Protein cleaning agent and protein cleaning method

Abstract

To provide a protein cleaning agent comprising an alkali and exhibiting superior storage stability, as well as a protein cleaning method employing the protein cleaning agent.SOLUTION: The protein cleaning agent comprises 40 mass% or more of water relative to the total amount of the composition, 1.85-6.8 mass% of bromine in terms of effective bromine concentration relative to the total amount of the composition, 1.3 mass% or more of sulfamic acid relative to the total amount of the composition, and an alkali adjusted to make the composition pH 12.8 or more and 1% pH in the range of 12.0-13.0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a protein detergent for cleaning stains such as proteins, and a protein cleaning method using the protein detergent. [Background technology]

[0002] For example, detergents for food factories that combine hypochlorous acid with alkali are used to clean pipes, tanks, and other manufacturing processes. By combining alkali with hypochlorous acid, protein stains can be removed more easily, but there is a problem that the active ingredients in hypochlorous acid tend to deteriorate when the amount of alkali added is high, resulting in poor storage stability and making it difficult to store for long periods of time.

[0003] Therefore, for example, in Patent Documents 1 and 2, a surfactant is blended with hypochlorous acid to increase the stability of the hypochlorous acid. However, some surfactants are persistent substances, and in the future, it may be desirable to avoid blending surfactants as much as possible in order to reduce the environmental load.

[0004] On the other hand, Patent Document 3 proposes a stabilized hypobromous acid composition in which hypobromous acid is stabilized as a disinfectant for suppressing the generation of slime in water treatment plants. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 51-005307 [Patent Document 2] Special Publication No. 49-026686 [Patent Document 3] Japanese Patent Application Publication No. 2018-090513 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a protein detergent containing alkali and having good storage stability, and a protein detergent method using the protein detergent. [Means for solving the problem]

[0007] The present invention provides a protein detergent comprising 40% by mass or more of water relative to the total amount of the composition, bromine in an effective bromine concentration of 1.85 to 6.8% by mass relative to the total amount of the composition, sulfamic acid in an amount of 1.3% by mass or more relative to the total amount of the composition, and an alkali blended in such a way that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0.

[0008] The protein-based cleaning agent preferably has a corrosion rate (MDD) of less than 2.5 when stainless steel is cleaned using a solution obtained by diluting the protein-based cleaning agent 20 to 1000 times.

[0009] The present invention is a method for cleaning proteins, which involves using the protein cleaning agent.

[0010] In the protein washing method, it is preferable to wash the protein by using the protein washing agent diluted in the range of 20 to 1000 times. [Effects of the Invention]

[0011] The present invention can provide a protein detergent containing alkali and having good storage stability, and a protein detergent method using the protein detergent. DETAILED DESCRIPTION OF THE INVENTION

[0012] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following describes an embodiment of the present invention. The embodiment is an example of implementing the present invention, and the present invention is not limited to the embodiment.

[0013] A protein detergent according to an embodiment of the present invention comprises water in an amount of 40% by mass or more relative to the total amount of the composition, bromine in an effective bromine concentration of 1.85 to 6.8% by mass relative to the total amount of the composition, sulfamic acid in an amount of 1.3% by mass or more relative to the total amount of the composition, and alkali blended so that the pH of the composition is 12.8 or more and the 1% pH is in the range of 12.0 to 13.0.

[0014] The inventors have discovered that a protein detergent that exhibits good storage stability even when containing alkali can be obtained by blending 40% by mass or more of water relative to the total amount of the composition, bromine in an effective bromine concentration of 1.85 to 6.8% by mass relative to the total amount of the composition, and 1.3% by mass or more of sulfamic acid relative to the total amount of the composition, and further blending alkali such that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0.

[0015] The amount of water in the protein detergent is 40% by mass or more, preferably 40 to 90% by mass, and more preferably 40 to 80% by mass, of the total amount of the composition. If the amount of water in the protein detergent is less than 40% by mass of the total amount of the composition, precipitation may occur, making formulation difficult. If the amount of water exceeds 90% by mass, cleaning ability may decrease.

