Germicidal cleaner composition

A composition of peracetic acid and a specific surfactant with a weakly acidic to neutral pH addresses the clogging issues in existing cleaning agents, achieving effective bactericidal and cleaning effects while maintaining membrane permeability.

JP2025094965APending Publication Date: 2025-06-26NICCA CHEM COMPANY
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Patent Information

Application Number
JP2023210669
Authority / Receiving Office
JP · JP
Patent Type
Applications
Current Assignee / Owner
Filing Date
2023-12-14
Publication Date
2025-06-26

AI Technical Summary

Technical Problem

Existing sterilizing and cleaning agents, particularly those used for dialysis devices and water treatment filtration membranes, often cause clogging and are not effective in maintaining membrane permeability due to their strong acidic or alkaline nature.

Method used

A composition containing peracetic acid and a specific surfactant with a particular structure, which maintains a pH of weakly acidic to neutral, thereby preventing membrane clogging and enhancing permeability.

Benefits of technology

The composition achieves excellent bactericidal and cleaning effects while maintaining the permeability of filtration membranes, reducing the likelihood of clogging and ensuring effective regeneration treatment of dialysis devices and water treatment membranes.

✦ Generated by Eureka AI based on patent content.

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Abstract

To provide a germicidal cleaning composition that is used for regeneration treatment of a filtration membrane for a dialysis device or a water treatment system, and that exhibits excellent permeability through the filtration membrane and prevents clogging of the filtration membrane.SOLUTION: The germicidal cleaner composition comprises peracetic acid (A), a specific surfactant (B), and water, and exhibits a pH from weakly acidic to neutral.SELECTED DRAWING: None
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Description

Technical Field

[0001] The present invention relates to a composition having excellent bactericidal and cleaning effects.

Background Art

[0002] In the sterilization and cleaning of dirt, generally strong acidic or strong alkaline sterilizing and cleaning agents are used. For example, in Patent Document 1, regarding a peracetic acid-based cleaning agent widely used for sterilization purposes, the pH of the cleaning agent is adjusted to be strongly acidic mainly from the viewpoint of the stability of peracetic acid. However, when such a strongly acidic cleaning agent is used, there are cases where the waste liquid causes adverse effects on sewer pipes and the parts to be cleaned. Regarding sewer pipes, a warning has been issued by the Tokyo Metropolitan Sewerage Bureau, and it is required to adjust the pH of the waste liquid to pH 5 to 9, which is the drainage standard. Also, regarding the parts to be cleaned, in parts such as metal and plastic, when a strongly acidic or strongly alkaline cleaning agent is used, the parts may discolor or become brittle, and a cleaning agent with a pH close to the neutral range is required. In Patent Document 2, a sterilizing and cleaning agent containing peracetic acid, hydrogen peroxide, acetic acid and / or its salt, and a specific anionic surfactant and having a pH of 4 to 10 is disclosed. Furthermore, in Patent Document 3, a sterilizing and cleaning agent containing peracetic acid, hydrogen peroxide, acetic acid and / or its salt, and an additive and having a pH of 4 to 10 is disclosed. However, for example, when used for cleaning a dialysis device or a filtration membrane for water treatment, the filtration membrane is likely to be blocked and it is likely to be difficult to reuse, so it is not sufficient.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0004] An object of the present invention is to provide a sterilizing and cleaning composition that is used for regeneration treatment of filtration membranes in dialysis devices and water treatment, has excellent permeability of the filtration membrane, and is less likely to cause clogging of the filtration membrane.

MEANS FOR SOLVING THE PROBLEMS

[0005] As a result of intensive studies, the present inventors have found that a sterilizing and cleaning composition containing peracetic acid and a surfactant having a specific structure solves the above-mentioned problems. That is, the present invention is characterized by the following points. 1. A sterilizing and cleaning agent composition containing peracetic acid (A), a surfactant (B), and water, The surfactant (B) contains at least one selected from the group consisting of a nonionic surfactant represented by the following formula (1), a nonionic surfactant represented by the following formula (2), an amphoteric surfactant represented by the following formula (3), an amphoteric surfactant represented by the following formula (4), and an anionic surfactant represented by the following formula (5), The sterilizing and cleaning agent composition exhibits a pH of weakly acidic to neutral, The sterilizing and cleaning agent composition.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0006] According to the present invention, it is possible to provide a composition for germicidal cleaning that is used for the regeneration treatment of dialysis devices, filtration membranes for water treatment, etc., has excellent permeability of the filtration membrane, and is less likely to cause clogging of the filtration membrane. The filtration membrane is not particularly limited as long as it is a filtration membrane generally used in membrane separation technology, and examples thereof include reverse osmosis membranes, microfiltration membranes, and ultrafiltration membranes.

Embodiments for Carrying Out the Invention

[0007] Hereinafter, embodiments of the present invention will be described in detail. The description of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these contents unless it exceeds the gist thereof.

[0008] <Composition for Germicidal Cleaning> The composition for germicidal cleaning of the present invention contains peracetic acid (A), a surfactant (B), and water. The content of peracetic acid (A) in the composition for germicidal cleaning is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.1 to 2% by mass. If it is less than the above range, the bactericidal property is likely to be inferior, and it is substantially difficult to increase it beyond the above range. Moreover, even if it is increased beyond the above range, the performance does not improve significantly, and the production cost increases. The content of surfactant (B) in the composition for sterilization and washing is preferably 0.05 to 10% by mass, more preferably 0.1 to 10% by mass, still more preferably 1 to 10% by mass, particularly preferably 1 to 7.5% by mass, and most preferably 1 to 5% by mass. If it is less than the above range, the detergency tends to be inferior. If it is more than the above range, the film permeability tends to be inferior or the manufacturing cost increases.

[0009] The composition for sterilization and washing of the present invention can preferably further contain a chelating agent (C). When containing the chelating agent (C), the content of the chelating agent (C) in the composition for sterilization and washing is preferably 0.01 to 10% by mass, more preferably 0.05 to 7.5% by mass, still more preferably 0.08 to 6% by mass, and particularly preferably 0.3 to 5% by mass. If it is less than the above range, the stability of peracetic acid tends to decrease. If it is more than the above range, the manufacturing cost increases. The composition for sterilization and washing of the present invention can preferably further contain a hydrotrope agent (D). When containing the hydrotrope agent (D), the content of the hydrotrope agent (D) in the composition for sterilization and washing is preferably 0.01 to 10% by mass, more preferably 0.05 to 10% by mass, still more preferably 0.08 to 10% by mass, and particularly preferably 0.3 to 10% by mass. If it is less than the above range, the effect of containing the hydrotrope agent (D) is difficult to occur. If it is more than the above range, the manufacturing cost increases.

[0010] The sterilizing and washing agent composition of the present invention can contain an aqueous solvent, a rust preventive, an antifoaming agent, a preservative, an antioxidant, a coloring agent, a deodorant, a fragrance, etc. within a range not impairing the effects of the present invention. And, the sterilizing and washing agent composition of the present invention may further appropriately contain various additives such as a thickener, a fragrance, an enzyme, etc. used in general drugs, etc., as necessary.

[0011] [pH of the composition for sterilization and washing] The composition for bactericidal cleaning of the present invention preferably exhibits a pH of weakly acidic to neutral. In the present invention, weakly acidic means a pH of 3.5 or more and less than 6.7, and neutral means a pH of 6.7 or more and 7.3 or less. As the pH of weakly acidic to neutral, 3.5 to 7.3 is preferable, 4 to 7 is more preferable, 4 to 6 is still more preferable, and 4 to 5.5 is particularly preferable. In order to increase the generation amount of peracetic acid and make it stable, the pH of the composition for bactericidal cleaning of the present invention is preferably within the above range. If it is lower than the above range, the waste liquid during sterilization and cleaning becomes strongly acidic, which may have an adverse effect on sewer pipes and parts to be cleaned. If it is higher than the above range, there is a risk that peracetic acid cannot exist stably, and the bactericidal property tends to be inferior.

