Oxidant compositions for suppressing loss of binder durability and uses thereof

Abstract

The present invention relates to a sterilizing composition, which is characterized by having an excellent effect of suppressing the durability loss of a synthetic binder and a high sterilizing effect. The sterilizing composition is characterized by containing at least 0.03% by mass to less than 1.0% by mass of peracetic acid, at least 0.045% by mass to less than 1.5% by mass of hydrogen peroxide, and at least 0.036% by mass of glycine.

Description

Technical Field

[0001] The present invention relates to a microbicidal composition comprising an oxidizing agent as an active ingredient, and the microbicidal composition has an effect of restricting a decrease in durability of an adhesive, particularly a synthetic adhesive, and a microbicidal effect. Therefore, the microbicidal composition according to the present invention can be suitably used for disinfecting and microbicidally treating a test object containing a synthetic adhesive, particularly an instrument and a device in the medical field (including the dental field, the same applies hereinafter) or the food field that require disinfection and microbicidal treatment. Background Art

[0002] Acidic oxidizing agents are widely used as disinfectants or microbicides in the medical field or the food field due to their excellent microbicidal activity against a wide range of microorganisms. In particular, acidic oxidizing agents containing percarboxylic acids such as peracetic acid or hydrogen peroxide can perform disinfection and microbicidal treatment in a short time, and thus are effective disinfectants and microbicides for instruments or environments where physical disinfection such as autoclaving or dry heat sterilization cannot be applied.

[0003] However, acidic oxidizing agents are corrosive and are therefore known to deteriorate or rust metals such as aluminum and aluminum alloys that are commonly used for materials for medical devices, for example, and interfere with the function and appearance of the metals. To reduce corrosion of metals, for example, chromates or molybdates are used as corrosion inhibitors (see Patent Document 1). However, these components are not practical because they are subject to the Pollutant Release and Transfer Register (PRTR) system. In addition to chromates and molybdates, acid salts such as nitrates, nitrites, tungstates, borates, silicates, and sulfites, and amine salts are known to be effective as metal corrosion inhibitors (see Patent Document 2). Patent Document 3 discloses the combined use of nitrites and molybdates from the above acid salts to reduce the metal corrosivity of acidic oxidizing agents such as percarboxylic acids.

[0004] Some medical devices and instruments contain adhesives used at the joints of components, or are covered with adhesives for protective purposes. For example, medical instruments such as endoscopes, etc. must be disinfected every day. However, measures need to be taken to ensure that the adhesive does not deteriorate and that the function and appearance of the medical device are not impaired due to the disinfection treatment. However, the medical and food fields need to consider the residues and toxicity of microbicidal components. Although acidic oxidizing agents such as percarboxylic acids (e.g., peracetic acid) and hydrogen peroxide are microbicidal components with relatively few residues and low toxicity, such acidic oxidizing agents are corrosive to adhesives, particularly synthetic adhesives. However, from the perspective of microbicidal compositions, there is no known method to solve this problem.

[0005] Patent Document 4 discloses a composition for cleaning and purifying a dialyzer, which contains an oxidizing agent formed from a peracid compound and a buffer. The composition contains a mixture of peracetic acid at 0.0050% weight / volume (W / V) to 0.5% weight / volume and hydrogen peroxide at 0.5% weight / volume to 50.0% weight / volume as the oxidizing agent, and a buffer with a pKa value in the range of 2 mM to 2 M and of about 4.5 to 11.5 as the buffer. Patent Document 4 specifically discloses that the buffer can be acetic acid, propionic acid, glycine, dihydrogen phosphate, hydrogen phosphate, bicarbonate or carbonate. However, the effect of such a composition for cleaning and purifying on adhesives has not been confirmed when applied to medical devices.

[0006] Citation List

[0007] Patent Document

[0008] Patent Document 1: US Patent Publication No. 5900256

[0009] Patent Document 2: JP2007 - 254693A

[0010] Patent Document 3: US Patent Publication No. 5077008

[0011] Patent Document 4: WO01 / 019414A Summary of the Invention

[0012] Technical Problem

[0013] An object of the present invention is to provide a microbicidal composition that can be used for disinfecting and / or microbiocidally treating a test object containing an adhesive. More preferably, an object of the present invention is particularly to provide a microbicidal composition capable of disinfecting and / or microbiocidally treating a test object containing a synthetic adhesive while limiting a reduction in the durability of the adhesive.

[0014] Another object of the present invention is to provide a combination of preparations (combination preparation) that can be suitably used for preparing a microbicidal composition.

[0015] Another object of the present invention is to provide a method for disinfecting a test object by using a microbicidal composition, and a disinfection device for disinfection.

[0016] Technical Solution

[0017] The inventors of the present invention have conducted extensive research to achieve the above object, and have found that a combination of peracetic acid and hydrogen peroxide, which are effective as microbicidal components, and glycine, which is one of the aminocarboxylic acids, in a specific ratio can limit the reduction in the durability of synthetic adhesives caused by peracetic acid and hydrogen peroxide while maintaining the desired disinfection effect. Then, the inventors have determined that a microbicidal composition containing these three components can be effectively used as a disinfectant for test objects containing synthetic adhesives, such as instruments and devices (e.g., endoscopes) in the medical or food fields that require disinfection and microbicidal treatment.

[0018] The present invention has been completed as a result of further research based on these findings, and includes the following embodiments.

[0019] (I) Microbicidal composition

[0020] (I-1) A microbicidal composition comprising:

[0021] Peracetic acid,

[0022] Hydrogen peroxide, and

[0023] Glycine,

[0024] wherein the amount of peracetic acid is at least 0.03% by mass and less than 1.0% by mass, the amount of hydrogen peroxide is at least 0.045% by mass and less than 1.5% by mass, and the amount of glycine is 0.036% by mass or more.

[0025] (I-2) The microbicidal composition according to (I-1), which is in the form of an aqueous solution having a pH of 2 or more.

[0026] (I-3) The microbicidal composition according to (I-1) or (I-2), further comprising at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

[0027] (I-4) The microbicidal composition according to any one of (I-1) to (I-3), which is a disinfectant and / or microbicide for a test object containing an adhesive, preferably a synthetic adhesive.

[0028] (I-5) The microbicidal composition according to (I-4), wherein the test object is an instrument or device in the medical or food fields that requires disinfection or microbicidal treatment.

[0029] (I-6) The microbicidal composition according to any one of (I-1) to (I-5), which does not contain at least nitrates, nitrites, tungstates, molybdates, chromates, borates, silicates, sulfites, and amine salts as corrosion inhibitors.

[0030] (II) Combined preparation

[0031] (II-1) A combined preparation, comprising:

[0032] (A) A preparation containing peracetic acid and hydrogen peroxide, and

[0033] (B) A preparation containing glycine,

[0034] wherein before use, preparation (A) and preparation (B) are mixed with an aqueous solvent to prepare an aqueous solution, the aqueous solution containing at least 0.03% by mass and less than 1.0% by mass of peracetic acid, at least 0.045% by mass and less than 1.5% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, and the pH of the aqueous solution is 2 or greater.

[0035] (II-2) The combined preparation according to (II-1), wherein preparation (B) further contains at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

[0036] (II-3) The combined preparation according to (II-1) or (II-2), which is used to prepare the microbicidal composition of any one of (I-1) to (I-6).

[0037] (III) Method for preparing a microbicidal composition

[0038] (III-1) A method for preparing the microbicidal composition of (I-2), comprising mixing (A) a preparation containing peracetic acid and hydrogen peroxide and (B) a preparation containing glycine with an aqueous solvent to prepare an aqueous solution, the aqueous solution containing at least 0.03% by mass and less than 1.0% by mass of peracetic acid, at least 0.045% by mass and less than 1.5% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, and the pH of the aqueous solution is 2 or greater.

[0039] (III-2) The method according to (III-1), wherein preparation (B) further contains at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

[0040] (IV) Disinfection device

[0041] (IV-1) A disinfection device, comprising:

[0042] A disinfection chamber, and

[0043] A disinfectant delivery system,

[0044] wherein the disinfectant delivery system is configured to separately supply (A) a formulation containing peracetic acid and hydrogen peroxide and (B) a formulation containing glycine to a disinfection chamber, in which the supplied formulation (A) and the supplied formulation (B) are mixed with separately supplied water to prepare an aqueous solution, the aqueous solution containing at least 0.03% by mass and less than 1.0% by mass of peracetic acid, at least 0.045% by mass and less than 1.5% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, and the pH of the aqueous solution being 2 or greater.

[0045] (IV-2) The disinfection device according to (IV-1), wherein the formulation (B) further contains at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

[0046] (IV-3) The disinfection device according to (IV-1) or (IV-2), which is used for disinfecting or microbiocidally treating a test object containing an adhesive, preferably a synthetic adhesive.

[0047] (IV-4) The disinfection device according to (IV-3), wherein the test object is an instrument or device in the medical or food field that needs to be disinfected or microbiocidally treated.