[0016] The amount of bromine in the protein detergent is in the range of 1.85 to 6.8 mass%, preferably 2.25 to 6.8 mass%, and more preferably 3.4 to 6.8 mass%, in terms of effective bromine concentration relative to the total amount of the composition. If the amount of bromine in the protein detergent is less than 1.85 mass%, in terms of effective bromine concentration relative to the total amount of the composition, cleaning will be insufficient, while if it exceeds 6.8 mass%, there is a risk of deterioration of metal components during cleaning.

[0017] The amount of sulfamic acid in the protein detergent is 1.3% by mass or more, preferably 1.3 to 4.3% by mass, and more preferably 2.14 to 4.3% by mass, based on the total mass of the composition. If the amount of sulfamic acid in the protein detergent is less than 1.3% by mass based on the total mass of the composition, cleaning properties will be reduced, and if it exceeds 4.3% by mass, precipitates may form, making formulation difficult.

[0018] The amount of alkali in the protein detergent is such that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0. The pH of the composition is preferably in the range of 13.8 to 14.6, more preferably in the range of 13.8 to 14.3. If the pH of the composition is less than 12.8, the cleaning properties will be poor, and if it exceeds 14.6, precipitates will form, making formulation difficult. The 1% pH of the composition is preferably in the range of 12.2 to 13.0, more preferably in the range of 12.2 to 12.8. If the 1% pH of the composition is less than 12.0, the bactericidal and cleaning effects may be reduced, and if it exceeds 13.0, precipitates will form, making formulation difficult. The "1% pH" of the composition refers to the pH of the composition diluted with water to a concentration of 1%.

[0019] The phrase "containing bromine and sulfamic acid" may include a stabilized hypobromous acid composition containing a mixture of "bromine" and "sulfamic acid," or may include a stabilized hypobromous acid composition containing a "reaction product of bromine and sulfamic acid."

[0020] Examples of water include tap water, pure water, and ultrapure water.

[0021] The sulfamic acid compound is a compound represented by the following general formula (1). R2NSO3H (1) (In the formula, R is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

[0022] As the sulfamic acid compound, sulfamic acid (amidosulfuric acid) in which both of the two R groups are hydrogen atoms is used.

[0023] Examples of alkali include alkali hydroxides such as sodium hydroxide and potassium hydroxide. From the viewpoint of product stability at low temperatures, sodium hydroxide and potassium hydroxide may be used in combination. The alkali may be used as an aqueous solution instead of a solid.

[0024] <Method of manufacturing protein detergent> The protein detergent according to this embodiment can be obtained by mixing water, bromine, sulfamic acid, and an alkali. For example, the following can be mixed: 40% by mass or more of water relative to the total amount of the composition; bromine at an effective bromine concentration of 1.85 to 6.8% by mass relative to the total amount of the composition; 1.3% by mass or more of sulfamic acid relative to the total amount of the composition; and an alkali blended so that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0.

[0025] A method for producing a protein detergent containing bromine and sulfamic acid preferably includes a step of adding bromine to a mixture containing water, an alkali, and sulfamic acid under an inert gas atmosphere to cause a reaction, or a step of adding bromine to a mixture containing water, an alkali, and sulfamic acid under an inert gas atmosphere to cause a reaction. By adding bromine under an inert gas atmosphere to cause a reaction, or by adding bromine under an inert gas atmosphere, the bromate ion concentration in the protein detergent is reduced.

[0026] The inert gas to be used is not limited, but from the viewpoint of production etc., at least one of nitrogen and argon is preferable, and from the viewpoint of production cost etc., nitrogen is particularly preferable.

[0027] The oxygen concentration in the reactor during the addition of bromine is preferably 6% or less, more preferably 4% or less, even more preferably 2% or less, and particularly preferably 1% or less. If the oxygen concentration in the reactor during the reaction of bromine exceeds 6%, the amount of bromic acid produced in the reaction system may increase.