[0012] The pH of the composition for bactericidal cleaning of the present invention can be adjusted with alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethanolamine so as to be a value within the above range. Also, a part of the acetic acid blended for the synthesis of peracetic acid may be neutralized in advance with the alkaline compound and blended in the state of acetate to adjust the pH. The method for adjusting the pH is not particularly limited, but from the viewpoint of safety, a method of neutralizing a part of acetic acid in advance with the alkaline compound and blending it in the state of acetate to adjust the pH is preferable. The pH of the composition for bactericidal cleaning of the present invention can be measured by a known method such as the glass electrode method.

[0013] <Peracetic acid (A)> Peracetic acid is a relatively safe compound because its decomposition products are acetic acid and water, and it exhibits high bactericidal and antiviral properties against bacteria, fungi, viruses, etc., and is therefore used in various bactericides and antiviral agents.

[0014] As peracetic acid (A), commercially available products can generally be used, and industrial products or peracetic acid as a reagent may be used, and it is not particularly limited. Alternatively, peracetic acid (A) may be synthesized and used, for example, by the equilibrium reaction of hydrogen peroxide and acetic acid. In this case, the production amount of peracetic acid depends on the concentrations of hydrogen peroxide and acetic acid in the equilibrium solution. The concentration of peracetic acid in the equilibrium solution is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.1 to 2% by mass. Next, hydrogen peroxide and acetic acid required for the production of peracetic acid will be described.

[0015] (Hydrogen peroxide) Hydrogen peroxide contributes to the production of peracetic acid by the equilibrium reaction with acetic acid. Therefore, the blending amount of hydrogen peroxide when preparing the equilibrium solution affects the production amount of peracetic acid. From the viewpoint of the production amount of peracetic acid, the blending amount of hydrogen peroxide is preferably 1 to 15% by mass, more preferably 1 to 10% by mass, and still more preferably 1 to 8.5% by mass. Commercially available hydrogen peroxide can generally be used.

[0016] (Acetic acid) Acetic acid contributes to the production of peracetic acid by the equilibrium reaction with hydrogen peroxide. Therefore, the blending amount of acetic acid when preparing the equilibrium solution affects the production amount of peracetic acid. From the viewpoint of the production amount of peracetic acid, the blending amount of acetic acid is preferably 0.01 to 50% by mass, more preferably 0.1 to 50% by mass, still more preferably 1 to 40% by mass, and particularly preferably 1 to 35% by mass. Commercially available acetic acid can generally be used.

[0017] (Surfactant (B)) The surfactant (B) preferably contains at least one selected from the group consisting of nonionic surfactants, amphoteric surfactants, and anionic surfactants. Also, the surfactant (B) may use a compound belonging to a nonionic surfactant, an amphoteric surfactant, or an anionic surfactant alone, or may use two or more in combination.

[0018] [Nonionic surfactant] As the nonionic surfactant used in the present invention, a compound represented by the following formula (1) or a compound represented by the following formula (2) is preferable. The composition for sterilization and cleaning of the present invention may contain one kind of nonionic surfactant or may contain two or more kinds. In order to obtain high detergency, it is preferable to contain the compound represented by the general formula (1).

[0019]

Chemical formula

[0020] In formula (1), R 1 - is a linear or branched alkyl group or a linear or branched alkenyl group. In order to obtain excellent filtration membrane permeability and detergency, R 1 - is preferably a linear or branched alkyl group having 8 to 16 carbon atoms or a linear or branched alkenyl group having 8 to 16 carbon atoms, more preferably a linear or branched alkyl group having 9 to 13 carbon atoms and a main chain carbon number of 7 to 12, or a linear or branched alkenyl group having 9 to 13 carbon atoms and a main chain carbon number of 7 to 12, and even more preferably a linear or branched alkyl group having 10 to 13 carbon atoms and a main chain carbon number of 7 to 12, or a linear or branched alkenyl group having 10 to 13 carbon atoms and a main chain carbon number of 7 to 12. When R 1 is a linear alkyl group or a linear alkenyl group, the number of carbon atoms of R 1 and the number of carbon atoms of the main chain of R 1 are the same value.

[0021] -A 1 O- is an alkyleneoxy group having 2 to 4 carbon atoms, and -EO- is an ethyleneoxy group. m is the repeating unit -A 1Represents the average number of repetitions of O-. To obtain excellent detergency, m is preferably 3 to 19, more preferably 3 to 15, still more preferably 5 to 15, and most preferably 7 to 11. Average m -A in one molecule 1 The O-'s may be the same or different, -(A 1 O) m -A in - 1 The connection order of the O-'s may be random or block - like. However, -(A 1 O) m The terminal of -EO-H is -EO-H, and the terminal group is an OH group. To obtain excellent detergency, the molar ratio [EO] / (m + 1) is preferably 0.8 to 1.0. Here, [EO] in the formula is the total molar amount of ethyleneoxy groups -EO- in one molecule.

[0022] Specific examples of the compound represented by formula (1) include polyoxyethylene(12)mono(2 - propyl - 1 - heptyl)ether, polyoxyethylene(12)mono(1 - octyl)ether, polyoxyethylene(12)mono(2 - ethyl - 1 - hexyl)ether, polyoxyethylene(12)mono(1 - decyl)ether, polyoxyethylene(12)mono(isodecyl)ether, polyoxyethylene(12)mono(2 - butyl - 1 - octyl)ether, polyoxyethylene(12)mono(1 - dodecyl)ether, polyoxyethylene(12)mono(isotridecyl)ether, polyoxyethylene(12)mono(1 - tetradecyl)ether, polyoxyethylene(12)mono(2 - hexyl - 1 - decyl)ether, polyoxyethylene(6)mono(2 - propyl - 1 - heptyl)ether, polyoxyethylene(8)mono(2 - propyl - 1 - heptyl)ether, polyoxyethylene(18)mono(2 - propyl - 1 - heptyl)ether, polyoxypropylene(2)polyoxyethylene(10)mono(2 - propyl - 1 - heptyl)ether, etc., but are not limited thereto. In the above, for example, in polyoxyethylene(12) mono(2-propyl-1-heptyl) ether, "polyoxyethylene(12)" indicates that 12 oxyethylene groups are connected in series, and "mono" indicates that one 2-propyl-1-heptyl group is ether-bonded to one end of polyoxyethylene(12), and the other end of polyoxyethylene(12) is an OH group.

[0023] [Chemical formula]

[0024] In formula (2), R 2 - is a linear or branched alkyl group or a linear or branched alkenyl group. To obtain excellent filtration membrane permeability and cleanability, R 2 - is preferably a linear or branched alkyl group having 8 to 16 carbon atoms or a linear or branched alkenyl group having 8 to 16 carbon atoms, more preferably a linear or branched alkyl group having 9 to 13 carbon atoms and a main chain carbon number of 7 to 12 or a linear or branched alkenyl group having 9 to 13 carbon atoms and a main chain carbon number of 7 to 12, and even more preferably a linear or branched alkyl group having 10 to 13 carbon atoms and a main chain carbon number of 7 to 12 or a linear or branched alkenyl group having 10 to 13 carbon atoms and a main chain carbon number of 7 to 12. R 2 When R 2 - is a linear alkyl group or alkenyl group, the carbon number of R 2 - and the carbon number of the main chain of R

[0025] -(A 2 O)- and -(A 3 O)- are each independently an alkyleneoxy group having 2 to 4 carbon atoms, and -EO- is an ethyleneoxy group. q represents the average number of repetitions of the repeating unit -A 2 O-, and r represents the repeating unit -A 3Represents the average number of repetitions of O-. To obtain excellent detergency, q and r are each independently 0 to 18, and q + r is preferably 2 to 18, more preferably 2 to 14, still more preferably 4 to 14, and particularly preferably 6 to 10. Also, the average of q -A in one molecule 2 The O- may be the same or different, and is -(A 2 O) q -A in 2 The connection order of the O- may be random or block-like. And the average of r -A in one molecule 3 The O- may be the same or different, and is -(A 3 O) r -A in 3 The connection order of the O- may be random or block-like. However, -(A 2 O) q -EO-H and -(A 3 O) r The terminals of -EO-H and -(A

[0026] Furthermore, to obtain excellent detergency, the molar ratio [EO] / (q + r + 2) is preferably 0.8 to 1.0. Here, [EO] in the numerator of the formula is the total molar amount of ethyleneoxy groups -EO- in one molecule.

