JP2007082900A - Disinfection or sterilization method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a disinfection and sterilization method suited to disinfect or sterilize an endoscope and the like and capable of exerting a sufficient sterilizing effect on spores with strong resistance in a short period of time. <P>SOLUTION: This disinfection or sterilization method for medical equipment such as the endoscope is characterized by combining a process using bactericide, for example, carboperoxoic acid with ultraviolet irradiation using, for example, ultraviolet light with wavelength of 300 nm or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a disinfection or sterilization method. More specifically, the present invention relates to a treatment method suitable for disinfection or sterilization of medical equipment such as an endoscope.

  Since medical devices such as endoscopes cannot be disposable and come into direct contact with the patient, it is necessary to perform safer disinfection or sterilization and use them for the next medical treatment and the like. However, a small scale hospital often uses a single device in a short time. Therefore, as a composition used for disinfection or sterilization of a medical device, a composition having an action of killing a wide range of microorganisms and capable of disinfecting or sterilizing a medical device in a short time is desired. From the viewpoint of safety, it is desirable that the amount of the compound and the like in the composition is as small as possible.

  Conventionally, as cleaning compositions and disinfecting or sterilizing compositions for medical devices such as endoscopes, compositions containing aldehydes such as glutaraldehyde and o-phthalaldehyde as active ingredients are known. It is marketed as a disinfectant. However, it is known that disinfectants containing these aldehyde compounds as main components have weak mutagenicity and toxicity, and weak antibacterial activity against highly resistant bacteria such as spores.

  Bacterial cells generally die when the surrounding environment is unfavorable for the growth of the bacteria. However, certain bacteria are known to survive by creating durable organs called spores when environmental conditions such as dryness and high temperature deteriorate. As bacteria that form these spores, relatively large Gram-positive bacilli such as bacteria belonging to the genus Bacillus which is an aerobic bacterium and bacteria belonging to the genus Clostridium which is an anaerobic bacterium are known. Even if the spore-forming bacteria are balanced in nutrients and divide and proliferate (nutritive type), they often do not form spores. When the balance is lost, spores are formed in the cells.

  Spores are known to be strongly resistant to physical or chemical stimuli. This is presumed to be due to the thick protoplasm and nuclei being covered with a thick shell in the spores. 60-70% of the water in the spore is in the form of bound water, dehydrated without free water. In addition, spore is characterized in that 5-12% of its weight is occupied by dipicolinic acid, and dipicolinic acid retains a large amount of Ca chelated.

  Since spores are in a dormant state where metabolism is not performed and biological activities such as bacterial growth are hardly observed, they are sometimes called bacterial spores or endospores. Since spores are known to have regenerative ability even after dormancy for several years to several decades, the sterilization standard is to completely kill spores in fields such as medicine and the food industry. It has become one. In particular, medical instruments and equipment used in hospitals and nursing homes need to be sufficiently sterilized and washed from the viewpoint of preventing internal infection.

  Various disinfectants or disinfectants for performing such disinfection and washing treatment are known, and glutaraldehyde and peracetic acid are widely used. As a sterilization cleaning process using glutaraldehyde or peracetic acid, for example, in the sterilization cleaning of an endoscope, a primary disinfection step using a quaternary ammonium salt-based disinfectant, alcohol, acidic water, or an amphoteric surfactant, After a washing process using an enzyme preparation, a neutral detergent or the like, sterilization with glutaraldehyde or peracetic acid is performed, and autoclave sterilization or dry heat sterilization is performed as necessary.

On the other hand, for UV disinfection, US Pat. No. 4,289,728 states that a spore suspension in 0.25% H ₂ O ₂ is used to reduce the number of spores in 0.25% H ₂ O ₂ by 4 + log cycles. It is described that it is necessary to heat at 85 ° C. for 60 seconds after irradiating with UV rays for 30 seconds. However, more time is required to achieve a 6 + log cycle reduction that results in a sterilization level that guarantees that the microbe's presence probability is less than 1 / 1,000,000, and multiple processing steps including ultraviolet irradiation and heat treatment. Therefore, it is a problem that it is complicated to implement in an actual clinical site.

