound selected from the group consisting of alkali metal hydroxides, alkali metal phosphates, alkali metal carbonates, and alkali metal salts of silicic acid, and is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; alkali metal phosphates such as trisodium phosphate; carbonates of alkali metals such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate; alkali metal salts of silicic acid such as sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4, potassium silicate (potassium metasilicate, potassium sesquisilicate, potassium orthosilicate), and the like. These alkaline agents can form hydrates. Among them, hydroxides of alkali metals and alkali metal salts of silicic acid are more preferable, and alkali metal salts of silicic acid are still more preferable. In addition, compounds exemplified as chelating agents to be described later are not included in the alkaline agent of the present invention.
When the cleaning agent composition contains an alkaline agent, the content of the alkaline agent is preferably 5 to 85% by mass based on the cleaning agent composition. If the content of the alkaline agent is in the above range, the cleaning power becomes higher. The content of the alkaline agent is preferably 10 to 50% by mass. When 2 or more alkaline agents are contained, the content is defined as the total content of the respective alkaline agents.
The chelating agent is preferably contained in the cleaning agent composition because the cleaning power is higher.
Examples of the chelating agent include: chelating agents such as aminocarboxylic acid, hydroxycarboxylic acid, phosphoric acid, ether carboxylate, and phosphonic acid. The chelating agent of the present invention is not a compound such as sodium polyacrylate, which will be described later as a polymer dispersant having a mass average molecular weight of 3000 to 300000.
Examples of the aminocarboxylic acid-based chelating agent include: ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), glutamic diacetic acid (GLDA), hydroxyethyliminodiacetic acid (HIDA), Dihydroxyethylglycine (DHEG), 1, 3-propanediaminetetraacetic acid (PDTA), 1, 3-diamino-2-hydroxypropanehexaacetic acid (DPTA-OH), aspartic acid diacetic acid (ASDA), ethylenediamine succinic acid (EDDS), or salts thereof.
Examples of the hydroxycarboxylic acid chelating agent include: malic acid, succinic acid, citric acid, lactic acid, tartaric acid, gluconic acid or their salts.
Examples of the phosphate chelating agent include: tripolyphosphoric acid, hexametaphosphate, and the like.
Examples of the phosphonic acid-based chelating agent include: hydroxyethylidene diphosphonic acid (HEDP), nitrilotrimethylene phosphonic acid (NTMP), phosphonobutane tricarboxylic acid (PBTC), ethylene diamine tetramethylene phosphonic acid (EDTMP), or salts thereof.
Examples of the salt of the chelating agent include: alkali metal salts such as potassium and sodium; salts of alkaline earth metals such as magnesium and calcium. Among them, a salt of an alkali metal is preferable, and a sodium salt or a potassium salt is more preferable.
The chelating agent in the present invention is preferably an aminocarboxylic acid-based chelating agent, a phosphonic acid-based chelating agent, or the like, more preferably nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid, or a salt thereof, or the like, and still more preferably nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, or a salt thereof.
When the cleaning agent composition contains a chelating agent, the content of the chelating agent is preferably 5 to 85% by mass based on the cleaning agent composition. If the chelating agent is less than 5 mass%, the generation of scale may be problematic. If the chelating agent exceeds 85 mass%, the cleaning power may be lowered. The content of the chelating agent is preferably 30 to 50% by mass. When 2 or more chelating agents are contained, the content is defined as the total content of the respective chelating agents.
When the detergent composition contains a solubilizer, the storage stability of the detergent composition is improved in the case of a liquid, which is preferable.
Examples of the solubilizer include: aromatic acids or salts thereof, carboxylic acids or salts thereof, alkyl polyglucosides, and the like. These may be used alone, or 2 or more of them may be used in combination.
Examples of the aromatic acid include: xylene sulfonic acid, toluene sulfonic acid, cumene sulfonic acid, benzoic acid, and the like.