[0048] (V) Disinfection method

[0049] (V-1) A method for disinfecting a test object, comprising treating the test object with a microbiocidal composition according to any one of (I-1) to (I-6).

[0050] (V-2) The method according to (V-1), comprising mixing (A) a formulation containing peracetic acid and hydrogen peroxide and (B) a formulation containing glycine with an aqueous solvent before treating the test object to prepare a microbiocidal composition according to any one of (I-1) to (I-6).

[0051] (V-3) The method according to (V-1) or (V-2), wherein the test object contains an adhesive, preferably a synthetic adhesive.

[0052] (V-4) The method according to (V-3), which is a method for disinfecting a test object while limiting a decrease in the durability of the adhesive.

[0053] Advantages of the invention

[0054] The microbicidal composition disclosed in the present invention (hereinafter simply referred to as "the microbicidal composition of the present invention") contains an effective amount of peracetic acid and hydrogen peroxide (which do not involve residue or toxicity problems) as microbicidal components, and can thus be used as a chemical disinfectant and / or microbicide in the medical or food fields. In particular, due to its effect of limiting the reduction in durability of synthetic adhesives, the microbicidal composition of the present invention can effectively be used as a disinfectant and / or microbicide (practical liquid) for test objects containing synthetic adhesives (for example, test objects having parts joined with synthetic adhesives or test objects having parts covered with synthetic adhesives (for example, medical devices such as endoscopes, and instruments and devices in the medical or food fields that require disinfection and microbicidal treatment)). Examples of "reduction in durability" include a decline in appearance (such as color change, foaming, and cracking) and / or a decline in function (such as a reduction in adhesiveness and peeling).

[0055] The combined preparation disclosed in the present invention (hereinafter simply referred to as "the combined preparation of the present invention") is a preparation containing a peracetic acid and hydrogen peroxide preparation as the microbicidal component of the microbicidal composition of the present invention in (A) and a preparation containing glycine in (B) to be mixed with the preparation (A), wherein each component is contained in a separate container at a relatively high concentration (the two reagents are mixed and diluted at the time of use). This allows for the storage of peracetic acid and hydrogen peroxide while maintaining their stability, and allows for the easy preparation of the microbicidal composition of the present invention by mixing the two preparations and diluting the mixture with an aqueous solvent such as water at the time of use.

[0056] The disinfection device disclosed in the present invention (hereinafter simply referred to as "the disinfection device of the present invention") allows for the easy preparation of the microbicidal composition of the present invention by using a preparation containing peracetic acid and hydrogen peroxide in (A) and a preparation containing glycine in (B); and also allows for the easy disinfection and microbicidal treatment of test objects containing synthetic adhesives (such as instruments and devices in the medical or food fields).

[0057] The disinfection method disclosed in the present invention (hereinafter simply referred to as "the disinfection method of the present invention") allows for an effective disinfection and microbicidal treatment of test objects containing synthetic adhesives (such as instruments and devices in the medical or food fields) by using the microbicidal composition of the present invention while limiting the reduction in durability of the adhesive. Detailed Description

[0058] Definition of terms

[0059] The term "microbicidal treatment" means killing microorganisms. There are no particular limitations on the type of target microorganisms and the degree of extinction. Therefore, the term is interpreted in a broad sense. A "microbicidal composition" means a composition having such a microbicidal action, and can be any composition having at least the action of killing some microorganisms, regardless of the degree of action. A "microbicide" means a preparation for microbicidal purposes.

[0060] The term "disinfection" means neutralizing toxicity by reducing the number of microorganisms to a harmless level or rendering them non-infectious (i.e., rendering the pathogenic microorganisms present in the target test object harmless). The phrase "rendering pathogenic microorganisms harmless" includes rendering pathogenic bacteria harmless by completely killing the bacteria (narrow sense of "microbicidal treatment"). In this sense, "disinfection" includes the microbicidal treatment in the narrow sense, which means killing almost all pathogenic bacteria for detoxification. The term "disinfectant" means a preparation for disinfection purposes. As described above, disinfectants include disinfectants having a microbicidal action, which can be called "disinfecting and microbicidal agents".

[0061] As shown in Table 1, according to the Spaulding disinfection level classification, disinfection is divided into sterilization, high-level disinfection, intermediate-level disinfection, and low-level disinfection. Appropriate disinfection treatments and / or disinfectants for each level are selected according to the intended use of the test object to be disinfected (Rutala WA: APIC Guideline for selection and use of disinfectants, 1996. Am J Infect Control 1996; 24: 313-342).

[0062] [Table 1]

[0063] [Spaulding's Disinfection Level Classification]

[0064]

[0065] For example, for instruments and devices used in the medical field, infection control guidelines stipulate that, as a standard precaution, highly critical instruments (highly critical items, such as surgical instruments, circulatory devices or catheters, implants, needles and scalpels) inserted into sterile tissue or blood vessels must be disinfected by sterilization. The infection control guidelines also stipulate that semi-critical instruments (semi-critical items, such as respiratory therapy devices, anesthesia devices, endoscopes, laryngoscopes, nebulizers, tracheal catheters and thermometers) used in contact with mucous membranes or unhealthy skin, such as damaged skin, must be subjected to high-level disinfection or intermediate-level disinfection. The infection control guidelines also stipulate that non-critical instruments (non-critical items, such as blood pressure cuffs, stethoscopes, crutches, bedpans and environmental surfaces including toilet seats and bed rails) used in contact only with healthy skin must be subjected to low-level disinfection.

[0066] (I) Microbicidal composition

[0067] The microbicidal composition of the present invention comprises peracetic acid, hydrogen peroxide and glycine. The microbicidal composition according to the present invention has a microbicidal action based on the microbicidal action of peracetic acid and hydrogen peroxide. The microbicidal composition of the present invention can be effectively used for microbicidal treatment of a test object, preferably disinfection and microbicidal treatment.

[0068] The amount of peracetic acid in the microbicidal composition of the present invention can be set in the range of at least 0.03% by mass and less than 1.0% by mass. As shown in the examples described later, the lower limit can be freely selected from the range of 0.03% by mass to 0.07% by mass, and the upper limit can be freely selected from the range of at least 0.4% by mass and less than 1.0% by mass. The amount of peracetic acid is preferably from 0.03% by mass to 0.9% by mass, more preferably from 0.03% by mass to 0.8% by mass, still more preferably from 0.03% by mass to 0.6% by mass, and particularly preferably from 0.03% by mass to 0.4% by mass.

[0069] The amount of hydrogen peroxide in the microbicidal composition of the present invention can be set in the range of at least 0.045% by mass and less than 1.5% by mass. As shown in the examples described later, the lower limit can be freely selected from the range of 0.45% by mass to 0.11% by mass, and the upper limit can be freely selected from the range of at least 0.6% by mass and less than 1.5% by mass. The amount of hydrogen peroxide is preferably from 0.045% by mass to 1.35% by mass, more preferably from 0.045% by mass to 1.2% by mass, still more preferably from 0.045% by mass to 0.9% by mass, and particularly preferably from 0.045% by mass to 0.6% by mass.

[0070] The amount of glycine in the microbicidal composition of the present invention can be set within the range of 0.036% by mass or more. There is no limit to the upper limit as long as it does not adversely affect the effect of the microbicidal composition of the present invention. Considering, for example, cost, it is not necessary to add an excessive amount of glycine. For example, the amount of glycine can be appropriately adjusted within the range of 0.036% by mass to 2% by mass. As shown in the examples described later, the lower limit can be freely selected from the range of 0.036% by mass to 0.08% by mass, and the upper limit can be freely selected from the range of 0.48% by mass to less than 1.2% by mass, or 0.48% by mass to 1.08% by mass. The amount of glycine is preferably 0.036% by mass to less than 1.2% by mass, more preferably 0.036% by mass to 1.08% by mass, still more preferably 0.036% by mass to 0.96% by mass, yet more preferably 0.036% by mass to 0.72% by mass, and particularly preferably 0.036% by mass to 0.48% by mass.

[0071] The microbicidal composition of the present invention as a practical liquid that can limit the corrosive action of peracetic acid and hydrogen peroxide on the synthetic binder while exhibiting the desired microbicidal action can be prepared by adding peracetic acid, hydrogen peroxide, and glycine to an aqueous solvent to obtain the above ratios and dissolving them.

[0072] Although there is no limit to the ratio of hydrogen peroxide to 100 parts by mass of peracetic acid in the microbicidal composition according to the present invention, it can be 50 parts by mass to 600 parts by mass, preferably 70 parts by mass to 450 parts by mass, and more preferably 100 parts by mass to 200 parts by mass. The ratio of glycine to 100 parts by mass of peracetic acid can be 15 parts by mass to 500 parts by mass, preferably 50 parts by mass to 350 parts by mass, and more preferably 80 parts by mass to 180 parts by mass. In addition, the ratio of glycine to 100 parts by mass of hydrogen peroxide can be 10 parts by mass to 350 parts by mass, preferably 30 parts by mass to 230 parts by mass, and more preferably 50 parts by mass to 120 parts by mass.