  Japanese Examined Patent Publication No.7-112489 discloses a method for sterilizing an article in which microorganisms are present. The article is irradiated with ultraviolet rays for 5 to 50 seconds, and a total of 15 to 25% by weight is exceeded. A method of treating with a solution containing hydrogen oxide and 0.01 to 1 wt% peracetic acid is disclosed. However, the disinfectant used in the method described in this publication is limited to peracetic acid, and disinfectants other than peracetic acid, particularly peroxycarboxylic acids other than peracetic acid, are not specifically disclosed in the above publications. . Moreover, although the food container is disclosed as an article to be sterilized in the above publication, a medical device, in particular, an endoscope is not disclosed as the article.

Furthermore, in the methods described in the above two publications, UV irradiation is performed in the presence of a disinfectant, but as a pre- or post-process of disinfection treatment with a disinfectant, the disinfectant is not included. The process of performing UV irradiation is not disclosed in any of the above publications. As described above, in addition to ultraviolet irradiation in a state where a peroxycarboxylic acid other than peracetic acid is used, and the sterilization target is a medical device, particularly an endoscope, and a disinfectant is present, The above publication does not describe a method of performing ultraviolet irradiation in a state in which no disinfectant is contained as a post-process.
U.S. Pat.No. 4,289,728 Japanese Patent Publication No.7-112489

  An object of the present invention is to provide a disinfection and sterilization method capable of exerting a sufficient bactericidal effect in a short time for a highly resistant spore. Another object of the present invention is to provide a disinfection or sterilization method having the above-described characteristics, which is suitable for disinfection or sterilization of medical equipment such as an endoscope.

  The present inventors have intensively studied to solve the above problems, and by combining a sterilization treatment using a bactericide with a sterilization treatment by ultraviolet irradiation, sufficient sterilization can be carried out in a short time even for highly resistant spores. It was found that the effect can be achieved. The present invention has been completed based on these findings.

That is, the present invention provides a disinfection or sterilization method that includes a combination of a disinfectant treatment and ultraviolet irradiation. The ultraviolet irradiation may be carried out in a solution containing a bactericidal agent or in the absence of a bactericidal agent, but preferably in the absence of a bactericidal agent before and / or after the treatment with a bactericidal agent. It is preferable to carry out.
According to a preferred embodiment of the present invention, there are provided the above-described disinfection or sterilization method for performing ultraviolet irradiation using ultraviolet light having a wavelength of 300 nm or less, and the above-mentioned method for performing ultraviolet irradiation for a period of 5 seconds to 10 minutes. . In addition, the above method in which the sterilization target is a medical device and the above method in which the sterilization target is an endoscope are also provided as preferable aspects.

（式中、Ｒ¹は置換若しくは無置換のＣ１−Ｃ１０のアルキル基（ただし、置換基としてヒドロキシ基を有する置換基は除く）、又は置換若しくは無置換のＣ６−Ｃ１０のアリール基を示し、Ｌは置換若しくは無置換のＣ２−Ｃ１２の２価の連結基を示し、Ｒ¹とＬは結合して環を形成してもよい）で表されるペルオキシカルボン酸が好ましい。Ｌとしては、−ＣＨ(Ｒ¹¹)−Ｌ¹²（Ｒ¹¹は水素原子又はＣ１〜Ｃ４の置換若しくは無置換のアルキル基を示し、Ｌ¹²は置換若しくは無置換のＣ１−Ｃ１１の２価の連結基を示す）が好ましい例として挙げられる。Ｌ¹²としては置換又は無置換のＣ１−Ｃ４の２価の連結基が好ましく、置換又は無置換のメチレン基がより好ましく、メチレン基又はメチル基置換メチレン基（−ＣＨ（ＣＨ₃）−）がさらに好ましく、メチレン基が最も好ましい。Ｒ¹が置換又は無置換のＣ１−Ｃ３のアルキル基であることが好ましく、Ｒ¹がメチル基又はエチル基であり、かつＲ¹¹が水素原子であることがさらに好ましい。 Moreover, according to another preferable aspect, said method whose disinfectant is peroxycarboxylic acid is provided. As peroxycarboxylic acid, peracetic acid or general formula (I):