Examples of the carboxylic acid include: citric acid, malic acid, succinic acid, tartaric acid, 2-ethylhexanoic acid (acrylic acid), octanoic acid (Caprylic acid), and the like.
Examples of the salt include: alkali metals such as potassium and sodium, and amines such as monoethanolamine, diethanolamine and triethanolamine, and among them, sodium salts are preferred.
Examples of the alkyl polyglucoside include butyl polyglucoside.
Among them, 1 or 2 or more of 2-ethylhexanoic acid (acrylic acid), octanoic acid (Caprylic acid) and butyl polyglucoside are preferable as the solubilizer.
When the detergent composition contains a solubilizer, the content of the solubilizer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably 1 to 5% by mass, based on the detergent composition. When 2 or more solubilizing agents are contained, the above content is defined as the total content of the respective solubilizing agents.
If the detergent composition contains a bleaching agent, the detergency, the antibacterial effect, the deodorizing action and the bleaching action are improved.
Examples of the bleaching agent include: chlorine bleaching agents such as chlorinated isocyanurates (sodium dichloroisocyanurates), potassium chlorinated isocyanurates (potassium dichloroisocyanurates), etc.), trichloroisocyanuric acid, hypochlorites (sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc.), etc. These bleaching agents may be used in 1 kind, or 2 or more kinds may be used in combination. In addition, these bleaching agents may be hydrates. Among these, chlorinated isocyanurates and hypochlorites are preferable as the bleaching agent, and sodium chlorinated isocyanurates and sodium hypochlorite are more preferable.
When the cleaning agent composition contains a bleaching agent, the content of the bleaching agent is preferably 0.1 to 20% by mass based on the cleaning agent composition. If the bleaching agent is less than 0.1% by mass, the improvement of detergency, a sterilizing effect, a deodorizing effect, or a bleaching effect obtained by adding the bleaching agent may be insufficient. If the bleaching agent exceeds 20% by mass, chlorine odor may be a problem when the bleaching agent is a chlorine-based bleaching agent, for example. The content of the bleaching agent is preferably 2 to 10% by mass. When 2 or more bleaching agents are contained, the above content is defined as the total content of the respective bleaching agents.
If the cleaning agent composition contains an anticorrosive agent, the anticorrosive action (anticorrosive action) of the cleaning agent composition is improved.
As the anticorrosive agent, an anticorrosive agent for aluminum, copper, or copper alloy is preferably used. As such an anticorrosive agent, for example, it is possible to suitably use: benzotriazole or a derivative thereof (e.g., benzotriazole, methylbenzotriazole, 5-dodecylbenzotriazole, 5-octylbenzotriazole, 5-hexylbenzotriazole, 5-butylbenzotriazole, 5-methylbenzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, carboxybenzotriazolemethyl ester, carboxybenzotriazolebutyl ester, carboxybenzotriazolohexyl ester, benzotriazoleoctyl ester, dicarboxypropylbenzotriazole, etc.), benzimidazole or a derivative thereof (e.g., benzimidazole, 2-mercaptobenzimidazole, thiazolylbenzimidazole, thiabendazole, etc.), benzothiazole or a derivative thereof (e.g., benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, etc.). Among them, benzimidazole, benzotriazole and methylbenzotriazole are preferable, and benzotriazole and methylbenzotriazole are more preferable.
When the cleaning agent composition contains an anticorrosive agent, the content of the anticorrosive agent is preferably 0.001 to 5% by mass based on the cleaning agent composition. If the content of the anticorrosive agent is less than 0.001% by mass, the anticorrosive effect may not be sufficiently exhibited. If the anticorrosive agent exceeds 5 mass%, the effect of odor peculiar to the anticorrosive agent may be enhanced. The content of the anticorrosive is preferably 0.1 to 2 mass%. When 2 or more kinds of anticorrosive agents are contained, the above content is defined as the total content of the respective anticorrosive agents.
If the cleaning agent composition contains a degerming agent, the degerming effect is improved.