[0027] Specific examples of the compound represented by formula (2) include, but are not limited to, N,N-dipolyoxyethylene(12)1-dodecylamine, N,N-dipolyoxyethylene(12)1-cocoalkylamine, etc. In the above, for example, the "di" in N,N-dipolyoxyethylene(12)1-dodecylamine indicates that two carbon atoms at the other end of the consecutive oxyethylene groups with one end being an OH group are connected to the N atom of 1-dodecylamine, and "polyoxyethylene(12)" indicates that the total number of consecutive oxyethylene groups is 12.

[0028] [Amphoteric surfactant] As the amphoteric surfactant used in the present invention, compounds represented by the following formula (3) or the following formula (4) are preferable. The composition for sterilizing and cleaning of the present invention may contain one kind of amphoteric surfactant, or may contain two or more kinds. In order to obtain excellent detergency, it is preferable to contain the compound represented by the formula (3).

[0029]

Chemical formula

[0030] Specific examples of the compound represented by the formula (3) include, but are not limited to, lauryldimethylamine oxide and the like.

[0031]

Chemical formula

[0032] In the formula (4), R 6 - is an alkyl group or an alkenyl group which may contain an amide bond. In order to obtain excellent detergency, the number of carbon atoms of R 6 - is preferably 8 to 18, more preferably 10 to 16. R 7 - and R 8 - are each independently an alkyl group. In order to obtain excellent detergency, the number of carbon atoms of R 7 - and R 8- The number of carbon atoms is, independently of each other, preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 2. -R 9 - is an alkylene group which may contain a hydroxy group. In order to obtain excellent detergency, -R 9 - preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. -Z - is -COO - or -SO3 - and is.

[0033] Specific examples of the compound represented by the formula (4) include, but are not limited to, lauryl betaine, lauryl hydroxysulfobetaine, lauric acid amidopropyl betaine, and the like.

[0034] [Anionic surfactant] As the anionic surfactant used in the present invention, a compound represented by the following formula (5) is preferred. The bactericidal cleaning composition of the present invention may contain one kind of anionic surfactant or two or more kinds of anionic surfactants.

[0035]

Chemical formula

[0036] In the formula (5), R 10 - is a monovalent hydrocarbon group, and -EO- is an ethyleneoxy group. In order to obtain excellent filtration membrane permeability and detergency, R 10 - preferably has 10 to 24 carbon atoms, more preferably 10 to 20 carbon atoms, still more preferably 12 to 20 carbon atoms, and particularly preferably 12 to 18 carbon atoms. R 10 Specific examples of - include alkyl groups such as dodecyl group and octadecyl group, and alkylbenzene groups to which an alkyl group having 4 to 18 carbon atoms is added. u represents the average number of repeating units of -EO-, and in order to obtain excellent filtration membrane permeability and detergency, u is preferably a number of 0 to 5, more preferably 0. When u is 0, -X is -SO3 - Y + , or -OSO3 - Y + ; when u is 1 to 5, -SO3 - Y + . Y + is an alkali metal cation or a quaternary organic ammonium cation. Specific examples of the alkali metal cation include Li + , Na + , K + , Rb + , Cs + , Fr + . Examples of the quaternary organic ammonium cation include compounds represented by formulas such as NH4 + , R 11 -NH3 + , R 12 -NH2 + -R 13 . Here, R 11 , R 12 , and R 13 are alkyl groups having 1 or more carbon atoms which may contain a hydroxy group. Specific examples of the quaternary organic ammonium cation include NH4 + , CH3-NH3 + , CH3-NH2 + -CH3 and the like, but are not limited thereto. The composition for sterilization and washing of the present invention may use one kind of the compound represented by formula (5) alone, or may use two or more kinds in combination.

[0037] Specific examples of the compound represented by formula (5) include sodium laurylbenzenesulfonate, sodium lauryl sulfate, sodium 1-octadecanesulfonate, sodium polyoxyethylene(3)1-lauryl ether sulfate, etc., but are not limited thereto.

[0038] <Water> The water contained in the disinfectant composition of the present invention preferably has a low metal salt content in order to increase the production amount of peracetic acid and stabilize it. Specific examples of water with a low metal salt content include, for example, ion-exchanged water, distilled water, pure water, ultrapure water, purified water, and water for injection, but are not limited thereto.

[0039] <Chelating agent (C)> The chelating agent (C) preferably contains a phosphoric acid-based chelating agent and / or a carboxylic acid-based chelating agent. When the phosphoric acid-based chelating agent and the carboxylic acid-based chelating agent are used in combination, the mass ratio of the amount of the phosphoric acid-based chelating agent / carboxylic acid-based chelating agent in the bactericidal cleaning composition of the present invention is preferably 1.0 / 39.0 to 39.5 / 0.5, more preferably 13.0 / 27.0 to 27.0 / 13.0. If it is smaller than the above range, the generation amount of peracetic acid may decrease, and if it is larger than the above range, the stability of peracetic acid may decrease, and in either case, the bactericidal property is likely to be inferior.

[0040] (Phosphoric acid-based chelating agent) The phosphoric acid-based chelating agent can be used without particular limitation as long as it is generally known as a phosphoric acid-based chelating agent. Specific examples of the phosphoric acid-based chelating agent include, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and its salts, 2-phosphonobutane 1,2,4-tricarboxylic acid (PBTC) and its salts, and tripolyphosphoric acid (STPP) and its salts, etc. Examples of the salts include sodium salts, potassium salts, etc., but are not limited thereto. From the viewpoints of the production amount of peracetic acid, the availability of the phosphoric acid-based chelating agent, and the economic aspect, one or more selected from the group consisting of HEDP and its salts, PBTC and its salts, and STPP and its salts are preferable, and HEDP and its salts are more preferable. These may be used alone or in combination of two or more.

[0041] (Carboxylic acid-based chelating agent) The carboxylic acid-based chelating agent can be used without particular limitation as long as it is generally known as a carboxylic acid-based chelating agent. Specific examples of the carboxylic acid-based chelating agent include, for example, diethylenetriaminepentaacetic acid (DTPA) and its salts, hydroxyethylethylenediaminetriacetic acid (HEDTA) and its salts, ethylenediaminetetraacetic acid (EDTA) and its salts, etc., which are known as aminocarboxylic acid-based chelating agents. Examples of the salts include sodium salts, potassium salts, etc., but are not limited thereto. From the viewpoints of the stability of peracetic acid, the availability of the carboxylic acid-based chelating agent, and economy, aminocarboxylic acid-based chelating agents are preferred, one or more selected from the group consisting of DTPA and its salts, EDTA and its salts, and HEDTA and its salts are more preferred, and one or more selected from DTPA and its salts, EDTA and its salts are even more preferred. These may be used alone or in combination of two or more.