[0073] The microbicidal composition of the present invention is a composition in the form of an aqueous solution prepared by dissolving the three components in an aqueous solvent. The aqueous solvent is preferably water, for example. The type of water is not particularly limited and can be tap water, distilled water, ion-exchanged water, or RO water. As shown in Experimental Example 1 described later, it has been confirmed that the microbicidal composition of the present invention exhibits a microbicidal action even when prepared with water having a relatively high hardness (hard water). Specifically, the microbicidal composition of the present invention can be prepared by using water having a hardness based on the following calcium carbonate concentration: at least 400 ppm or lower, and more preferably 60 ppm to 400 ppm.

[0074] The microbicidal composition of the present invention may comprise another aqueous solvent in combination with water, provided that it does not adversely affect the dissolution of the three components and the effect of the present invention. Examples of such aqueous solvents include those compatible with water, such as ethanol, propanol, isopropanol, butanol, acetone, and acetonitrile.

[0075] The microbicidal composition of the present invention may also comprise at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffers, provided that it does not adversely affect the dissolution of the three components and the effect of the present invention.

[0076] Hydrogen phosphates include alkali metal hydrogen phosphates, such as dipotassium hydrogen phosphate, disodium hydrogen phosphate, potassium dihydrogen phosphate, and sodium dihydrogen phosphate. Preferably, the hydrogen phosphate is dipotassium hydrogen phosphate and disodium hydrogen phosphate, and more preferably dipotassium hydrogen phosphate. The amount of hydrogen phosphate in the microbicidal composition of the present invention may be set in the range of 0% by mass to 0.3% by mass, preferably 0% by mass to 0.2% by mass, and more preferably 0% by mass to 0.12% by mass, but is not limited thereto. An example of the minimum amount of hydrogen phosphate added is (but is not limited to) 0.009% by mass.

[0077] Chelating agents can be used for the purpose of chelating metals in tap water, such as calcium, magnesium, divalent copper ions, divalent iron ions, trivalent iron ions, and manganese ions. Specifically, examples include but are not limited to ethylenediaminetetraacetates, diethylenetriaminepentaacetates, hydroxyethylethylenediaminetriacetates, L-glutamic acid diacetates, hydroxyethanediphosphonates, nitrilotrimethylenephosphonates, phosphonobutane tricarboxylates, and ethylenediaminetetramethylenephosphonates. The chelating agent is preferably tetrasodium hydroxyethanediphosphonate. The chelating agent can be used in a proportion that can achieve the above purpose. The amount of chelating agent in the microbicidal composition of the present invention may be set in the range of 0% by mass to 0.15% by mass, preferably 0% by mass to 0.1% by mass, and more preferably 0% by mass to 0.06% by mass, but is not limited thereto. An example of the minimum amount of chelating agent added is (but is not limited to) 0.0045% by mass.

[0078] The pH buffer is used to adjust the pH of the microbicidal composition of the present invention and to buffer the pH. Preferably, the pH buffer is used to adjust or buffer the pH of the microbicidal composition of the present invention to 2 or higher, and more preferably 3 or higher. The upper limit of the pH of the microbicidal composition of the present invention is preferably (but is not limited to) 7. The pH range is, for example, 2 to 7, preferably 3 to 7, and more preferably 3 to 6. Specifically, examples of the pH buffer include but are not limited to hydroxide salts such as potassium hydroxide and sodium hydroxide, organic acids or their salts such as citric acid and citrate salts, and phosphoric acid or its salts (e.g., trisodium phosphate and dipotassium phosphate).

[0079] The microbicidal composition of the present invention may also contain, for example, stabilizers and preservatives as optional components. The stabilizers are for the purpose of stabilizing microbicidal components such as peracetic acid and hydrogen peroxide, and the stabilizers specifically include water-soluble solvents, amphiphilic solvents, and surfactants. The stabilizer is preferably a polyol such as propylene glycol, dipropylene glycol, or butylene glycol. The stabilizer can be used in a proportion that can achieve the said purpose. The amount of the stabilizer in the microbicidal composition of the present invention can be set in the range of 0% by mass to 1% by mass, preferably 0% by mass to 0.7% by mass, and more preferably 0% by mass to 0.4% by mass, but is not limited thereto. Examples of the minimum amount of the stabilizer are (but not limited to) 0.03% by mass.

[0080] The preservative can be, for example, benzoic acid or its salts (e.g., alkali metal salts such as sodium benzoate), parabens (e.g., ethyl paraben), isothiazoline compounds (e.g., methylisothiazolinone), phenoxyethanol, and hexylene glycol. The amount of the preservative in the microbicidal composition of the present invention can be set in the range of 0% by mass to 0.1% by mass, preferably 0% by mass to 0.07% by mass, and more preferably 0% by mass to 0.04% by mass, but is not limited thereto. Examples of the minimum amount of the preservative are (but not limited to) 0.003% by mass.

[0081] The microbicidal composition of the present invention can be prepared by dissolving the above-mentioned peracetic acid, hydrogen peroxide, and glycine in the above-mentioned proportions in an aqueous solvent, and optionally adjusting the pH of the liquid to preferably 2 to 7, and more preferably 3 to 7 with a pH buffer. In this preparation process, in addition to the said three components, auxiliary components such as hydrogen phosphates or chelating agents, or optional components such as stabilizers or preservatives as described above can also be optionally added.

[0082] The microbicidal composition of the present invention preferably does not contain at least one member known as a corrosion inhibitor selected from chromates, molybdates, nitrates, nitrites, tungstates, borates, silicates, sulfites, and amine salts; and preferably does not contain any of these.

[0083] The microbicidal composition of the present invention has a microbicidal effect on microorganisms such as common bacteria, acid-fast bacteria, fungi, viruses, and spores due to the microbicidal action of peracetic acid and hydrogen peroxide. In particular, the bactericidal composition of the present invention has a microbicidal effect on the following: common bacteria including Gram-negative bacteria and Gram-positive bacteria (Staphylococcus aureus, Enterococcus faecium, Escherichia coli, Pseudomonas aeruginosa), acid-fast bacteria (Mycobacterium terrae), fungi (Candida albicans or Aspergillus brasiliensis), viruses (Poliovirus, Adenovirus, Norovirus, Influenzavirus, Coronavirus), and spores such as Bacillus subtilis spores (Bacillus subtilis) and Clostridium sporogenes spores (Clostridium sporogenes). The microbicidal effect on these microorganisms can be evaluated in a suspension test or a carrier test according to methods commonly used in the art.

[0084] In addition, the microbicidal composition of the present invention has the property of limiting the reduction in the durability of synthetic adhesives caused by the action of peracetic acid and hydrogen peroxide.

[0085] Due to the deterioration of the adhesive component, the synthetic adhesive may change color. The deterioration of the adhesive component may also form fine bubbles (foaming phenomenon) or cracks. In addition, a gap may form between the adherend and the adhesive, and the adherend may eventually fall off. If the durability of the adhesive deteriorates and the adhesive component deteriorates in this way, the adhesive strength decreases or disappears, which may further cause the adherend or the adhesive to fall off (detachment), or damage the strength of the instrument or device, or cause the adhesive component to leach (leak). Foreign body contamination caused by the fall of the adherend or the adhesive or the leaching (leakage) of the adhesive component may have an adverse effect on the human body, especially in the case of medical devices or devices applied to the human body, tableware, and kitchen utensils.

[0086] When used on test objects containing synthetic adhesives, the microbicidal composition of the present invention can effectively perform microbicidal treatment and / or disinfection treatment while preventing a reduction in the durability of the adhesive due to peracetic acid and hydrogen peroxide. Therefore, the microbicidal composition of the present invention is particularly useful as a disinfectant and / or microbicide (including disinfection and microbicide) for test objects containing synthetic adhesives. In particular, the microbicidal composition of the present invention can be suitably used for microbicidal treatment and / or disinfection of test objects that cannot withstand microbicidal treatments (such as high-temperature microbicidal treatment and microbicidal treatment using highly corrosive microbicides) that may have an adverse effect on synthetic adhesives.

[0087] Test objects containing synthetic adhesives are, for example, test objects formed by joining parts with a synthetic adhesive (test objects having parts joined with a synthetic adhesive), test objects completely or partially covered with a synthetic adhesive, or test objects formed by filling depressions, but are not limited thereto. Preferred examples of test objects include, but are not limited to, medical devices such as endoscopes, ventilators, anesthesia machine circuits, cystoscopes, laryngoscope blades, bite blocks, nebulizers, catheters, puncture devices for blood collection, ultrasonic echo probes, dental probes, curettes, files, mirrors, impression trays, scalers, jaw instruments, and reamers; and devices for food such as baby bottles, baby bottle nipples, plates, and cups. Examples of materials forming these test objects include, but are not limited to, glass, plastics, elastomers, ceramics, aluminum, aluminum alloys, stainless steel, tungsten alloys, nickel-titanium alloys, nickel-chromium alloys, titanium alloys, cobalt alloys, and cobalt-chromium alloys.