Examples of the degerming agent include: n, N '-tris (hydroxyethyl) hexahydro-s-triazine, 4, 4-dimethyloxazolidine, 2-octyl-4-isothiazolin-3-one, alkyldimethylbenzylammonium chloride, benzethonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium chloride, cetylpyridinium chloride, alkyldimethylhydroxylammonium chloride, 4, 4' - (tetramethylenedicarbonylamino) bis (1-decylpyridyl bromide), chlorhexidine gluconate, chlorhexidine hydrochloride, polyhexamethylene biguanide hydrochloride, pyridine-2-thiol-1-sodium oxide, isopropylmethylphenol, 2,4,4 '-trichloro-2' -hydroxydiphenyl ether, alkylpolyaminoethylglycine, sorbic acid, acetic acid, succinic acid, maleic acid, benzoic acid, propionic acid, alkyl dimethyl hydroxyethyl ammonium chloride, and the like. Among them, didecyl dimethyl ammonium chloride, dioctyl dimethyl ammonium chloride, alkyl dimethyl hydroxyethyl ammonium chloride and the like are preferable.
When the cleaning agent composition contains the antibacterial agent, the content of the antibacterial agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 15% by mass, based on the cleaning agent composition. When 2 or more kinds of the degerming agents are contained, the above content is defined as the total content of the respective degerming agents.
If the detergent composition contains an enzyme, the cleaning power is improved.
Examples of the enzyme include: protease, esterase, lipase, nuclease, cellulase, amylase, pectinase, and the like. When the enzyme is contained, the detergency is improved by the function of the enzyme. Among them, protease, amylase and lipase are preferable.
Examples of commercially available enzymes that can be used as proteases include: alcalase, Savinase, Everlase, Kannase, Esperase, Ovozyme (Novozymes Japan Ltd.), Purafect, Properase, Purafect OX (Genencor International, Inc.), and the like.
Examples of commercially available enzymes that can be used as amylases include: rapidase (ギストーブロカーズ Co.), Termamyl, Duramyl, Stainzyme (Novo Nordisk BioIndustry Co., Ltd.), Purastar ST, Purastar Oxam (Genencor International, Inc.), etc.
Commercially available enzymes that can be used as lipases include, for example: enchiron AKG-2000 (manufactured by Rockyok chemical industries, Ltd.), Lipozyme (Novozymes Japan Ltd.), and the like.
When the detergent composition contains an enzyme, the content of the enzyme is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the mass of the enzyme protein in the detergent composition. When 2 or more enzymes are contained, the above content is defined as the total content of the respective enzymes.
When the detergent composition of the present invention contains an enzyme and an alkaline agent, it is preferable to contain an enzyme stabilizer in order to suppress enzyme deactivation in a neutral to weakly alkaline aqueous solution containing an alkaline agent. The enzyme stabilizer is preferably one containing 1 or more kinds selected from boric acid, a boron compound capable of forming boric acid, and a water-soluble calcium salt. The amount of the enzyme stabilizer is preferably 0.001 to 10% by mass, more preferably 0.01 to 8% by mass, and still more preferably 1 to 5% by mass, based on the detergent composition.
The detergent composition of the present invention may contain a polymeric dispersant having a mass average molecular weight of 3000 to 300000. When such a polymer dispersant is contained, the scale-preventing ability is improved. The polymer dispersant may be used alone or in combination of 2 or more.
Examples of the polymer dispersant having a mass average molecular weight of 3000 to 300000 include: polyacrylic acid, aconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymaconic acid, poly-alpha-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, olefin-maleic acid copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methylvinyl ether copolymer, maleic anhydride-ethylene crosslinked copolymer, maleic anhydride-acrylic acid copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylate copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, poly-beta-ketonic acid, polyketone acid derived from maleic anhydride and carbon monoxide, and mixtures thereof, Itaconic acid, ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid methylene copolymer, itaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, metal salts thereof, and the like.