[0028] The reaction temperature during the addition of bromine is preferably controlled within a range of 0° C. to 25° C., but from the viewpoint of production costs, it is more preferably controlled within a range of 0° C. to 15° C. If the reaction temperature during the addition of bromine exceeds 25° C., the amount of bromic acid produced in the reaction system may increase, and if it is below 0° C., freezing may occur.

[0029] <Protein cleaning method> The protein cleaning method according to this embodiment is a cleaning method for cleaning proteins using the protein cleaning agent.

[0030] For example, the protein detergent may be diluted in the range of 20 to 1000 times, preferably in the range of 20 to 225 times, and then used to wash the protein.

[0031] In the protein cleaning method according to this embodiment, the protein cleaning agent may be diluted with a solvent such as water so that the effective bromine concentration is in the range of 2.2 to 6.8%, for example.

[0032] The protein-containing cleaning agent according to this embodiment can be used to clean pipes, tanks, pumps, etc. in food factories, cleaning companies, hospitals, etc., and can mainly remove dirt containing protein.

[0033] The protein-containing stains to be removed are not particularly limited, but examples include stains containing proteins such as casein, whey protein, and lactoferrin.

[0034] The protein cleaning method according to this embodiment is not particularly limited as long as it can clean the object to be cleaned. For example, the method can be carried out by diluting the protein cleaning agent with a solvent such as water and spraying it onto the object to be cleaned, diluting the protein cleaning agent with a solvent such as water and soaking it into a cloth or the like used in the cleaning process and wiping it off, or diluting the protein cleaning agent with a solvent such as water and soaking the object to be cleaned in it. [Example]

[0035] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0036] [Composition A: Preparation of Stabilized Hypobromous Acid Composition] A stabilized hypobromous acid composition was prepared by mixing 16.9% by weight (wt%) liquid bromine, 10.7% by weight sulfamic acid, 12.9% by weight sodium hydroxide, 3.94% by weight potassium hydroxide, and the remainder water under a nitrogen atmosphere. The pH of the stabilized hypobromous acid composition was 14, and the total chlorine concentration was 7.5% by weight. The total chlorine concentration was measured (mg Cl / L) using a HACH DR / 4000 multi-parameter water quality analyzer by the total chlorine measurement method (DPD (diethyl-p-phenylenediamine) method). The detailed preparation method of the stabilized hypobromous acid composition is as follows.

[0037] While controlling the nitrogen gas flow rate with a mass flow controller to maintain the oxygen concentration in the reaction vessel at 1%, 1436 g of water and 361 g of sodium hydroxide were added to a sealed 2 L four-neck flask and mixed. 300 g of sulfamic acid was then added and mixed. After mixing, 473 g of liquid bromine was added while maintaining cooling so that the reaction solution temperature was 0-15°C. Further, 230 g of 48% potassium hydroxide solution was added to obtain the desired stabilized hypobromous acid composition, which was 10.7% sulfamic acid and 16.9% bromine by mass relative to the total composition, with an equivalent ratio of sulfamic acid to bromine of 1.04. The pH of the resulting solution was measured by the glass electrode method to be 14. The bromine content of the resulting solution was 16.9%, determined by redox titration with sodium thiosulfate after converting bromine to iodine with potassium iodide, which was 100.0% of the theoretical content (16.9%). The oxygen concentration in the reaction vessel during the bromine reaction was measured using an oxygen monitor JKO-02 LJDII manufactured by Jiko Co., Ltd. The bromate concentration was less than 5 mg / kg.

[0038] The pH was measured under the following conditions. Electrode type: Glass electrode pH meter: DKK Toa, IOL-30 Calibration of the electrode: Two-point calibration was performed using Kanto Chemical's neutral phosphate pH (6.86) standard solution (type 2) and the same company's borate pH (9.18) standard solution (type 2). Measurement temperature: 25℃ Measurement value: Immerse the electrode in the measurement solution, and use the value after stabilization as the measurement value, and take the average of three measurements.