(Wherein R ¹ represents a substituted or unsubstituted C1-C10 alkyl group (excluding a substituent having a hydroxy group as a substituent) or a substituted or unsubstituted C6-C10 aryl group; Represents a substituted or unsubstituted C2-C12 divalent linking group, and R ¹ and L may combine to form a ring), and a peroxycarboxylic acid represented by L represents —CH (R ¹¹ ) —L ¹² (R ¹¹ represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group, and L ¹² represents a substituted or unsubstituted C1-C11 divalent linkage. A group) is a preferred example. L ¹² is preferably a substituted or unsubstituted C1-C4 divalent linking group, more preferably a substituted or unsubstituted methylene group, and a methylene group or a methyl group-substituted methylene group (—CH (CH ₃ ) —). More preferred is a methylene group. R ¹ is preferably a substituted or unsubstituted C1-C3 alkyl group, more preferably R ¹ is a methyl group or an ethyl group, and R ¹¹ is more preferably a hydrogen atom.

  The disinfection or sterilization method provided by the present invention can achieve complete disinfection or sterilization in a very short time even for highly resistant spores and the like.

  In this specification, disinfection means removing, killing, or inactivating almost all microorganisms that are problematic in preventing infection, and sterilization means killing, inactivating, or removing all microorganisms. means. It is usually called “sterilization” by guaranteeing that the existence probability of microorganisms is 1 / 1,000,000 or less. Although the concept of disinfection and sterilization may be used interchangeably in some cases, the term “disinfection or sterilization” in this specification includes such overlapping concepts. The term “bactericidal agent” used in the present specification means a drug having a bactericidal or antibacterial action against microorganisms, but is used for the purpose of cleaning or the like in addition to a drug used for the purpose of disinfection or sterilization. Includes drugs. The term bactericides should be interpreted in the broadest sense and the term bactericides should not be interpreted in any way restrictive.

  The disinfectant used in the disinfecting or sterilizing method of the present invention exerts a disinfecting action against various microorganisms mainly by a chemical action, and high, medium and low level disinfectants classified by Spalding. Any of these may be used. According to Spaulding, low-level (low) fungicides that can kill mainly breeding general bacteria, medium-level (moderate) fungicides that can kill even resistant tuberculosis bacteria, most Those that can kill even highly resistant bacterial spores are classified as high-level (high) fungicides. In general, examples of the low-level bactericides include quaternary ammonium salts, chlorhexidine, and amphoteric surfactants, and examples of the medium-level bactericides include alcohol-type bactericides, iodine-type bactericides, and phenol-type bactericides. Or a hypochlorous acid-based germicide, and the high-level germicide can include an aldehyde-based germicide, chlorine dioxide, or peracetic acid.

  The disinfection or sterilization method of the present invention can be used for disinfection or sterilization of various objects. Many objects are liquid or solid. Typical examples of objects in liquid form include microbially contaminated aqueous materials such as recycled process water or aqueous effluent prior to disposal. Such process water and effluents occur in many industries and can be contaminated with bacteria, algae, or yeast, and rarely contaminated with viruses. Contaminated process water is inevitably generated by the treatment of plant and animal material, such as paper and pulp industry, food processing (eg sugar refining industry, brewing, wine making, and alcohol distillation industry), spill from straw processing Wastewater from wastewater, wastewater from sewage treatment plants (eg, wastewater from partially treated or simply filtered sewage, and drainage from pipelines extending to the sea), slaughterhouses, animal fat refining operations, and livestock breeding and so on. Examples of other liquid objects include irrigation water in the horticultural industry, aqueous fertilizer and circulating water in hydroponics, and aquaculture water in the fishery industry. Still another important source of polluted water can include industrial cooling water, such as cooling water from air conditioners installed in large buildings (eg, hotels, offices, and hospitals). Can be mentioned. The disinfection or sterilization method of the present invention can also be used to disinfect or sterilize non-aqueous liquid materials such as cutting oil.