Examples of the metal salt include: alkali metal salts such as potassium and sodium; salts of alkaline earth metals such as magnesium and calcium. Among them, a salt of an alkali metal is preferable, and a sodium salt or a potassium salt is more preferable.
The polymeric dispersant having a mass average molecular weight of 3000 to 300000 in the present invention is preferably a polyacrylate or a salt of an olefin-maleic acid copolymer, and more preferably a sodium polyacrylate or a sodium salt of an olefin-maleic acid copolymer.
When the detergent composition contains a polymeric dispersant having a mass average molecular weight of 3000 to 300000, the content thereof is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the detergent composition. When 2 or more kinds of polymer dispersants having a mass average molecular weight of 3000 to 300000 are contained, the above content is defined as the total content of the respective polymer dispersants.
The mass average molecular weight was determined by gel permeation chromatography using a phosphoric acid buffer solution and acetonitrile as developing solvents and polyacrylic acid as a standard substance.
In the cleaning agent composition of the present invention, a surfactant other than the component (b) (hereinafter, referred to as other surfactant) may be used as long as the effect of the present invention is not impaired. The component (a) is not included in the surfactant of the present invention.
As the other surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and the like can be used, and a nonionic surfactant is preferable. Examples of the nonionic surfactant include: polyoxyalkylene dialkyl ethers, polyoxyalkylene alkylphenyl ethers, fatty acid alkanolamides, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkyl polyglycosides, polyoxyethylene methyl ether fatty acid esters, polyoxyalkylene alkylamines, and the like.
When the cleansing composition contains a surfactant other than the component (b), the content thereof is preferably 10% by mass or less, more preferably 5% by mass or less, and most preferably substantially no surfactant other than the component (b) is contained in the cleansing composition.
The cleaning agent composition of the present invention may contain other ingredients such as a solvent and an extender which can be compounded into the cleaning agent composition as needed. Further, an antifoaming agent may be contained in addition to the components (a) and (b) as required. These may be used alone in 1 kind, or in combination of 2 or more kinds.
Examples of the solvent include water and an organic solvent. As the organic solvent, 1 to 3-membered alcohols can be suitably used, and examples thereof include: 1-membered alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methoxyethanol, 2-ethoxyethanol and the like; 2-or 3-membered polyhydric alcohols such as ethylene glycol, propylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerin, polyethylene glycol, and polypropylene glycol. Among them, 2-or 3-membered polyhydric alcohols are preferable, and polypropylene glycol, propylene glycol, and 1, 2-propanediol are more preferable.
Examples of the extender include: sodium sulfate (mirabilite), powdered silica, and the like.
Examples of the defoaming agent include silicone defoaming agents.
The formulation of the detergent composition of the present invention may be any of liquid, solid (powder, granule (granule), tablet (tablet), flake (flake), block (block), or the like). Liquids and solids are preferred. In addition, the detergent composition of the present invention is also suitable for use in cartridge (cartridge) detergents and the like.
The method for producing the detergent composition of the present invention is not particularly limited, and may be appropriately selected depending on the formulation. For example, the component (a) and the component (b) can be produced by mixing or stirring the components and other components blended as desired. The order of mixing the components, the method of mixing or stirring, and the like are not particularly limited.
For example, in the case of producing a solid detergent composition such as a block, for example, it is preferable that: first, water and a raw material of the detergent composition other than water are stirred and mixed to prepare a slurry, and then the slurry is put into a desired mold, a container, or the like and cooled to be solidified.
Specifically, first, a raw material of the detergent composition other than water is added to water, and then, the mixture is stirred while maintaining the temperature at 30 to 100 ℃, thereby preparing a slurry solution containing water and the raw material of the detergent composition.
The amount of the raw material of the detergent composition other than water is preferably 35 to 100% by mass based on the total amount of the slurry.