[0042] <Hydrotrope (D)> The hydrotrope (D) is an amphiphilic compound having a relatively low molecular weight and having a hydrophilic group and a hydrophobic group in the molecule. By containing the hydrotrope (D), the germicidal cleaning composition can solubilize hydrophobic molecules and prevent changes in the viscosity of the germicidal cleaning composition (mainly viscosity reduction) and precipitation at low or high temperatures. Unlike surfactants, the hydrotrope (D) has low cooperativity of aggregation and can function at molar concentrations. Examples of the hydrophilic group include a hydroxyl group, a sulfonic acid group, an ester group, an ether group, etc. Examples of the hydrophobic group include aliphatic hydrocarbon groups such as an alkyl group and an alkylene group, and aromatic hydrocarbon groups such as a phenyl group and a phenylene group. The hydrotrope (D) is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group as described above. Specific examples of the hydrotrope (D) include, for example, sodium xylene sulfonate, sodium p-toluene sulfonate, etc., but are not limited thereto.

[0043] <Aqueous solvent> Examples of the aqueous solvent contained in the bactericidal cleaning agent composition of the present invention include alcohols such as ethanol and isopropanol, and glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, but are not limited thereto.

[0044] <Rust inhibitor> Examples of the rust inhibitor contained in the bactericidal cleaning agent composition of the present invention include long-chain fatty acid salts and triazole compounds, but are not limited thereto.

[0045] <Defoaming agent> Examples of the defoaming agent contained in the bactericidal cleaning agent composition of the present invention include long-chain fatty acid esters and silicone compounds, but are not limited thereto.

[0046] <Preservative> Examples of the preservative contained in the bactericidal cleaning agent composition of the present invention include benzoates, parabens, phenoxyethanol, etc., but are not limited thereto.

[0047] <Antioxidant> Examples of the antioxidant contained in the bactericidal cleaning agent composition of the present invention include ascorbic acid, dibutylhydroxytoluene (BHT), etc., but are not limited thereto.

[0048] <Object to be bactericidally cleaned> Examples of the object to be bactericidally cleaned by the bactericidal cleaning agent composition of the present invention include medical devices and instruments, containers, industrial wastewater, cooling water for air conditioning equipment, clothing, cooking utensils, tableware, bathrooms, kitchens, washing machines, bathtubs, and furniture, etc., but are not limited thereto. Among the above, particularly in the regeneration treatment of dialysis devices and filtration membranes for water treatment, the bactericidal cleaning agent composition of the present invention is useful.

[0049] <Bactericidal cleaning treatment liquid> The bactericidal detergent composition of the present invention may be used directly as a bactericidal cleaning treatment liquid, or it may be diluted with water, an aqueous solvent, or a solvent other than these to prepare a bactericidal cleaning treatment liquid for use. For the water used for dilution, for example, tap water, well water, ion-exchanged water, distilled water, pure water, ultrapure water, purified water, and water for injection can be preferably used, but are not limited thereto. As the aqueous solvent used for dilution, the aqueous solvent contained in the bactericidal detergent composition can be used.

[0050] The dilution ratio may be any dilution ratio as long as the bactericidal detergent composition is within the concentration range capable of exerting a bactericidal cleaning effect, and is not particularly limited. For example, it is preferably diluted 1 to 1000 times, and more preferably diluted 1 to 100 times. The concentration of peracetic acid (A) in the bactericidal cleaning treatment liquid is preferably 0.00001 to 10% by mass, and more preferably 0.0001 to 10% by mass. The concentration of the surfactant (B) in the bactericidal cleaning treatment liquid is preferably 0.00005 to 10% by mass, and more preferably 0.0005 to 10% by mass. When the bactericidal cleaning treatment liquid contains a chelating agent (C), the concentration of the chelating agent (C) in the bactericidal cleaning treatment liquid is preferably 0.00001 to 10% by mass, and more preferably 0.0001 to 10% by mass.

[0051] <Bactericidal cleaning method> The bactericidal cleaning method using the bactericidal cleaning treatment liquid is not particularly limited as long as it includes a step of bringing the bactericidal cleaning treatment liquid into contact with an object such as an instrument to be bactericidally cleaned. For example, a method of spraying the bactericidal cleaning treatment liquid onto the surface of the object to be treated using an instrument equipped with a nozzle or the like, a method of simply wetting or immersing the surface of the object to be treated with the bactericidal cleaning treatment liquid, a method of impregnating a substrate such as a wipe with the bactericidal cleaning treatment liquid and using it as a cleaning article, and a method of circulating the bactericidal cleaning treatment liquid inside the equipment can be mentioned. In addition, the temperature of the sterilizing and cleaning treatment liquid during treatment is not particularly limited, but from the viewpoints of bactericidal property, cleaning property, and economy, it is preferably 0 to 80°C, more preferably 10 to 40°C. The sterilizing and cleaning treatment time varies depending on the shape and size of the object to be sterilized and cleaned, the sterilizing and cleaning treatment method, and the sterilizing and cleaning treatment conditions, and is not particularly limited.

[0052] The sterilizing and cleaning treatment liquid preferably exhibits a pH of weakly acidic to neutral, for example, preferably exhibits a pH of 4 to 7. In the present invention, weakly acidic means a pH of 3.5 or more and less than 6.7, and neutral means a pH of 6.7 or more and 7.3 or less. When the sterilizing and cleaning treatment liquid is strongly acidic, for example, has a pH of less than 3.5, the waste liquid during sterilizing and cleaning becomes strongly acidic, which may have an adverse effect on sewer pipes and the parts to be cleaned. Also, from the viewpoint of the stability of peracetic acid, the pH of the sterilizing and cleaning treatment liquid is preferably 3.5 to 7.3, more preferably 4 to 6, and even more preferably 4 to 5.5. When the sterilizing and cleaning treatment liquid is strongly acidic, for example, has a pH of less than 4, it is preferable to neutralize the waste liquid with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and triethanolamine.

[0053] <Filter membrane> The filter membrane, which is the object to be treated with the sterilizing and cleaning agent composition and the sterilizing and cleaning treatment liquid of the present invention, is, for example, a reverse osmosis membrane (RO membrane), an ultrafiltration membrane, or a microfiltration membrane. In the present invention, these are described as "filter membrane" as their upper concept. Generally, the pore size of a reverse osmosis membrane is approximately 2 nm or less, the pore size of an ultrafiltration membrane is approximately 0.05 to 0.001 μm, and the pore size of a microfiltration membrane is approximately 50 to 0.05 μm. However, the pore size of the filter membrane in the present invention includes these. Examples of the material of the filter membrane include, but are not limited to, resin or ceramic. Examples of the resin type include, but are not limited to, cellulose acetate, cellulose, polyamide, polyvinyl alcohol, polyethersulfone, polysulfone, polyvinylidene fluoride, polyethylene, polypropylene, polyacrylonitrile, polycarbonate, polytetrafluoroethylene, etc. In addition, examples of the shape of the filtration membrane include, but are not limited to, hollow fiber membrane, spiral membrane, tubular membrane, flat membrane, etc.

Examples

[0054] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these specific examples. The raw materials used in the synthesis examples are shown below.