[0088] Synthetic adhesives include thermoplastic resin adhesives (such as vinyl acetate resin adhesives, polyvinyl acetal adhesives, ethylene vinyl acetate resin adhesives, vinyl chloride resin adhesives, acrylic resin adhesives, polyamide adhesives, cellulose adhesives, and α-olefin adhesives), thermosetting resin adhesives (such as urea resin adhesives, melamine resin adhesives, phenolic resin adhesives, resorcinol resin adhesives, epoxy resin adhesives, polyester adhesives, polyurethane adhesives, and polyaromatic adhesives), and elastomer adhesives (chloroprene rubber adhesives, nitrile rubber adhesives, styrene-butadiene rubber adhesives, polysulfide adhesives, butyl rubber adhesives, silicone adhesives (including modified silicone adhesives), acrylic adhesives, urethane adhesives, silylated urethane resin adhesives, and telechelic polyacrylate adhesives). The microbicidal composition of the present invention has the property of limiting a reduction in durability of at least, but not limited to, the following: vinyl acetate resin adhesives belonging to the thermoplastic resin adhesive category, epoxy resin adhesives belonging to the thermosetting resin adhesive category, and silicone adhesives belonging to the elastomer adhesive category.

[0089] Whether the microbicidal composition of the present invention has the property of limiting the reduction in durability of the synthetic binder can be easily evaluated as described, for example, in Experimental Example 2 below: A test piece to which the synthetic binder is applied is immersed in the microbicidal composition of the present invention and maintained at 40°C for 16 hours, then the test piece is washed with distilled water, and the appearance of the naturally dried binder is visually observed. The items to be evaluated in this evaluation are mainly the presence or absence of discoloration, bubbles, cracks, and / or gaps and peeling. If none of these is observed, it is determined that the microbicidal composition in question has the property of limiting the reduction in durability of the synthetic binder due to peracetic acid and hydrogen peroxide. In particular, as shown by the relationship between Example 2-1 and Comparative Example 2-1, the microbicidal composition of the present invention in which at least one of the evaluation items is improved is evaluated as being able to limit the reduction in durability of the binder due to peracetic acid and hydrogen peroxide due to the addition of glycine, as compared with a composition (comparative composition) formed by removing glycine only from the microbicidal composition of the present invention.

[0090] (II) Combined preparation

[0091] The above-described microbicidal composition of the present invention is a practical liquid that can be used as it is for the microbicidal treatment and / or disinfection treatment of a test object. However, considering the stability of peracetic acid and hydrogen peroxide in water, the microbicidal composition is preferably prepared by mixing the components and adjusting the mixture by diluting with an aqueous solvent to obtain the contents of the respective components as described above before use.

[0092] Therefore, the present invention provides a combined preparation comprising (A) a preparation containing peracetic acid and hydrogen peroxide and (B) a preparation containing glycine, wherein the preparations (A) and (B) are each filled in a single separate container. As an embodiment of the combined preparation, an example is a combined preparation of a two-preparation product or a kit product that contains the preparations (A) and (B) that are each concentrated, filled in separate containers, and packaged for supply to the market. The two-preparation product or the kit product is in such a form of use that the user mixes the two preparations (A) and (B) and dilutes the mixture with an aqueous solvent before use. In addition to glycine, the preparation (B) may optionally contain at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents. The preparation (B) may also contain a stabilizer and / or a preservative as optional components.

[0093] The aqueous solvent, hydrogen phosphate, chelating agent, pH buffering agent, stabilizer, and preservative for this case may be those described in the above part (I).

[0094] The preparations (A) and (B) may be in the form of a liquid or in the form of a solid such as a powder, granule, or tablet.

[0095] There is no particular limitation on the ratio of peracetic acid and hydrogen peroxide in formulation (A) and the ratio of glycine, auxiliary components and / or optional components in formulation (B), as long as the microbicidal composition of the present invention described in part (I) can be prepared by mixing these components with an aqueous solvent. Specifically, if formulation (A) and formulation (B) are mixed and the mixture is diluted with an aqueous solvent to result in an amount of peracetic acid of at least 0.03% by mass and less than 1.0% by mass, an amount of hydrogen peroxide of at least 0.045% by mass and less than 1.5% by mass, an amount of glycine of 0.036% by mass or more (preferably 0.036% by mass to 2% by mass), an amount of hydrogen phosphate of 0% by mass to 0.3% by mass, an amount of chelating agent of 0% by mass to 0.15% by mass, and an amount of stabilizer of 0% by mass to 1% by mass, it is sufficient. Although not limited thereto, the ratio of the components in formulation (A) and formulation (B) is preferably such that after mixing and dilution, the amount of peracetic acid is 0.03% by mass to 0.9% by mass, the amount of hydrogen peroxide is 0.045% by mass to 1.35% by mass, and the amount of glycine is 0.036% by mass to 1.08% by mass; more preferably, after mixing and dilution, the amount of peracetic acid is 0.03% by mass to 0.8% by mass, the amount of hydrogen peroxide is 0.045% by mass to 1.2% by mass, and the amount of glycine is 0.036% by mass to 0.96% by mass; still more preferably, after mixing and dilution, the amount of peracetic acid is 0.03% by mass to 0.6% by mass, the amount of hydrogen peroxide is 0.045% by mass to 0.9% by mass, and the amount of glycine is 0.036% by mass to 0.72% by mass; and particularly preferably, after mixing and dilution, the amount of peracetic acid is 0.03% by mass to 0.4% by mass, the amount of hydrogen peroxide is 0.045% by mass to 0.6% by mass, and the amount of glycine is 0.036% by mass to 0.48% by mass.

[0096] When mixed and diluted with an aqueous solvent, formulations (A) and (B) are set to obtain a pH of 2 to 7, and preferably 3 to 7. The ratio of the pH buffer optionally added to formulation (B) can also be appropriately set as high as the limit at which the pH can be adjusted to fall within these ranges.

[0097] The dilution factor of the aqueous solvent is not particularly limited, but can be about 20 times to 300 times. Examples of the combined formulation as described above include, but are not limited to, a combined formulation including formulation (A) containing 5% by mass to 45% by mass of peracetic acid and 5% by mass to 35% by mass of hydrogen peroxide and formulation (B) containing 3% by mass to 54% by mass of glycine.

[0098] The combined preparation of the present invention can be suitably used for preparing the microbicidal composition of the present invention described above. Specifically, the microbicidal composition of the present invention can be easily prepared by mixing formulation (A) and formulation (B) included in the combined preparation of the present invention and diluting the mixture with an aqueous solvent.

[0099] (III) Disinfection device

[0100] The microbicidal composition of the present invention prepared from formulation (A) and formulation (B) can be suitably used for the microbicidal treatment and / or disinfection treatment (collectively referred to as "disinfection and microbicidal treatment" hereinafter) of a test object containing a synthetic binder. Without any limitation, such treatment can be carried out with any disinfection device.

[0101] The disinfection device can be, for example, a device provided with at least a disinfection chamber and a disinfectant delivery system. The disinfection chamber is an openable compartment (chamber) for the disinfection and microbicidal treatment of the test object. As described above, this compartment can be used for preparing the microbicidal composition of the present invention, disinfecting and microbicidally treating the test object with the microbicidal composition, and / or performing a washing treatment after the disinfection and microbicidal treatment. The disinfectant delivery system includes a pipeline for delivering formulation (A) into the disinfection chamber and a pipeline for delivering formulation (B) into the disinfection chamber, and supplies formulation (A) and formulation (B) into the disinfection chamber separately. The disinfectant delivery system also includes a water injection pipeline for delivering an aqueous solvent into the disinfection chamber, which is separated from the above pipelines. The disinfectant delivery system supplies formulation (A), formulation (B), and an aqueous solvent into the disinfection chamber through separate pipelines, and mixes the components to prepare an aqueous solution (the microbicidal composition of the present invention) having a pH of 2 or higher and containing at least 0.03% by mass and less than 1.0% by mass of peracetic acid, at least 0.045% by mass and less than 1.5% by mass of hydrogen peroxide, and 0.036% by mass or more, preferably 0.036% by mass to 2% by mass of glycine.

[0102] The disinfection and microbicidal treatment with the disinfection device can be carried out by exposing (e.g., dipping, spraying, or coating) the target test object in the aqueous solution (the microbicidal composition of the present invention) in the disinfection chamber. The temperature of the microbicidal composition of the present invention for the disinfection and microbicidal treatment is preferably (but not limited to) 10°C or higher, preferably 15°C or higher, and more preferably 20°C or higher. Although the limit is 100°C, the upper limit of the temperature can be any temperature, such as 60°C or lower, and preferably 40°C or lower. The exposure time is also not limited as long as the microbicidal effect can be achieved. The exposure time can be selected, for example, from the range of 1 minute to 24 hours, preferably 5 minutes to 16 hours.