Next, the slurry is put into a desired mold or container, and then the slurry is left to stand at room temperature for 1 to 24 hours to be cured, thereby producing a cleaning agent composition comprising a solid cured into the shape of the mold or container.
In the production of a granular (particulate) detergent composition, the components (a) and (b) as raw materials of the detergent composition and other granular raw materials may be mixed as desired. As the mixing, a screw mixer, a nauta mixer, or a drum mixer can be suitably used.
In addition, in the production of a powdery detergent composition, the components (a) and (b) as raw materials of the detergent composition and powdery raw materials of other components to be blended as desired may be mixed. The mixing may be suitably carried out using a screw mixer, nauta mixer, or drum mixer.
The liquid detergent composition can be produced by mixing or stirring any of the components, without any particular limitation. The order of mixing the components, the method of mixing or stirring, and the like are not particularly limited.
The automatic cleaning machine using the cleaning agent composition for an automatic cleaning machine of the present invention is not particularly limited, and examples thereof include a spray type automatic cleaning machine. Examples of the spray type automatic cleaning machine include: automatic dish washing machines, container washing machines, and the like. Examples of the container include plastic containers used for transporting food and the like. Among them, the detergent composition of the present invention is suitable for use as a detergent composition for an automatic dishwasher or a container washing machine, and more suitable for use as a detergent composition for an automatic dishwasher. The detergent composition of the present invention is suitable for use in automatic cleaning machines for business use or home use, more suitable for use in professional automatic cleaning machines, and particularly suitable for use in automatic dish washing machines for business use.
When the detergent composition for an automatic washing machine of the present invention is used to wash dishes or the like with the automatic washing machine, the detergent composition diluted with or dissolved in water may be brought into contact with the dishes or the like in the automatic washing machine, and the concentration of the detergent composition in the detergent composition is preferably 0.04 to 0.3% by mass.
[ examples ]
Hereinafter, examples for more specifically explaining the present invention are shown. The present invention is not limited to these examples.
< examples 1 to 100>
The components shown in tables 1 to 8 were mixed in the ratios shown in tables 1 to 8, and mixed or dissolved by heating to produce the respective cleaning agent compositions of examples 1 to 100. The numerical values in tables 1 to 8 are the ratios (% by mass) of the net contents of the respective components to the cleaning agent composition.
< comparative examples 1 to 116>
The components shown in tables 9 to 18 were mixed in the ratios shown in tables 9 to 18, and mixed or dissolved by heating to produce the respective cleaning agent compositions of comparative examples 1 to 116. The values in tables 9 to 18 are the ratio (% by mass) of the net content of each component to the cleaning agent composition.
The cleaning agent compositions produced in examples 1 to 100 and comparative examples 1 to 116 were evaluated for foam suppressing property and cleaning ability by the following methods.
< foam suppressing Property >
(foam suppressing Condition)
In the test of foam suppression, in the washing step, a detergent composition was charged so that the concentration of the detergent composition became 0.15 mass% with respect to the amount of water in the automatic dish washing machine to prepare a washing liquid, the automatic dish washing machine was operated, and foaming after 2 minutes and foaming after 30 seconds after the operation was stopped were observed.
As the automatic dishwasher, a single-tank conveyor type dishwasher (model C44B) manufactured by Hobart Corporation was used.
(1) Foam inhibition at low temperature
The height of the bubbles when the automatic dishwasher was operated at a washing temperature of 20 ℃ was observed.
(2) Foam inhibition in the presence of soil
45g of whole eggs (egg liquid of eggs) were put into an automatic dish washer, and the height of bubbles was observed when the dish washer was operated at a washing temperature of 50 ℃.