[0055] · 2-Propyl-1-heptanol (manufactured by Evonik Japan Co., Ltd., trade name "2-PH") · 1-Octanol (manufactured by Kishida Chemical Co., Ltd., trade name "1-Octanol") · 2-Ethyl-1-hexanol (manufactured by Mitsubishi Chemical Corporation, trade name "2-Ethylhexanol") · 1-Decanol (manufactured by Kao Corporation, trade name "Calcohol 1098") · Isodecanol (manufactured by KH Neochem Co., Ltd., trade name "Decanol") · 2-Butyl-1-octanol (manufactured by Sasol Limited, trade name "ISOFOL12") · 1-Dodecanol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "1-Dodecanol") · Isotridecanol (manufactured by KH Neochem Co., Ltd., trade name "Oxocol C-13") · 1-Tetradecanol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "1-Tetradecanol") · 2-Hexyl-1-decanol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "2-Hexyl-1-decanol") · 1-Dodecylamine (manufactured by Kao Corporation, trade name "Farmin 20D") · Asian alkylamine (manufactured by Kao Corporation, trade name "Farmin CS") · 1-Hexyl alcohol (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "1-Hexanol") · 4-Methyl-2-pentyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "4-Methyl-2-pentanol") · 1-Octadecyl alcohol (manufactured by Tokyo Chemical Industry, "1-Octadecanol") · Isooctadecyl alcohol (manufactured by Sasol Limited, trade name "ISOFOL18T") · Ethylene oxide (manufactured by Mitsubishi Chemical Corporation, trade name "Ethylene Oxide") · Propylene oxide (manufactured by Sumitomo Chemical Co., Ltd., trade name "Propylene Oxide") · Potassium hydroxide (manufactured by Toagosei Co., Ltd., trade name "Caustic Potash") · Lauric acid (manufactured by NOF Corporation, trade name "NAA-102") · Sodium hydroxide (manufactured by Toagosei Co., Ltd., trade name "Caustic Soda") · 2-Butyloctanoic acid (manufactured by Sasol Limited, trade name "ISOCARB")

[0056] The raw materials used in the examples are shown below. <Hydrogen peroxide solution> · 35 mass% hydrogen peroxide solution (manufactured by Hodogaya Chemical Co., Ltd., trade name "Cassanca Suiiso")

[0057] <Acetic acid> · 90 mass% acetic acid (manufactured by Resonac Co., Ltd., trade name "Acetic Acid") · Sodium acetate (manufactured by Yonoyama Chemical Industry Co., Ltd., trade name "Sodium Acetate")

[0058] <Surfactant (B)> [Compound represented by formula (1)] · B1: Polyoxyethylene (12) mono(2-propyl-1-heptyl) ether (synthesized in-house) · B2: Polyoxyethylene (12) mono(1-octyl) ether (synthesized in-house) ·B3: Polyoxyethylene (12) mono(2-ethyl-1-hexyl) ether (synthesized in-house) ·B4: Polyoxyethylene (12) mono(1-decyl) ether (synthesized in-house) ·B5: Polyoxyethylene (12) mono(isodecyl) ether (synthesized in-house) ·B6: Polyoxyethylene (12) mono(2-butyl-1-octyl) ether (synthesized in-house) ·B7: Polyoxyethylene (12) mono(1-dodecyl) ether (synthesized in-house) ·B8: Polyoxyethylene (12) mono(isotridecyl) ether (synthesized in-house) ·B9: Polyoxyethylene (12) mono(1-tetradecyl) ether (synthesized in-house) ·B10: Polyoxyethylene (12) mono(2-hexyl-1-decyl) ether (synthesized in-house) ·B11: Polyoxyethylene (6) mono(2-propyl-1-heptyl) ether (manufactured by BASF Japan Ltd., trade name "Lutensol XP60") ·B12: Polyoxyethylene (8) mono(2-propyl-1-heptyl) ether (manufactured by BASF Japan Ltd., trade name "Lutensol XP-80") ·B13: Polyoxyethylene (18) mono(2-propyl-1-heptyl) ether (synthesized in-house) ·B14: Polyoxyethylene (10) polyoxypropylene (2) mono(2-propyl-1-heptyl) ether (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Neugen XL-100")

[0059] [Compound represented by formula (2)] ·B15: N,N-dipolyoxyethylene (12) 1-dodecylamine (synthesized in-house) ·B16: N,N-dipolyoxyethylene (12) coconut alkylamine (synthesized in-house)

[0060] [Compound represented by formula (3)] ·B17: Lauryl dimethylamine oxide (manufactured by Kao Corporation, trade name "Anhitol 20N")

[0061] [Compound represented by formula (4)] ·B18: Lauryl betaine (manufactured by Shin Nippon Rika Co., Ltd., trade name "Rikabion A-100") ·B19: Lauryl hydroxysulfobetaine (manufactured by Kao Corporation, trade name "Anhitol 20HD") ·B20: Lauramidopropyl betaine (manufactured by Kawaken Fine Chemicals Co., Ltd., trade name "Softazoline LPB")

[0062] [Compound represented by formula (5)] ·B21: Sodium laurylbenzenesulfonate (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Sodium dodecylbenzenesulfonate") ·B22: Sodium lauryl sulfate (manufactured by Kao Corporation, trade name "Emal 10G") ·B23: Sodium 1-octadecanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Sodium 1-octadecanesulfonate") ·B24: Sodium polyoxyethylene (3) lauryl ether sulfate (manufactured by Kao Corporation, trade name "Emal 327")

[0063] <Surfactant (b)> ·b1: Polyoxyethylene (12) mono(1-hexyl) ether (synthesized in-house) ·b2: Polyoxyethylene (12) mono(4-methyl-2-pentyl) ether (synthesized in-house) ·b3: Polyoxyethylene (12) mono(1-octadecyl) ether (synthesized in-house) ·b4: Polyoxyethylene (12) mono(isooctadecyl) ether (synthesized in-house) ·b5: Polyoxyethylene (3) mono(2-propyl-1-heptyl) ether (synthesized in-house) ·b6: Polyoxyethylene (25) mono(2-propyl-1-heptyl) ether (synthesized in-house) ·b7: Polyoxypropylene (2) polyoxyethylene (10) mono(2-propyl-1-heptyl) ether (synthesized in-house) · b8: Sodium polyoxyethylene (4.5) lauryl acetate (manufactured by Kao Corporation, trade name "KAO-ACIPOL RLM-45NV") · b9: Sodium monododecyl phosphate (manufactured by Tokyo Chemical Industry Co., Ltd., trade name "Sodium Monododecyl Phosphate") · b10: Sodium laurate (synthesized in-house) · b11: Sodium 2-butyl-1-octanoate (synthesized in-house)

[0064] <Chelating agent (C)> [Phosphoric acid-based chelating agent] · C1: 1-Hydroxyethane-1,1-diphosphonic acid (HEDP) (manufactured by Italmatch Japan Co., Ltd., trade name "Dquest 2010") · C2: Sodium 2-phosphonobutane 1,2,4-tricarboxylate (PBTC) (manufactured by Kirest Co., Ltd., trade name "Kirest PH-430") · C3: Sodium tripolyphosphate (STPP) (manufactured by Shimonoseki Mitsui Chemicals Co., Ltd., trade name "Sodium Tripolyphosphate")

[0065] [Carboxylic acid-based chelating agent] · C4: Ethylenediaminetetraacetic acid (EDTA) tetrasodium (manufactured by Nagase Sangyo Co., Ltd., trade name "Kurewatt S2") · C5: Diethylenetriaminepentaacetic acid (DTPA) pentasodium (manufactured by Nagase Sangyo Co., Ltd., trade name "Kurewatt DP80") · C6: Hydroxyethylethylenediaminetriacetic acid (HEDTA) trisodium (manufactured by Kirest Co., Ltd., trade name "Kirest HC-SD")

[0066] <Hydrotrope (D)> · D1: Sodium p-xylene sulfonate (synthesized in-house) · D2: Sodium p-toluenesulfonate (manufactured by Meiyu Sangyo Co., Ltd., trade name "Sodium Toluenesulfonate") · D3: 3-Methoxy-3-methyl-1-butanol (manufactured by Kuraray Co., Ltd., trade name "Solfit")