[0103] After disinfection and microbicidal treatment with the microbicidal composition of the present invention, the test object can be optionally washed with water and dried, and then the disinfection and microbicidal treatment can be completed.

[0104] (IV) Disinfection method

[0105] The disinfection method of the present invention can be carried out by treating a test object with the above-mentioned microbicidal composition of the present invention.

[0106] The target test object to be treated is not limited, but preferably a test object containing an adhesive. The adhesive includes the above-mentioned synthetic adhesive. Although not limited thereto, test objects containing an adhesive include, for example, test objects formed by joining components with an adhesive and test objects partially covered with an adhesive. Preferably, the test object containing an adhesive is a test object having a part joined with an adhesive.

[0107] Examples of the target test objects to be treated include, but are not limited to, instruments and devices in the medical or food fields that require disinfection or microbicidal treatment. Examples of instruments and devices in the medical field include, but are not limited to, endoscopes, respiratory therapy devices, anesthesia devices, cystoscopes, laryngeal lenses, bite blocks, nebulizers, catheters (such as endotracheal catheters and nasal catheters), puncture devices for blood collection, ultrasonic echo probes, dental mirrors, impression trays, scalers, palatal instruments, and reamers. These include those classified as highly hazardous instruments or moderately hazardous instruments as described above. Examples of instruments and devices in the food field include food utensils (including tableware), such as baby bottles, baby bottle nipples, plates, and cups, cooking utensils, cooking appliances, and cooking tables.

[0108] The disinfection treatment can be, for example, a method of keeping the test object in contact with the microbicidal composition of the present invention. Specific examples include a method of immersing the test object in the microbicidal composition of the present invention, a method of spraying or coating the test object with the microbicidal composition of the present invention, a method of passing the microbicidal composition of the present invention through the test object, and a method of wiping the test object with a cloth moistened with the microbicidal composition of the present invention. After disinfection treatment with the microbicidal composition of the present invention, the disinfected test object can be optionally washed with water and dried.

[0109] In the disinfection treatment, the microbicidal composition of the present invention used can be, without limitation, the composition prepared by mixing formulation (A) and formulation (B) with an aqueous solvent as described in the above part (II) before use. In other words, in addition to the step of treating the test object with the microbicidal composition of the present invention, one embodiment of the disinfection method of the present invention further includes a preliminary step of preparing the microbicidal composition of the present invention by mixing formulation (A) and formulation (B) with an aqueous solvent.

[0110] Since the microbicidal composition of the present invention can limit the reduction in the durability of the synthetic binder caused by the action of peracetic acid and hydrogen peroxide, the microbicidal composition of the present invention is suitably applicable to, for example, the disinfection treatment of test objects containing synthetic binders as described above.

[0111] In this specification, the terms "comprising", "containing" and "including" include the meanings of "consisting of" and "consisting essentially of".

[0112] Examples

[0113] The present invention will be described below with reference to experimental examples to facilitate understanding of the elements and effects of the present invention. However, the present invention is not limited by any of these experimental examples. Unless otherwise indicated, the following experiments are carried out at atmospheric pressure at room temperature (25 °C ± 5 °C). Unless otherwise specified, the following unit "%" represents mass %, and the unit "parts" represents parts by mass.

[0114] Experimental example 1: Evaluation of microbicidal effect

[0115] The microbicidal effect of the microbicidal composition according to the present invention was evaluated by using Aspergillus brasiliensis (ATCC 16404) as the microorganism. Aspergillus brasiliensis is an environmentally air-borne microorganism that may pose a risk of contamination in the medical field and forms highly drug-resistant spores among filamentous fungi.

[0116] (1) Preparation of test compositions

[0117] The components shown in Table 2 were dissolved in synthetic hard water to obtain the respective concentrations and pH specified in Table 2, thereby preparing test compositions (Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-7). The synthetic hard water used was prepared as follows: 6 mL of the following Solution A and 8 mL of the following Solution B were mixed, and the mixture was adjusted with distilled water to obtain a total volume of 1000 mL (the same applies to the experimental examples described below).

[0118] Solution A: Dissolve MgCl2 (1.984 g) + CaCl2 (4.624 g) in distilled water and adjust to obtain a volume of 100 mL.

[0119] Solution B: Dissolve MgHCO3 (3.502 g) in distilled water and adjust to obtain a volume of 100 mL.

[0120] (2) Preparation of inoculum solution

[0121] Inoculate the glycerol stock solution of Aspergillus brasiliensis in malt extract agar medium (malt extract agar: Oxoid Limited) and culture it at 30 °C for 7 days. After the culture, add an aqueous solution of 0.05% by mass of polysorbate 80, and scrape off the spores with a cell spreader. Place the obtained spore liquid in a 50 mL centrifuge tube, add 5 g of sterile glass beads, and then stir for 1 minute. After stirring, filter the liquid twice through a cell filter (mesh size: 40 μm) for use.

[0122] Evaluation test for microbicidal effect

[0123] Evaluate the microbicidal effect of the test compositions (Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-7) according to the test method (suspension test) specified in EN 13624:2013 (cleaning conditions). In this test method, the test compositions determined to have a microbicidal effect can be used as high-level disinfectants according to Spaulding classification for disinfecting moderately hazardous instruments or devices in the medical field. Specifically, it was determined that the test compositions determined to have a microbicidal effect in this test method have a killing effect on yeast-like fungi (including Candida) and filamentous fungi.

[0124] Specifically, the following operations were carried out to evaluate the microbicidal effect.

[0125] (i) Place 0.5 mL of the inoculum solution pre-maintained at 35 °C and 0.5 mL of an aqueous solution of the interfering substance (0.3% BSA (bovine serum albumin), the same below) under clean conditions in a test tube, stir, and let it stand at 35 °C for 2 minutes.

[0126] (ii) Place 4 mL of the test composition (test sample) pre-maintained at 35 °C in the test tube of item (i), mix, and let it act at 35 °C.

[0127] (iii) After the action duration indicated in Table 2, take 0.5 mL of the mixture solution and place it in 4.5 mL of a neutralizing agent (0.1% sodium thiosulfate, catalase) to inactivate it.

[0128] (iv) Apply 0.5 mL of the inactivated mixture solution to the surface of a solid malt extract agar medium and culture it at 30.

[0129] (v) After culturing for three days, measure the viable fungal count.

[0130] (vi) According to the requirements of EN 13624:2013, for 4Log 10A logarithm reduction value of the fungal count before and after the test of 0 or higher is determined as "○: having an effective microbicidal effect", and other cases are determined as "×: not having an effective microbicidal effect".

[0131] (4) Evaluation results of the microbicidal effect

[0132] Table 2 also shows the results.

[0133] [Table 2]

[0134]

[0135] As shown in Table 2, when the peracetic acid concentration is 0.03% or less and the hydrogen peroxide concentration is 0.045% or less, and glycine is not included, even an aqueous solution containing peracetic acid and hydrogen peroxide (microbicidal components) does not exhibit the desired microbicidal effect (Comparative Example 1-1). In contrast, an aqueous solution having a peracetic acid concentration of 0.03% and a hydrogen peroxide concentration of 0.045%, and containing 0.036% by mass or more of glycine exhibits the desired microbicidal effect (Example 1-1). When the peracetic acid concentration is less than 0.03%, an aqueous solution having a hydrogen peroxide concentration of 0.045% or more and a glycine concentration of 0.036% or more does not exhibit the desired microbicidal effect (Comparative Example 1-2), and when the hydrogen peroxide concentration is less than 0.045%, an aqueous solution having a peracetic acid concentration of 0.03% or more and a glycine concentration of 0.036% or more does not exhibit the desired microbicidal effect (Comparative Example 1-3).

[0136] These results show that a microbicidal composition containing relatively low concentrations of peracetic acid and hydrogen peroxide can exhibit an enhanced microbicidal effect by containing glycine, and that the minimum concentrations of the respective components exhibiting the desired microbicidal effect are as follows: 0.03% for peracetic acid, 0.045% for hydrogen peroxide, and 0.036% for glycine. These results also show that the microbicidal effect of a microbicidal composition containing a predetermined concentration of peracetic acid, hydrogen peroxide, and glycine can be enhanced by adding auxiliary components such as hydrogen phosphates, chelating agents, and stabilizers (Examples 1-2 and 1-3, and Comparative Examples 1-4 and 1-5). These results also show that the microbicidal effect of the microbicidal composition can be enhanced by increasing the amount of peracetic acid, hydrogen peroxide, or glycine (Example 1-4). However, even when the amounts of peracetic acid and hydrogen peroxide are increased or when other auxiliary components are added, an aqueous solution not containing glycine does not exhibit the desired microbicidal effect (Comparative Examples 1-6 and 1-7).