[0039] [Composition B: Preparation of Stabilized Hypobromous Acid Composition] This composition was prepared according to the following procedure based on the contents of JP-A-11-506139: Stabilized hypobromous acid composition B had a pH of 14 and a bromine content of 9.2 mass %. (1) 50.0 grams of a 12% by mass sodium hypochlorite solution was added to 60.0 grams of a 40% by mass sodium bromide pure aqueous solution and stirred. (2) A stabilizing solution was prepared from 20.6 grams of purified water, 9.6 grams of sulfamic acid, and 6.6 grams of sodium hydroxide. (3) The stabilizing solution (2) was added to the solution (1) with stirring to obtain the target stabilized hypobromous acid composition B.

[0040] [Composition C] The composition contained 84.2 grams of pure water, 12.6 grams of sodium bromide, and 50 g of a 12% by mass aqueous solution of sodium hypochlorite.

[0041] [Composition D] This is a composition of a 12% by mass aqueous solution of sodium hypochlorite.

[0042] [Measurement of free bromine concentration and total halogen concentration of each composition] The free bromine concentration and total halogen concentration (both converted into available chlorine concentrations) of each composition were measured according to the following procedure (note that the free bromine concentration and total halogen concentration in Experiment 3 were also measured according to the following procedure). The free bromine concentration, total halogen concentration, free bromine concentration / total halogen concentration ratio, and molar ratio of sulfamic acid to the total halogen amount of each composition are shown in Table 1.

[0043] (1) Measurement of free bromine concentration The composition was diluted with pure water to a concentration of 20 mg / L, and 0.1 mL of a 20% by mass glycine solution was added to 10 mL of this sample water and mixed.Then, the concentration was measured using a HACH multi-parameter water quality analyzer DR / 4000 (measurement item: "free chlorine") by the DPD (diethyl-p-phenylenediamine) method. (2) Measurement of total halogen concentration The composition was diluted with pure water to a concentration of 20 mg / L, and the test water was measured using a HACH multi-parameter water quality analyzer DR / 4000 (measurement item: "total chlorine") by the DPD (diethyl-p-phenylenediamine) method.

[0044] [Table 1]

[0045] <Experiment 1: Examples 1 to 3, Comparative Examples 1 and 2, Reference Examples 1 and 2> [Confirmation of storage stability of composition] Detergents were formulated according to the composition shown in Table 2, stored at 50°C for 7 days, and the free bromine concentration was measured. The residual free bromine rate (%) was calculated from the theoretical free bromine concentration, and the stability after formulation was evaluated according to the following criteria. The pH and 1% pH of the detergents were measured with a pH meter. The results are shown in Table 2. Reference Example 1 corresponds to Example 5 of Patent Document 3, and Reference Example 2 corresponds to Example 6 of Patent Document 3.

[0046] (Evaluation criteria) 〇: Active ingredient remaining rate is 65% or more ×: Less than 65% of the active ingredient remains

[0047] [Table 2]

[0048] The cleaning agents of Examples 1 to 3 had good storage stability. In Reference Examples 1 and 2, the active bromine concentration was too high. Therefore, applying this composition directly to a protein-containing cleaning agent would clean the protein, but would be an expensive process and could potentially cause degradation of rubber and other materials. By blending an alkali into a bromine solution with an effective bromine concentration of 1.85 to 6.8 mass % as in the cleaning agents of Examples 1 to 3, so that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0, a cleaning agent with good storage stability can be obtained.

[0049] <Experiment 2: Examples 4 to 6, Comparative Examples 3 and 4> [Evaluation of cleaning properties, formulation, and corrosivity of cleaning agents] The cleaning properties, formulation properties, and corrosiveness of the detergents were evaluated under the following conditions and according to the following criteria.