[0067] [Protein detergency evaluation] · Sodium chloride: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Sodium chloride" · Potassium chloride: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Potassium chloride" · Calcium chloride dihydrate: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Calcium chloride dihydrate" · Magnesium chloride hexahydrate: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Magnesium chloride hexahydrate" · Sodium acetate: manufactured by Yoneyama Chemical Industry Co., Ltd., product name "Sodium acetate" · Glacial acetic acid: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Glacial acetic acid" · Sodium hydrogen carbonate: manufactured by FUJIFILM Wako Pure Chemical Corporation, product name "Sodium hydrogen carbonate" · Silicon tube: manufactured by AS ONE Corporation, product name "Labolan(R) Silicon tube 5×11m 1 roll (11m)" · Sheep blood: manufactured by Japan Biosera Co., Ltd., product name "Heparin-added sheep blood" Product number: 027-H0044

[0068] [Synthesis example]

[0069] [Synthesis example B1] 2-Propyl-1-heptyl alcohol and potassium hydroxide were charged into an autoclave at a molar ratio of 2-propyl-1-heptyl alcohol / potassium hydroxide = 1 / 0.02, and the inside of the container was purged with nitrogen. Next, the temperature was raised to 120°C and a dehydration treatment under reduced pressure was carried out for 30 minutes. Thereafter, the supply of ethylene oxide was started while the temperature was 120°C or higher, and the reaction was carried out while maintaining the reaction temperature at 120 - 130°C and the pressure at 0.5 MPa or less. Ethylene oxide was supplied until the molar ratio of propylheptyl alcohol / ethylene oxide reached 1 / 12, and aging was carried out until the internal pressure became constant to obtain B1, which is the surfactant (B) represented by the formula (1).

[0070] [Synthesis examples B2 - B10] 2-Propyl-1-heptyl alcohol was changed to the alcohols shown in Tables 1 and 2, and the same operations as in Synthesis Example B1 were carried out to obtain surfactants (B) represented by the formula (1), namely B2 to B10.

[0071] [Synthesis Examples B11 to B13] The same operations as in Synthesis Example B1 were carried out except that the molar ratio of 2-propyl-1-heptyl alcohol / ethylene oxide was changed to the molar ratio described in Table 2, to obtain surfactants (B) represented by the formula (1), namely B11 to B13.

[0072] [Synthesis Example B14] 2-Propyl-1-heptyl alcohol and potassium hydroxide were charged into an autoclave at a molar ratio of 2-propyl-1-heptyl alcohol / potassium hydroxide = 1 / 0.02, and the inside of the container was replaced with nitrogen. Next, the temperature was raised to 120°C and a dehydration treatment under reduced pressure was carried out for 30 minutes. Thereafter, the supply of propylene oxide was started while the temperature was 120°C or higher, and the reaction was carried out while maintaining the reaction temperature at 120 to 130°C and the pressure at 0.5 MPa or less. Propylene oxide was supplied until the molar ratio of 2-propyl-1-heptyl alcohol / propylene oxide reached 1 / 2, aged until the internal pressure became constant, and degassed for 30 minutes. Next, nitrogen gas was supplied to return to normal pressure, the supply of ethylene oxide was started, and the reaction was carried out while maintaining the reaction temperature at 120 to 130°C and the pressure at 0.5 MPa or less. Ethylene oxide was supplied until the molar ratio of 2-propyl-1-heptyl alcohol / ethylene oxide reached 1 / 10, aged until the internal pressure became constant, to obtain surfactant (B) represented by the formula (1), namely B14.

[0073] [Synthesis Example B15] 1-Dodecylamine and potassium hydroxide were charged into an autoclave at a molar ratio of 1-dodecylamine / potassium hydroxide = 1 / 0.02, and the inside of the container was replaced with nitrogen. Next, the temperature was raised to 120°C and a dehydration treatment under reduced pressure was carried out for 30 minutes. Subsequently, the supply of ethylene oxide was started at 120 °C or higher, and the reaction was carried out while maintaining the reaction temperature at 120 - 130 °C and the pressure at 0.5 MPa or lower. Ethylene oxide was supplied until the molar ratio of 1-dodecylamine / ethylene oxide reached 1 / 12, and aging was carried out until the internal pressure became constant to obtain B15, which is a surfactant (B) represented by the formula (2).

[0074] [Synthesis Example B16] B16, which is a surfactant (B) represented by the formula (2), was obtained by operating in the same manner as in Synthesis Example B15, except that coconut alkylamine was used instead of 1-dodecylamine.

[0075] [Synthesis Example E1] E1 was obtained by reacting xylene sulfonic acid and sodium hydroxide at a molar ratio of xylene sulfonic acid / sodium hydroxide = 1 / 1 at 25 °C and 1 atm.

[0076]

Table 1

[0077]

Table 2

[0078] [Comparative Synthesis Examples b1 - b4] b1 - b4, which are other surfactants, were obtained by operating in the same manner as in Synthesis Example B1, except that 2-propyl-1-heptyl alcohol in Synthesis Example B1 was changed to the alcohol shown in Table 2.

[0079] [Comparative Synthesis Examples b5, b6] b5 and b6, which are other surfactants, were obtained by operating in the same manner as in Synthesis Example B1, except that the molar ratio of 2-propyl-1-heptyl alcohol / ethylene oxide was changed to the molar ratio described in Table 3.

[0080] [Comparative Synthesis Example b7] 2-Propyl-1-heptanol and potassium hydroxide were charged into an autoclave at a molar ratio of 2-propyl-1-heptanol / potassium hydroxide = 1 / 0.02, and the inside of the container was purged with nitrogen. Next, the temperature was raised to 120 °C and a dehydration treatment under reduced pressure was carried out for 30 minutes. Thereafter, the supply of ethylene oxide was started while the temperature was maintained at 120 °C or higher, and the reaction was carried out while maintaining the reaction temperature at 120 - 130 °C and the pressure at 0.5 MPa or less. Ethylene oxide was supplied until the molar ratio of 2-propyl-1-heptanol / ethylene oxide reached 1 / 10, aged until the internal pressure became constant, and degassed for 30 minutes. Next, nitrogen gas was supplied to return to normal pressure, the supply of propylene oxide was started, and the reaction was carried out while maintaining the reaction temperature at 120 - 130 °C and the pressure at 0.5 MPa or less. Ethylene oxide was supplied until the molar ratio of 2-propyl-1-heptanol / propylene oxide reached 1 / 2, aged until the internal pressure became constant, and surfactant b7 was obtained.

[0081] [Comparative Synthesis Example b10] At 25 °C and 1 atm, lauric acid and sodium hydroxide were reacted at a molar ratio of lauric acid / sodium hydroxide = 1 / 1 to obtain surfactant b10.

[0082] [Comparative Synthesis Example b11] At 25 °C and 1 atm, 2-butyl-1-octanoic acid and sodium hydroxide were reacted at a molar ratio of 2-butyl-1-octanoic acid / sodium hydroxide = 1 / 1 to obtain surfactant b11.

[0083]

Table 3

[0084] [Example 1] First, the following raw materials were mixed to prepare an equilibrium liquid containing peracetic acid. 35.5 parts by mass of pure water 20 parts by mass of 90% by mass acetic acid 25 parts by mass of sodium acetate Next, 2.5 parts by mass of B1 was added as the surfactant (B) component and mixed. Then, 17 parts by mass of 35% by mass hydrogen peroxide solution was further added, and the mixture was allowed to stand in a constant temperature bath at 45°C for 7 days. Then, the temperature was restored to 25°C to obtain a germicidal cleaning agent composition.

[0085] [Example 2] First, the following raw materials were mixed to prepare an equilibrium liquid containing peracetic acid. 35.1 parts by mass of pure water 20 parts by mass of 90% by mass acetic acid 25 parts by mass of sodium acetate Next, 0.2 parts by mass of C1, 0.2 parts by mass of C4 as the chelating agent (C) component, and 2.5 parts by mass of B1 as the surfactant (B) component were added and mixed. Then, 17 parts by mass of 35% by mass hydrogen peroxide solution was further added, and the mixture was allowed to stand in a constant temperature bath at 45°C for 7 days. Then, the temperature was restored to 25°C to obtain a germicidal cleaning agent composition.