[0137] To determine that the achieved effect is specific to the use of glycine, in the formulation of Example 1-1, the same test was conducted using an equimolar amount of a buffer (acetic acid, trisodium phosphate, or dipotassium hydrogen phosphate) with a pKa range of 4.5 to 11.5 disclosed in the cited Patent Document 4 instead of glycine. Table 3 shows the results of this test as well as the results of Example 1-1 and Comparative Example 1-1.

[0138] [Table 3]

[0139]

[0140] *1: Potassium hydroxide or citric acid

[0141] Note: "-" indicates not evaluated.

[0142] Note: A logarithmic reduction value of 4 Log or higher is "○", and a logarithmic reduction value less than 4 Log is "×".

[0143] As is clear from the results, unlike glycine, acetic acid, trisodium phosphate, and dipotassium hydrogen phosphate cannot enhance the microbicidal activity of acidic oxidants such as peracetic acid and hydrogen peroxide.

[0144] Experimental example 2: Evaluation of the effect of restricting the reduction of the durability of synthetic adhesives

[0145] The effect of limiting the reduction in the durability of the adhesive (corrosion inhibition effect) by the microbicidal composition was evaluated by using silicone adhesives, epoxy adhesives, and vinyl acetate resin adhesives as synthetic adhesives.

[0146] (1) Preparation of the microbicidal composition

[0147] The components listed in Tables 4 to 9 were dissolved in distilled water to obtain the concentrations and pH indicated in these tables, thereby preparing the microbicidal composition.

[0148] (2) Preparation of the adhesive test piece

[0149] A vinyl tape (3 cm × 5 cm) with two punches (diameter: 14 mm, 2 × 1 row) was adhered to one surface of a test piece (3 cm × 5 cm, thickness: 1.0 mm) made of SUS304 (austenitic stainless steel), and the adhesive was poured into the holes. The surface was evenly spread with a spatula so that the height of the adhesive matched the height of the vinyl tape, and the test piece was allowed to stand at room temperature for 24 hours or longer. After drying, the vinyl tape was peeled off, thereby preparing an adhesive test piece with the adhesive adhered to two points on one surface.

[0150] For the adhesives, three types of adhesives (silicone adhesive (Adhesive A), epoxy resin adhesive (Adhesive B), and vinyl acetate resin adhesive (Adhesive C)) were used, and adhesive test pieces A, B, and C were prepared.

[0151] [Adhesive]

[0152] A: Silicone adhesive (Super X No. 8008 Black: Cemedine Co., Ltd.) (Main component: Acrylic acid-modified silicone resin)

[0153] B: Epoxy resin adhesive (3MPanel Bond Mini 38315N: 3M) (Main component: Epoxy resin, curing agent: Amine-based resin)

[0154] C: Vinyl acetate resin adhesive (Coagulant CA-131: Cemedine Co., Ltd.) (Components: 25% vinyl acetate resin, 50% inorganic substance, 25% organic solvent)

[0155] (3) Evaluation test for restricting the effect of durability reduction

[0156] (i) Immerse test pieces A, B, and C in each microbicidal composition maintained at 40 °C and let them stand for 16 hours.

[0157] (ii) After 16 hours, take out each test piece from the immersion solution, rinse it with distilled water, and let it stand at room temperature to air-dry.

[0158] (iii) After drying, visually observe the appearance of the adhesive on each test piece.

[0159] (iv) Evaluate the effect of restricting the durability reduction for four items based on the properties of the adhesive: "Whether the color changes: Yes (×) / No (○)", "Whether foaming (bubbles) occurs: Yes (×) / No (○)", "Whether there are gaps and peeling: Yes (×) / No (○)", and "Whether there are cracks: Yes (×) / No (○)".

[0160] (4) Evaluation results of the effect of restricting the durability reduction

[0161] Table 4 shows the results regarding the effect of glycine and the influence of hydrogen peroxide in the microbicidal composition.

[0162] [Table 4]

[0163] Concentration (mass%) in the microbicidal composition (aqueous solution)

[0164]

[0165] *1: Dipotassium hydrogen phosphate

[0166] *2: Tetrasodium hydroxyethane diphosphonate

[0167] *3: Dipropylene glycol

[0168] *4: Potassium hydroxide or citric acid

[0169] As shown in Table 4, the results indicate that the addition of glycine restricted the reduction in durability (in particular, foaming) of silicone adhesives or vinyl acetate resin adhesives due to peracetic acid and hydrogen peroxide (in particular, Examples 2-1 and 2-2 and Comparative Example 2-1). However, although glycine was included, all of the silicone adhesive, epoxy resin adhesive, and vinyl acetate resin adhesive had foaming or gaps and peeling and were determined to have reduced (altered) durability when the concentration of hydrogen peroxide was 5% or higher (Comparative Examples 2-2 and 2-3).

[0170] Table 5 shows the results of the effects of the concentrations of peracetic acid, hydrogen peroxide, and glycine in the microbicidal composition.

[0171] [Table 5]

[0172] Concentration (mass %) in the microbicidal composition (aqueous solution)

[0173]

[0174] *1: Potassium hydroxide or citric acid

[0175] The results indicate that the microbicidal composition with a peracetic acid concentration of 1.0%, a hydrogen peroxide concentration of 1.5%, and a glycine concentration of 1.2% (Comparative Example 3-1) slightly reduced the durability of silicone adhesives and vinyl acetate resin adhesives, but did not reduce the durability of epoxy resin adhesives. This indicates that the peracetic acid concentration and hydrogen peroxide concentration that can produce an effect of restricting the reduction in durability of these adhesives are less than 1.0% and less than 1.5% respectively. As described above, even when glycine was added in an amount of 1.2%, an aqueous solution with a peracetic acid concentration of 1.0% or higher and a hydrogen peroxide concentration of 1.5% or higher did not sufficiently restrict the reduction in durability of the adhesive. However, for example, even when containing more than 1.2% glycine, an aqueous solution with a peracetic acid concentration of 0.9% and a hydrogen peroxide concentration of 1.35% as in Example 3-5 can provide the same effect as in Example 3-5. This indicates that for an aqueous solution with a peracetic acid concentration of less than 1.0% and a hydrogen peroxide concentration of less than 1.5%, there is no upper limit to the amount of glycine from the perspective of the effect of restricting the reduction in durability of the adhesive.

[0176] Table 6 (silicone adhesives), Table 7 (epoxy adhesives), and Table 8 (vinyl acetate resin adhesives) show the results regarding the effect of the pH of the antimicrobial composition.

[0177] [Table 6]

[0178] Concentration (mass %) in the antimicrobial composition (aqueous solution)

[0179]

[0180] *1: Potassium hydroxide or citric acid

[0181] [Table 7]

[0182] Concentration (mass %) in the antimicrobial composition (aqueous solution)

[0183]

[0184] *1: Potassium hydroxide or citric acid

[0185] [Table 8]

[0186] Concentration (mass %) in the antimicrobial composition (aqueous solution)

[0187]

[0188] *1: Potassium hydroxide or citric acid

[0189] The results show that the antimicrobial composition has the property of limiting the reduction in the durability of these adhesives at a pH of 2 to 7, preferably 3 to 7.

[0190] To determine that the achieved effect is specific to the use of glycine, the same tests were carried out using an equimolar amount of the buffers (acetic acid, trisodium phosphate, dipotassium hydrogen phosphate) disclosed in cited Patent Document 4 instead of glycine in the formulations of Examples 3 - 5. The same tests were also carried out without using a buffer and glycine as a control. Table 9 shows the results and the results of Examples 3 - 5.

[0191] [Table 9]

[0192]

[0193] *1: Potassium hydroxide or citric acid

[0194] Note: Evaluation was carried out based on color change, foaming, cracking, and gaps or peeling (○ or ×).

[0195] As shown in the results, unlike glycine, acetic acid, trisodium phosphate, and dipotassium hydrogen phosphate do not have the effect of restricting the reduction in durability of the synthetic binder caused by the oxidizing agent. This indicates that the effect of restricting the reduction in durability of the binder caused by the oxidizing agents (peracetic acid and hydrogen peroxide) is unique to the combined use of glycine.

[0196] Experimental example 3: Evaluation of microbicidal effect on different microorganisms (No. 1)

[0197] The microbicidal effect of the microbicidal composition according to the present invention was evaluated by in vitro testing based on European standards using the following as microorganisms: general bacteria (Enterococcus faecalis ATCC 6057), acid-fast bacteria (Mycobacterium terrae ATCC 15755), spores (Bacillus subtilis ATCC 19659), and viruses (poliovirus type 1 Sabin strain (LS-c, 2ab strain) / host cell: African green monkey kidney cell JCRB 9013).

[0198] (1) Preparation of the test composition

[0199] The components listed in Table 10 were dissolved in synthetic hard water to obtain the concentrations and pH indicated in Table 10, thereby preparing the test compositions (Examples 7-1 to 7-3).