[0050] (Evaluation criteria) 〇: Protein removal rate of 70% or more ×: Protein removal rate less than 70%

[0051] (Protein removal test) 10 μL of Meiji Dairies' Oishii Gyunyuu (Tasty Milk) was dropped onto the surface of a SUS304 test piece and spread over a 2 cm diameter area. The piece was heated at 40°C for 16 hours and then dried at 140°C for 2 hours. A cleaning agent was formulated with the composition shown in Table 3. A 1% by mass aqueous solution of the formulated cleaning agent was prepared, heated to 70°C, and the test piece was immersed in the solution and washed for 30 minutes.

[0052] After cleaning, the surface was rinsed with pure water to remove any remaining detergent. 100 μL of 0.1 M NaOH was added, and the remaining protein on the test piece surface was vigorously wiped with a swab. The swab was then dipped 10 times into 200 μL of Modified Lowry Reagent added to a microplate reader and immediately mixed for 30 seconds on a plate mixer. Then, 20 μL of 2x Folinciocalteu Reagent (2x diluted) was added to each well and mixed for 30 seconds on a plate mixer. The microplate was then covered, and after 30 minutes at room temperature (25°C), the absorbance at 750 nm was measured using a microplate reader (Thermo Scientific, Multiskan FC). The blank value was subtracted from the measured value to calculate the protein removal rate, with the untreated value set at 100%. The results are shown in Table 3.

[0053] (Formulation testing) A detergent was formulated according to the composition shown in Table 3. If a clear liquid was prepared without turbidity, the formulation was deemed acceptable, but if a precipitate was formed in the formulation, the formulation was deemed unacceptable. The results are shown in Table 3.

[0054] (corrosion rate) Mass loss per volume in a given time (MDD (mg / dm 2 The corrosion rate was calculated from the calculated values ​​and the results are shown in Table 3.

[0055] [Table 3]

[0056] In Examples 4 to 6, it was confirmed that pharmaceutical preparations were possible, that the coating was less corrosive, and that the cleaning properties for proteins were good.

[0057] <Experiment 3: Examples 7 to 9, Comparative Examples 3, 5, and 6> [Evaluation of cleaning properties and formulation properties of the composition] (Test conditions) Cleaning agents were formulated with the compositions shown in Table 4 in the same manner as in Experiment 2 and evaluated in the same manner. The results are shown in Table 4.

[0058] [Table 4]

[0059] In Examples 7 to 9, it was confirmed that pharmaceutical preparations were possible and that proteins were easily washed away.

[0060] <Experiment 4: Examples 10 to 12, Comparative Example 7> [Evaluation of cleaning properties of the composition] (Test conditions) Cleaning agents were formulated with the compositions shown in Table 5 in the same manner as in Experiment 2 and evaluated in the same manner. The results are shown in Table 5.

[0061] [Table 5]

[0062] In Examples 10 to 12, it was confirmed that the protein washing properties were good.

[0063] Thus, in the examples, a protein detergent containing alkali and having good storage stability was obtained.

Claims

1. 40% by mass or more of water based on the total amount of the composition; an effective bromine concentration of 1.85 to 6.8% by mass based on the total amount of the composition; 1.3% by mass or more of sulfamic acid relative to the total amount of the composition; an alkali formulated so that the pH of the composition is 12.8 or higher and the 1% pH is in the range of 12.0 to 13.0; A protein detergent comprising:

2. 2. The protein detergent of claim 1, The protein detergent is characterized in that when a solution of the protein detergent diluted 20 to 1000 times is used to clean stainless steel, the corrosion rate (MDD) is less than 2.

5.

3. A method for cleaning proteins, comprising cleaning proteins with the protein cleaning agent according to claim 1 or 2.

4. The protein washing method according to claim 3, A protein cleaning method, characterized in that the protein cleaning agent is diluted in the range of 20 to 1000 times and used to clean the protein.

Images