(evaluation criteria for foam suppressing Property)
Very good: high foam suppressing ability (height of foam 2 minutes after start of operation is less than 100mm and height of foam 30 seconds after stop of operation is less than 70mm)
Good: low foam inhibition (foam height 2 minutes after start of operation is 100mm or more or foam height 30 seconds after stop of operation is 70mm or more)
X: very low foam inhibition (foam height 2 minutes after start of operation is 100mm or more and foam height 30 seconds after stop of operation is 70mm or more)
< cleaning force >
(cleaning conditions)
The test of the cleaning power was carried out by charging the detergent composition so that the concentration of the detergent composition in the cleaning step became 0.15% with respect to the amount of water in the automatic dish washing machine to prepare a cleaning liquid, cleaning the sample for the cleaning test (1 g of complex dirty and dirty person was applied to a polyethylene-made lunch box) with the automatic dish washing machine, and visually evaluating the appearance of the sample.
As an automatic dishwasher, a door-made dishwasher (model JW-650UF) made by Hoshizaki, inc was used under the following cleaning conditions: the cleaning time is 60 seconds, the cleaning temperature is 60 ℃, the rinsing time is 5 seconds, and the rinsing temperature is 80 ℃. Tap water was used as the washing water.
(evaluation criteria for detergency)
The cleaning power of the cleaning agent composition was evaluated as follows.
Very good: no adhesion of dirt was observed.
O: substantially no adhesion of dirt was observed.
X: significant soil residue was observed.
The compositions and evaluation results of the cleaning agent compositions produced in examples and comparative examples are shown in tables 1 to 18.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
[ Table 5]
[ Table 6]
[ Table 7]
[ Table 8]
[ Table 9]
[ Table 10]
[ Table 11]
[ Table 12]
[ Table 13]
[ Table 14]
[ Table 15]
[ Table 16]
[ Table 17]
[ Table 18]
The polyoxypropylene triol in the table is a propylene oxide adduct of glycerin. In the table, PO means propyleneoxy.
The "remainder" of the table means: the mass% of the components other than water and mirabilite is subtracted from 100 mass% of the cleaning agent composition, and the remaining part is water or mirabilite.
The compounds of component (b) in tables 1 to 16 are as follows.
Reverse pluronic type block polymer (mass average molecular weight 4000): EO/PO molar ratio of 1/3
Reverse pluronic type block polymer (mass average molecular weight 4500): EO/PO molar ratio of 1/3.5
Reverse quaternary ketone block polymer (mass average molecular weight 4000)
Reverse quaternary ketone block polymer (mass average molecular weight 5000)
Pluronic type block polymer (mass average molecular weight 2000): EO/PO molar ratio of 1/7
Pluronic type block polymer (mass average molecular weight 3000): EO/PO molar ratio of 1/7
Quaternary ketone type block polymer (mass average molecular weight 2500): EO/PO molar ratio of 1/7
Quaternary ketone type block polymer (mass average molecular weight 3000): EO/PO molar ratio of 1/7
The compounds used as component (a') are as follows.
Polyoxyethylene triol (mass average molecular weight 3000): ethylene oxide adduct of glycerol
Polyoxyethylene polyoxypropylene triol (mass average molecular weight 2500): ethylene oxide and propylene oxide adducts of glycerol
Fatty alcohol alkoxylates: product name Plurafac LF403 manufactured by BASF
Polyoxyethylene polyoxypropylene alkyl ether 1: product name of Peporu AS-054C manufactured by Toho chemical Co., Ltd
According to tables 1 to 8, the cleaning agent compositions of examples 1 to 100 exhibited high foam inhibition at low temperatures and in the presence of dirt. Further, the cleaning agent compositions of the examples were excellent in cleaning power. The cleaning agent compositions of comparative examples 1 to 116 could not suppress foaming at low temperatures or in the presence of dirt.