[0086] [Examples 3 to 17] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that B2 to B16 were used as the surfactant (B) component according to Table 4.

[0087] [Examples 18 to 21] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that the blending amount of B1 was changed to the amounts shown in Tables 4 and 5.

[0088] [Examples 22 to 25] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that C2 to C6 were used as the chelating agent (C) component according to Table 5.

[0089] [Examples 26 to 27] As the chelating agent (C) component, except for changing to using only C1 in the blending amounts shown in Tables 5 and 6 without using C4, the operation was the same as in Example 2 to obtain a germicidal detergent composition.

[0090] [Example 28] As the chelating agent (C) component, except for changing to using only C4 in the blending amount shown in Table 6 without using C1, the operation was the same as in Example 2 to obtain a germicidal detergent composition.

[0091] [Examples 29 to 38] As the chelating agent (C) component, except for changing the blending amounts of C1 and C4 to the blending amounts shown in Table 6, the operation was the same as in Example 2 to obtain a germicidal detergent composition.

[0092] [Examples 39 to 42] Except for changing the blending amount of 35% by mass hydrogen peroxide solution to the blending amounts shown in Tables 6 and 7, the operation was the same as in Example 2 to obtain a germicidal detergent composition.

[0093] [Examples 43 to 45] Except for changing the blending amounts of acetic acid (90% by mass), sodium acetate, and 35% by mass hydrogen peroxide solution to the blending amounts shown in Table 7, the operation was the same as in Example 2 to obtain a germicidal detergent composition.

[0094] [Example 46] First, the following raw materials were mixed to prepare an equilibrium liquid containing peracetic acid. 32.6 parts by mass of pure water 20 parts by mass of acetic acid (90% by mass) 25 parts by mass of sodium acetate Next, 0.2 part by mass of C1 and 0.2 part by mass of C4 as the chelating agent (C) component, 2.5 parts by mass of B1 as the surfactant (B) component, and 2.5 parts by mass of D1 as the hydrotrope (D) were added and mixed. 0.2 part by mass of C1 0.2 part by mass of C4 2.5 parts by mass of B1 2.5 parts by mass of D1 Furthermore, 17 parts by mass of 35% by mass hydrogen peroxide solution was added, and the mixture was allowed to stand in a thermostat at 45°C for 7 days. Then, it was cooled to 25°C to obtain a germicidal cleaning agent composition.

[0095] [Examples 47 - 48] A germicidal cleaning agent composition was obtained in the same manner as in Example 46, except that D2 and D3 were used as the hydrotrope agent (D).

[0096] [Examples 49 - 50] A germicidal cleaning agent composition was obtained in the same manner as in Example 46, except that the blending amount of D1 was changed to the blending amount shown in Table 7.

[0097] [Examples 51 - 54] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that B18 - B21 were used as the surfactant (B) component according to the description in Table 8.

[0098] [Examples 55 - 56] A germicidal cleaning agent composition was obtained in the same manner as in Example 51, except that the blending amount of B18 was changed to the blending amount described in Table 8.

[0099] [Examples 57 - 60] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that B22 - B25 were used as the surfactant (B) component.

[0100] [Examples 61 - 62] A germicidal cleaning agent composition was obtained in the same manner as in Example 58, except that the blending amount of B22 was changed to the blending amount shown in Table 8.

[0101] [Comparative Examples 1 - 11] A germicidal cleaning agent composition was obtained in the same manner as in Example 2, except that b1 - b11 were used as the surfactant component instead of the surfactant (B) component.

[0102] [Comparative Example 12] The amount of sodium acetate was changed to the amount shown in Table 9, and the same operations as in Example 2 were carried out except that acetic acid (90% by mass) was not added, to obtain a bactericidal cleaning agent composition.

[0103] [Comparative Example 13] The same operations as in Example 2 were carried out except that 35% by mass hydrogen peroxide solution was not added, to obtain a bactericidal cleaning agent composition.

[0104] [Comparative Example 14] The same operations as in Example 2 were carried out except that sodium acetate and acetic acid (90% by mass) were not added, to obtain a bactericidal cleaning agent composition.

[0105] [Comparative Example 15] The same operations as in Example 2 were carried out except that B1 was not added, to obtain a bactericidal cleaning agent composition.

[0106] [Various Measurement and Evaluation Methods] [Peracetic Acid Concentration] 0.5 g of the bactericidal cleaning agent composition adjusted in a 100 mL conical beaker was sampled with a micropipettor, and 5 mL of 10% sulfuric acid solution and 5 mL of ion-exchanged water were added (sample). Next, 0.1 N potassium permanganate standard solution was added dropwise and titrated until it showed a light pink color. Then, 4 mL of 50% potassium iodide solution was added, and 0.01 N sodium thiosulfate standard solution was added dropwise until it showed a pale yellow color. Next, 1 mL of 1% starch solution was added to turn the sample dark blue. Furthermore, 0.01 N sodium thiosulfate standard solution was added dropwise until the dark blue color disappeared. Also, as a blank, titration was carried out in the same manner as above for 0.5 g of purified water. Then, the peracetic acid concentration was calculated by the following calculation formula (2). Calculation formula (2): Peracetic acid concentration (w / v%) = (J - J0) × (0.038 × F2 / 0.5) ·J0 (mL): Amount of 0.01 N sodium thiosulfate standard solution required for titration of the blank ·J (mL): Volume of 0.01N sodium thiosulfate standard solution required for titration of the sample ·F2: Factor of 0.01N sodium thiosulfate standard solution

[0107] [Filter membrane permeability] In this evaluation, a high-speed centrifugal filtration unit (manufactured by Sartorius Japan Co., Ltd., trade name "Vivaspin 20", product number "VS2022", with an ultrafiltration membrane part made of polyethersulfone (PES)) incorporating an ultrafiltration membrane as a filter (filter membrane) was used to evaluate the filter membrane permeability of the bactericidal detergent composition. First, the bactericidal detergent composition was diluted with ion-exchanged water to prepare a test solution with a concentration of 2% by mass of the bactericidal detergent composition. 20 g of the test solution was placed on the filter of the above high-speed centrifugal filtration unit, and centrifuged at 1500 rpm for 120 minutes using a tabletop multi-tube centrifuge (manufactured by Tomy Seiko Co., Ltd., tabletop multi-tube centrifuge, model number: LC-220). The filtrate of the test solution that passed through the filter and accumulated at the bottom of the high-speed centrifugal filtration unit was discarded by centrifugation.

[0108] Subsequently, 20 g of ion-exchanged water was placed on the filter of the high-speed centrifugal filtration unit and centrifuged at 1500 rpm for 10 minutes, which was repeated twice. Then, the total weight K (g) of the test solution and ion-exchanged water that passed through the filter and accumulated at the bottom of the high-speed centrifugal filtration unit by a total of two centrifugation operations was measured. Also, as a blank, ion-exchanged water was used instead of the test solution, and centrifugation was performed twice in the same manner. The total weight K0 (g) of the ion-exchanged water that passed through the filter and accumulated at the bottom of the high-speed centrifugal filtration unit by a total of two centrifugation operations was measured. Then, the membrane passage rate of the test solution was calculated from the following calculation formula (3), and the filter membrane permeability of the bactericidal detergent composition was determined. When the filter membrane permeability of the bactericidal detergent composition is high, K becomes a value close to K0.