[0200] (2) Preparation of the microbial solution

[0201] (a) General bacteria

[0202] A glycerol stock solution of Enterococcus faecalis ATCC 6057 was inoculated in tryptic soy agar medium (hereinafter "TSA medium") and cultured at 37°C. After culturing, a diluent (aqueous solution containing 0.85% NaCl and 0.1% tryptone peptone, hereinafter "diluent 1") was added, and the medium was scraped off. The obtained microbial solution was placed in a 50 mL centrifuge tube, and 5 g of sterile glass beads were added, followed by stirring for 1 minute. After stirring, only the microbial solution was collected in another centrifuge tube. After centrifugation, the supernatant was removed, and the microbial solution was resuspended with the diluent.

[0203] (b) Acid-fast bacilli

[0204] A glycerol stock solution of Mycobacterium terrae ATCC 15755 was inoculated in a medium (Mycobacterium 7H11 agar + 10% OADC enrichment medium, hereinafter "7H11 medium") and cultured at 37°C. After culturing, the bacteria were scraped off and collected in a 50 mL centrifuge tube containing sterile glass beads. Distilled water was added to the tube, and the mixture was stirred and diluted accordingly. The diluted mixture was allowed to stand, and then the microbial solution in the middle layer was collected.

[0205] (c) Spores

[0206] Inoculate the glycerol stock solution of Bacillus subtilis ATCC 19659 into NB medium (Nutrient Broth No. 2), culture it at 37 °C, subculture it onto a spore-forming medium plate, and then culture it at 37 °C. After culturing, pour in sterile water to scrape off the bacteria, then place the scraped bacteria into a 50 mL centrifuge tube containing sterile glass beads and stir, and then filter through sterile gauze. After centrifugation, perform the operation of rinsing the filtrate with sterile water three times and centrifuging the filtrate, and then resuspend it with sterile water. Heat the obtained product at 80 °C for 15 minutes to prepare a microbial solution.

[0207] (d) Virus

[0208] Dilute the cryopreservation solution of Sabin strain of poliovirus type 1 and inoculate it into a cell culture plate. Add MEM medium containing FBS, culture it at 37 °C in 5% CO2, and then scrape off the cells to collect the culture broth. Subject the collected culture broth to three freeze-thaw cycles at -80 °C, and centrifuge the obtained culture broth to collect the supernatant to prepare a microbial solution.

[0209] (3) Evaluation test for microbicidal effect (a) General bacteria: EN 13727: 2012 / Dirty condition

[0210] (i) Mix the test composition, microbial solution, and interfering substances under dirty conditions (3% BSA + 3% red blood cells: the same below) pre-kept at 35 °C at a ratio of 8:1:1, and let it act at 35 °C.

[0211] (ii) After acting for 5 minutes, add a neutralizing agent (0.1% sodium thiosulfate, catalase) to inactivate the mixture solution.

[0212] (iii) Apply the inactivated mixture solution to the surface of TSA medium and culture it at 37 °C.

[0213] (iv) After culturing for one day, count the number of microorganisms.

[0214] (v) According to the requirements of EN 13727: 2012, a logarithmic reduction value of the microbial count before and after the test of 6 Log 10 or higher is judged as "○: having an effective microbicidal effect", and other cases are judged as "×: having no effective microbicidal effect".

[0215] (b) Acid-fast bacteria: EN 14348: 2005 / Dirty condition

[0216] (i) Mix the test composition, microbial solution, and interfering substance, which have been pre - maintained at 35°C, at a ratio of 8:1:1 and allow them to act at 35°C.

[0217] (ii) After acting for 5 minutes or 20 minutes, add a neutralizing agent (0.1% sodium thiosulfate, catalase) to inactivate the mixture solution.

[0218] (iii) Apply the inactivated mixture solution to the surface of 7H11 medium and incubate at 37°C.

[0219] (iv) After culturing for three weeks, count the number of bacteria.

[0220] (v) According to the requirements of EN 14348:2005, a logarithmic reduction value of the microbial count before and after the test of 4 Log 10 or higher is judged as "○: having an effective microbicidal effect", and other cases are judged as "×: having no effective microbicidal effect".

[0221] (c) Spores: EN 17126:2018 / Turbid conditions or clean conditions

[0222] (i) Mix the test composition, microbial solution, and interfering substance under turbid conditions or dry conditions, which have been pre - maintained at 35°C, at a ratio of 8:1:1 and allow them to act at 35°C.

[0223] (ii) After acting for 5 minutes (turbid conditions) or 20 minutes (clean conditions), add a neutralizing agent (0.1% sodium thiosulfate, catalase) to inactivate the mixture solution.

[0224] (iii) Apply the inactivated mixture solution to the surface of TSA medium and incubate at 37°C.

[0225] (iv) After culturing for one day, count the number of spores.

[0226] (v) According to the requirements of EN 17126:2018, a logarithmic reduction value of the microbial count before and after the test of 4 Log 10 or higher is judged as "○: having an effective microbicidal effect", and other cases are judged as "×: having no effective microbicidal effect".

[0227] (d) Viruses: EN 14476:2013 / Turbid conditions

[0228] (i) Pre - maintain the test composition and interfering substance at 35°C. Store the virus solution and neutralizing agent (MEM + 0.5% sodium thiosulfate, catalase containing 10% FBS) in ice.

[0229] (ii) Mix the test composition, the virus solution, and the interfering substance at a ratio of 8:1:1 and allow them to act at 35°C.

[0230] (iii) After acting for 5 minutes, add a neutralizing agent to inactivate the mixture solution.

[0231] (iv) Gradually dilute the stock solution (MEM containing 2% FBS) 10-fold to prepare diluents. Disperse each diluent into 8 wells in a 96-well microtiter plate (MEM medium containing FBS) in which host cells (African green monkey kidney cells JCRB9013) have been pre-cultured, and culture the cells at 37°C in the presence of 5% CO2 for 1 hour.

[0232] (v) After one hour, remove the medium, pour fresh medium into each well, and then culture at 37°C in the presence of 5% CO2.

[0233] (vi) After four days, calculate the virus infectivity (Log 10 TCID 50 ) according to the Behrens-Karber method.

[0234] (vii) According to the requirements of EN 14476:2013, a log reduction value of virus infectivity of 4 Log 10 or higher before and after the test is judged as "○: having an effective microbicidal effect", and other cases are judged as "×: having no effective microbicidal effect".

[0235] (4) Evaluation results of the microbicidal effect

[0236] Table 10 also shows the results.

[0237] [Table 10]

[0238] Concentration (mass%) in the test composition (aqueous solution)

[0239]

[0240] In the table, "-" indicates that the evaluation was not performed.

[0241] *1: Chelating agent 1) Sterilization conditions: 35°C, acting for 5 minutes

[0242] *2: Stabilizer 2) Sterilization conditions: 35°C, acting for 20 minutes

[0243] *3: Potassium hydroxide or citric acid

[0244] As shown in Table 10, it was determined that the antimicrobial composition according to the present invention used as a test composition has an effective antimicrobial effect against a wide range of microorganisms such as general bacteria, acid-fast bacilli, spores, and viruses. Among them, acid-fast bacilli, especially spores, are microorganisms highly resistant to disinfectants. However, since it was determined that the antimicrobial composition according to the present invention has an effective antimicrobial effect against these microorganisms even at low concentrations, it is considered that the antimicrobial composition is a useful antimicrobial composition having an effective antimicrobial effect against a wide range of microorganisms at low concentrations.

[0245] Experimental example 4: Evaluation of microbicidal effect on different microorganisms (No. 2)

[0246] By the test method specified in EN 17126:2018 (cleaning conditions), using the spores (Bacillus subtilis) used in Experimental Example 3 as the microorganism, antimicrobial treatment was carried out at 20 °C for 5 minutes, and the antimicrobial effect of the antimicrobial composition according to the present invention was evaluated in the same manner as in Experimental Example 3.

[0247] Table 11 shows the formulation of the test composition (Example 8-1) and its antimicrobial effect.

[0248] [Table 11]

[0249] Concentration (mass %) in the test composition (aqueous solution)

[0250]

[0251] *1: Potassium hydroxide or citric acid

[0252] As shown in Table 11, it was determined that the antimicrobial composition according to the present invention used as a test composition has an effective antimicrobial effect against spores with high physicochemical resistance during the treatment at room temperature of 20 °C.

[0253] Experimental Example 5: Antimicrobial effect under detergent contamination conditions

[0254] Usually, highly hazardous instruments, moderately hazardous instruments, and low-hazard instruments are washed with detergent and rinsed with water before antimicrobial treatment (disinfection treatment). However, if these operations are carried out inside the device or if rinsing is not carried out sufficiently after washing, the detergent may be introduced into the antimicrobial treatment process.

[0255] Therefore, assuming detergent contamination, the influence of detergent contamination on the antimicrobial effect of the antimicrobial composition was evaluated.