Claims (7)
1. A detergent composition for an automatic cleaning machine, comprising:
0.01 to 10 mass% in total of (a) at least 1 compound selected from the group consisting of an alkylene oxide adduct of a polyhydric alcohol represented by the following general formula (1) and a polyoxyalkylene monoalkyl ether represented by the following general formula (2); and the number of the first and second groups,
0.1 to 10 mass% in total of (b) at least 1 surfactant selected from the group consisting of reverse pluronic block polymers, reverse quaternary ketone block polymers, pluronic block polymers and quaternary ketone block polymers,
in the formula (1), R1A residue obtained by removing all hydroxyl groups from a 3-to 8-membered C3-20 polyhydric alcohol, A1O represents oxypropylene, n represents the average molar number of addition of oxypropylene groups and is a number of 2 to 1000, m represents an integer of 3 to 8, and m [ (O- (A) ]1O) n-H are optionally the same or different,
in the formula (2), R2Represents a C12-15 branched alkyl group A2O represents oxypropylene, and t represents an average molar number of addition of oxypropylene groups and is a number of 2 to 100.
2. The detergent composition for an automatic cleaning machine as claimed in claim 1, wherein in the general formula (2), t is a number of 2 to 60.
3. The detergent composition for an automatic cleaning machine as claimed in claim 1, wherein the polyoxyalkylene monoalkyl ether represented by the general formula (2) is polyoxypropylene tridecyl ether.
4. The detergent composition for automatic cleaning machines according to claim 1, wherein R in the general formula (1)1Represents a residue obtained by removing all hydroxyl groups from a 3-membered aliphatic alcohol having 3 to 5 carbon atoms, n is a number of 2 to 250, and m is 3.
5. The detergent composition for automatic cleaning machines according to claim 1, wherein the molar ratio of oxyethylene (EO) groups to oxypropylene (PO) (EO/PO) groups in the reverse pluronic block polymer is 1/10 to 1/2.
6. The detergent composition for an automatic cleaning machine according to claim 1, further comprising at least 1 selected from the group consisting of an alkaline agent, a chelating agent, a solubilizing agent, a bleaching agent, an anticorrosive agent, a bactericide and an enzyme.
7. The detergent composition for automatic cleaning machines according to claim 1, which is a detergent composition for automatic dish washing machines or container washing machines.
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| JP2016107252A JP6035447B1 (en) | 2016-05-30 | 2016-05-30 | Cleaning composition for automatic cleaning machine |
| PCT/JP2016/077325 WO2017208472A1 (en) | 2016-05-30 | 2016-09-15 | Detergent composition for automatic dishwasher |
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| CN115678687A (en) * | 2022-09-15 | 2023-02-03 | 河南海利未来科技集团有限公司 | Low-foam sterilization dish-washing machine cleaning agent and preparation method thereof |
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| JPS5872000A (en) * | 1981-10-23 | 1983-04-28 | 第一工業製薬株式会社 | Alkali detergent |
| JPS62297399A (en) * | 1986-06-18 | 1987-12-24 | ライオン株式会社 | Detergent composition for tableware washing machine |
| JPS6335697A (en) * | 1986-07-24 | 1988-02-16 | ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン | Low fomable and/or foam control surfactant mixture and its use |
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| JP2937635B2 (en) * | 1992-07-15 | 1999-08-23 | 新高化学工業株式会社 | Cleaning agents for automatic dishwashers |
| DE69515331T2 (en) * | 1994-12-09 | 2000-10-19 | The Procter & Gamble Company, Cincinnati | COMPOSITIONS CONTAINING DIACYL PEROXIDE PARTICLES FOR AUTOMATIC DISHWASHING |
| JP4026873B2 (en) * | 1996-07-05 | 2007-12-26 | 株式会社ニイタカ | Detergent composition for dishwashers |
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- 2016-05-30 JP JP2016107252A patent/JP6035447B1/en active Active
- 2016-09-15 WO PCT/JP2016/077325 patent/WO2017208472A1/en active Application Filing
- 2016-09-15 CN CN201680003793.XA patent/CN107709531B/en active Active
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| Publication number | Publication date |
|---|---|
| WO2017208472A1 (en) | 2017-12-07 |
| JP2017214447A (en) | 2017-12-07 |
| JP6035447B1 (en) | 2016-11-30 |
| CN107709531A (en) | 2018-02-16 |
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