[0109] On the one hand, when the filtration membrane permeability of the bactericidal cleaning agent composition is low, clogging of the filter of the high-speed centrifugal filtration unit occurs, so K becomes a value smaller than K0. Calculation formula (3): Filtration membrane permeability (%) = K / K0 × 100 · K (g): The passing amount of the test solution and ion-exchanged water after a total of two centrifugations. · K0 (g): The passing amount of ion-exchanged water after a total of two centrifugations (blank). Judgment criteria for filtration membrane permeability 1: The filtration membrane permeability is less than 60% by mass 2: The filtration membrane permeability is 60% by mass or more and less than 80% by mass 3: The filtration membrane permeability is 80% by mass or more

[0110] [Protein detergency] The following compounds were mixed to prepare Solution 1 for preparing simulated dialysate. Sodium chloride 20.25 parts by mass Potassium chloride 0.65 parts by mass Calcium chloride dihydrate 0.9 parts by mass Magnesium chloride hexahydrate 0.53 parts by mass Sodium acetate 1.72 parts by mass Glacial acetic acid 0.42 parts by mass Ion-exchanged water 75.53 parts by mass

[0111] Next, the following compounds were mixed to prepare Solution 2 for preparing simulated dialysate. Sodium hydrogen carbonate 7 parts by mass Ion-exchanged water 93 parts by mass

[0112] Solution 1 for preparing simulated dialysate, Solution 2 for preparing simulated dialysate, and ion-exchanged water were mixed at a weight ratio of Solution 1 for preparing simulated dialysate / Solution 2 for preparing simulated dialysate / ion-exchanged water = 16.00 / 20.16 / 33.84 to prepare a simulated dialysate. Next, the simulated dialysate prepared above was sealed in the path of a silicone tube and allowed to stand for 72 hours. Thereafter, the mock dialysate in the path of the silicone tube was discharged, and a sheep blood solution obtained by diluting sheep blood 5-fold by weight with ion-exchanged water was enclosed in the silicone tube and allowed to stand for 16 hours. By the above operation, a composite stain of mock dialysate and sheep blood solution was deposited in the path of the silicone tube.

[0113] Next, a bactericidal cleaning agent composition was diluted with ion-exchanged water so that the concentration of the bactericidal cleaning agent composition became 2% by mass to prepare a test solution. A circulation pump (manufactured by BETA Technology Inc., trade name "L5000Plus") and a cleaning bath filled with the test solution were connected with a silicone tube to create a path with a circumference of 2 m, and a part (10 cm) of the silicone tube connecting the circulation pump and the cleaning bath was replaced with the silicone tube (10 cm) on which the above composite stain was deposited.

[0114] Then, the test solution was circulated in the path of the silicone tube with the circulation pump, and the silicone tube with the composite stain deposited in the path was cleaned under the following conditions. Test solution temperature: 25 °C Flow rate of the circulation pump: 580 mL / min Cleaning time: 10 minutes

[0115] Thereafter, while taking care that the composite stain remaining in the path of the silicone tube did not fall off, the test solution remaining in the path of the silicone tube was discharged. Then, the inner wall of the path of the silicone tube after cleaning was stained with amido black 10B (manufactured by Fujifilm Wako Pure Chemical Corporation, trade name "Amido Black 10B"). The degree of staining was visually confirmed, and the protein detergency was judged according to the following criteria. Judgment criteria for protein detergency 1: The entire silicone tube is deeply stained. 2: A part of the silicone tube is stained, or the whole is lightly stained. 3: The silicone tube is hardly stained.

[0116]

Table 4

[0117]

Table 5

[0118]

Table 6

[0119]

Table 7

[0120]

Table 8

[0121]

Table 9

Industrial Applicability

[0122] The composition for sterilizing and cleaning of the present invention is excellent in bactericidal property, filtration membrane permeability, and detergency, and is less likely to cause clogging of the filtration membrane. Therefore, for example, it can be used as a cleaning solution for regeneration treatment of filtration membranes for dialysis devices, water treatment, etc.

Claims

1. A germicidal cleaning composition containing peracetic acid (A), a surfactant (B), and water, wherein the surfactant (B) contains at least one selected from the group consisting of a nonionic surfactant represented by the following formula (1), a nonionic surfactant represented by the following formula (2), an amphoteric surfactant represented by the following formula (3), an amphoteric surfactant represented by the following formula (4), and an anionic surfactant represented by the following formula (5); the germicidal cleaning composition exhibits a pH of weakly acidic to neutral; the above-mentioned germicidal cleaning composition. 【Chemical 1】 (In the formula, R 1 - is a linear or branched alkyl group having 8 to 16 carbon atoms, or a linear or branched alkenyl group having 8 to 16 carbon atoms. -(A 1 O)- is an alkyleneoxy group having 2 to 4 carbon atoms, and -EO- is an ethyleneoxy group. m is a number from 3 to 19 representing the average number of repeating units of -A 1 O-. The average m -A 1 O- in one molecule may be the same or different, and the connection order of -A 1 O) m - within -A 1 O- may be random or block-like.) [Chemical 2] (wherein, R 2 - is a linear or branched alkyl group having 8 to 16 carbon atoms, or a linear or branched alkenyl group having 8 to 16 carbon atoms. -A 2 O- and -A 3 O- are each independently an alkyleneoxy group having 2 to 4 carbon atoms, and -EO- is an ethyleneoxy group. q represents the average number of repeating units of -A 2 O-, and r represents the average number of repeating units of -A 3 O-. q and r are each independently a number from 0 to 18, and q + r is a number from 2 to 18. The average q -A 2 O- and the average r -A 3 O- may be the same or different, and the connection order of A 2 O in - (A q O) 2 - and the connection order of A 3 O in - (A r O) 3 - may each be random or block-like.) 【Chemical Formula 3】 (In the formula, R 3 - is an alkyl group or an alkenyl group having 8 to 18 carbon atoms. R 4 - and R 5 - are each independently an alkyl group having 1 to 6 carbon atoms.) 【Chemical Formula 4】 (wherein, R 6 - is an alkyl group or an alkenyl group having 8 to 18 carbon atoms which may contain an amide bond. R 7 - and R 8 - are each independently an alkyl group having 1 to 6 carbon atoms. -R 9 - is an alkylene group having 1 to 6 carbon atoms which may contain a hydroxy group. -Z - is -COO - or -SO 3 - .) 【Chemical Formula 5】 (In the formula, R 10 - is a monovalent hydrocarbon group having 10 to 24 carbon atoms. -EO- is an ethyleneoxy group. u is a number from 0 to 5 representing the average number of repeating units of -EO-. -X is, when u is 0, -SO 3 - Y + or -OSO 3 - Y + and when u is 1 to 5, it is -SO 3 - Y + . Y + is an alkali metal cation or a quaternary organic ammonium cation.)

2. A germicidal cleaning composition further containing a chelating agent (C), wherein the chelating agent (C) contains a phosphoric acid-based chelating agent and / or a carboxylic acid-based chelating agent; the germicidal cleaning composition according to Claim 1.

3. A germicidal cleaning composition further containing a hydrotrope (D), wherein the hydrotrope (D) has a hydrophilic group and a hydrophobic group, the hydrophilic group is one or more selected from the group consisting of a hydroxyl group, a sulfonic acid group, an ester group, and an ether group, the hydrophobic group is an aliphatic hydrocarbon group or an aromatic hydrocarbon group; the germicidal cleaning composition according to Claim 2.

4. The content in the germicidal cleaning composition is as follows: Peracetic acid (A) is 0.01 to 10% by mass, The surfactant (B) is 0.05 to 10% by mass; the germicidal cleaning composition according to Claim 1.

5. The content of the chelating agent (C) in the germicidal cleaning composition is 0.01 to 10% by mass; the germicidal cleaning composition according to Claim 2.

6. The content of the hydrotrope (D) in the germicidal cleaning composition is 0.01 to 10% by mass; the germicidal cleaning composition according to Claim 3.

7. A germicidal cleaning treatment liquid comprising the germicidal cleaning composition according to any one of Claims 1 to 6.

8. A germicidal cleaning method using the germicidal cleaning treatment liquid according to Claim 7.

Citation Information

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