[0256] (1) Test method

[0257] (a) Evaluation test 1

[0258] Detergent was added to the test composition adjusted to pH 4 (Examples 9-1 to 9-3, Comparative Examples 9-1 to 9-3) to obtain a final concentration of 0.01%, and the test composition contaminated with detergent was maintained at 35°C. The detergent concentration (0.01%) was determined based on the following assumption: 2% contamination of the entire washing solution used in the washing step occurred during the microbicidal treatment. Table 12 shows the formulation of the test composition.

[0259] The peracetic acid concentration of the test composition contaminated with detergent was measured immediately after the addition of detergent (initial) and after warming for 30 minutes, and the remaining percentage of peracetic acid was calculated according to the following formula. A remaining percentage of 90% or higher was judged as "○ (good microbicidal effect under detergent contamination condition)", and a remaining percentage of less than 90% was judged as "× (poor)".

[0260] [Formula 1]

[0261] Remaining percentage (%) = (Peracetic acid concentration after warming for 30 minutes / Initial peracetic acid concentration) × 100

[0262] (b) Evaluation Test 2

[0263] Detergent was added to the test composition adjusted to pH 6 (Example 10-1 and Comparative Example 10-1) to obtain a final concentration of 0.05%, and the test composition contaminated with detergent was maintained at 35°C. The detergent concentration (0.05%) was determined based on the following assumption: 10% contamination of the entire washing solution used in the washing step occurred during the microbicidal treatment. Table 13 shows the formulation of the test composition.

[0264] As in Evaluation Test 1, the peracetic acid concentration of the test composition contaminated with detergent was measured immediately after the addition of detergent (initial) and after warming for 30 minutes. The remaining percentage of peracetic acid was calculated, and the microbicidal effect under detergent contamination condition was evaluated.

[0265] (2) Test Results

[0266] Tables 12 and 13 show the results of Evaluation Tests 1 and 2.

[0267] [Table 12]

[0268] Concentration (mass %) in the test composition (aqueous solution)

[0269]

[0270] *1pH regulator: KOH or citric acid

[0271] *2 Alkaline detergent A: Biotect DX, ultrasonic spraying, vendor: Sakura Seiki Co., Ltd.

[0272] *3 Alkaline detergent B: EndoQuick, vendor: Olympus Corporation

[0273] *4 Enzyme detergent A: Power Quick, multi-purpose enzyme cleaner, manufacturer: Saraya Co., Ltd.

[0274] [Table 13]

[0275] Concentration (mass %) in the test composition (aqueous solution)

[0276]

[0277] *1 pH regulator: KOH or citric acid

[0278] *2 Enzyme detergent A: Power Quick, multi-purpose enzyme cleaner,

[0279] manufacturer: Saraya Co., Ltd.

[0280] The results of Evaluation Test 1 (Table 12) show that peracetic acid is stable when the pH is acidic; and show that if the amount of the incorporated detergent is small, an effective amount of peracetic acid is maintained regardless of whether glycine is added, without an adverse effect on the microbicidal action. The results of Evaluation Test 2 (Table 13) show that peracetic acid becomes less stable when the pH value approaches neutral from acidic, and show that the incorporation of the detergent further reduces the remaining amount of peracetic acid (Comparative Example 10-1); however, even when the detergent is incorporated, an effective amount of peracetic acid is maintained in the test composition containing glycine, without an adverse effect on the microbicidal action (Example 10-2).

[0281] As described above, even when a detergent is incorporated into the microbicidal composition according to the present invention which further contains glycine in addition to peracetic acid and hydrogen peroxide, the composition exhibits high peracetic acid stability and effective microbicidal action in the pH range from acidic to neutral. Therefore, the microbicidal composition according to the present invention is suitably applicable to manual disinfection operations or, for example, disinfection operations using a disinfection device provided with a disinfection chamber and a disinfectant delivery system.

Claims

1. A microbicidal composition comprising: peracetic acid, hydrogen peroxide, and glycine, wherein the amount of peracetic acid is from 0.03% to 0.9% by mass, the amount of hydrogen peroxide is from 0.045% to 1.35% by mass, and the amount of glycine is 0.036% by mass or more; the ratio of hydrogen peroxide to 100 parts by mass of peracetic acid is from 100 parts by mass to 200 parts by mass, the ratio of glycine to 100 parts by mass of peracetic acid is from 80 parts by mass to 180 parts by mass, and the ratio of glycine to 100 parts by mass of hydrogen peroxide is from 50 parts by mass to 120 parts by mass; and the microbicidal composition is in the form of an aqueous solution having a pH of 2 to 7.

2. The microbicidal composition according to claim 1, wherein the pH of the microbicidal composition is 3 to 7.

3. The microbicidal composition according to claim 1 or 2, further comprising at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

4. The microbicidal composition according to any one of claims 1 to 2, which is a disinfectant and / or microbicide for a test object containing an adhesive, wherein the test object is a device or apparatus in the medical or food field that requires disinfection or microbicidal treatment.

5. The microbicidal composition according to claim 3, which is a disinfectant and / or microbicide for a test object containing an adhesive, wherein the test object is a device or apparatus in the medical or food field that requires disinfection or microbicidal treatment.

6. A combined preparation comprising: (A) a preparation containing peracetic acid and hydrogen peroxide, and (B) a preparation containing glycine, wherein the preparations (A) and (B) are mixed with an aqueous solvent before use to prepare an aqueous solution, the aqueous solution containing 0.03% to 0.9% by mass of peracetic acid, 0.045% to 1.35% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, wherein the ratio of hydrogen peroxide to 100 parts by mass of peracetic acid is from 100 parts by mass to 200 parts by mass, the ratio of glycine to 100 parts by mass of peracetic acid is from 80 parts by mass to 180 parts by mass, and the ratio of glycine to 100 parts by mass of hydrogen peroxide is from 50 parts by mass to 120 parts by mass, and the pH of the aqueous solution is 2 to 7.

7. The combined preparation according to claim 6, wherein the preparation (B) further comprises at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffering agents.

8. A method for preparing the microbicidal composition according to claim 1, comprising mixing a preparation (A) containing peracetic acid and hydrogen peroxide and a preparation (B) containing glycine with an aqueous solvent to prepare an aqueous solution, wherein the aqueous solution contains 0.03% to 0.9% by mass of peracetic acid, 0.045% to 1.35% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, wherein the ratio of the hydrogen peroxide to every 100 parts by mass of the peracetic acid is 100 parts by mass to 200 parts by mass, the ratio of the glycine to every 100 parts by mass of the peracetic acid is 80 parts by mass to 180 parts by mass, and the ratio of the glycine to every 100 parts by mass of the hydrogen peroxide is 50 parts by mass to 120 parts by mass, and the pH of the aqueous solution is 2 to 7.

9. The method according to claim 8, wherein the formulation (B) further comprises at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffers.

10. A disinfection device, comprising: a disinfection chamber, and a disinfectant delivery system, wherein the disinfectant delivery system comprises (A) a formulation containing peracetic acid and hydrogen peroxide filled in a container and (B) a formulation containing glycine filled in a container; and the disinfectant delivery system is configured to separately supply the formulation (A) and the formulation (B) to the disinfection chamber, and the supplied formulation (A) and the supplied formulation (B) in the disinfection chamber are mixed with separately supplied aqueous solvent to prepare an aqueous solution, the aqueous solution contains 0.03% to 0.9% by mass of peracetic acid, 0.045% to 1.35% by mass of hydrogen peroxide, and 0.036% by mass or more of glycine, wherein the ratio of the hydrogen peroxide to every 100 parts by mass of the peracetic acid is 100 parts by mass to 200 parts by mass, the ratio of the glycine to every 100 parts by mass of the peracetic acid is 80 parts by mass to 180 parts by mass, and the ratio of the glycine to every 100 parts by mass of the hydrogen peroxide is 50 parts by mass to 120 parts by mass, and the pH of the aqueous solution is 2 to 7.

11. The disinfection device according to claim 10, wherein the formulation (B) further comprises at least one auxiliary component selected from hydrogen phosphates, chelating agents, and pH buffers.

12. The disinfection device according to claim 10 or 11, which is used for disinfection or microbicidal treatment of a test object containing an adhesive, wherein the test object is an instrument or device in the medical or food field that requires disinfection or microbicidal treatment.

13. A method for disinfecting a test object, comprising treating the test object with the microbicidal composition according to any one of claims 1 to 5.

14. The method according to claim 13, comprising mixing (A) a formulation containing peracetic acid and hydrogen peroxide and (B) a formulation containing glycine with an aqueous solvent before treating the test object to prepare the microbicidal composition according to any one of claims 1 to 5.

15. The method according to claim 13 or 14, wherein the test object contains an adhesive.

16. The method according to claim 15, which is a method for disinfecting the test object while limiting a reduction in the durability of the adhesive.

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