  The disinfection or sterilization method of the present invention can also be used on solids. For example, it can be used for disinfection or sterilization of hard surfaces, or for disinfection or sterilization of contaminated articles intended for reuse in food processing, animal breeding, horticulture, catering, home or hospital environments. As a hard surface, the surface which consists of members, such as a metal, wood, ceramics, glass, a fiber, or a plastic, can be mentioned, for example. Articles having a hard surface include, for example, food packages, contact lenses, worktables, walls, floors, sanitary ware, pools, plants, clothing, or sheets or covers, or devices, containers, tools, machines, plants, or Piping etc. can be mentioned. Contaminated articles intended for reuse in a hospital environment can include various medical devices such as dialysis machines, endoscopes, or implantable materials. The disinfection or sterilization method of the present invention can also be used to disinfect or sterilize hygroscopic materials such as contaminated linen or especially dirty baby diapers (such as those manufactured on terry toweling).

  The disinfection or sterilization method of the present invention can be used for disinfection or sterilization of harvested plants or plant products such as seeds, corms, tubers, fruits, or vegetables. The disinfecting or sterilizing method of the present invention can be used for growing plants, especially plants in the growth stage prior to harvest, such as vegetable crops for cereals, leafy vegetables, or salads, or root vegetables, legumes, berries, citrus fruits, or nuts. It can also be used for disinfection or sterilization. Although the object to which the disinfection or sterilization method of the present invention can be applied has been specifically described, the application target of the disinfection or sterilization method of the present invention is not limited to the above-described specific examples, and the disinfection or sterilization is performed. It can be applied to any object intended.

By using the disinfection or sterilization method of the present invention, spores having particularly high resistance to commonly used fungicides, such as Bacillus subtilis, can be killed in a short time. The use of the disinfection or sterilization method of the present invention is not particularly limited, and can be applied to the various objects exemplified above, but is suitable for disinfection or sterilization of medical devices on the premise of repeated use. It can be used, and can be particularly suitably used for sterilization or sterilization of dental equipment and medical equipment that are required to achieve complete disinfection or sterilization in a short time.
Hereinafter, the disinfection or sterilization method of the present invention may be specifically referred to only when applied to a medical device such as an endoscope, but such description should be understood as an explanation of a preferred embodiment of the present invention. And should not be construed as limiting in any way.

  The type of ultraviolet rays used in the method of the present invention is not particularly limited. For example, the wavelength is preferably 300 nm or less, more preferably 200 to 280 nm, and particularly preferably about 254 nm. In general, the greater the irradiation energy, the greater the sterilization effect on the spores. Moreover, the time required for disinfection or sterilization can be shortened by ultraviolet irradiation with large energy. When disinfecting or sterilizing medical devices such as endoscopes, generally adjust the amount of irradiation energy appropriately according to the shape of the medical device, etc., so that sufficient ultraviolet irradiation is performed on the surface of the device. There is a need. Further, the irradiation energy can be appropriately adjusted according to the irradiation condition (distance between the lamp and the object), the type of microorganism, and the like.

  In performing the disinfection or sterilization method of the present invention, for example, a method of sterilizing a medical device or the like by bringing them into contact with an aqueous solution containing a bactericide is preferable. Although the kind of aqueous solvent which forms an aqueous solution is not specifically limited, The mixture of water and the aqueous organic solvent (ethanol, methanol, acetone, etc.) which mix with water, etc. other than water are mentioned. In the immersion, the aqueous solution may be stirred, the medical device may be shaken, or an automatic washing machine may be used. Further, it may include a step of washing medical devices and the like before and / or after the immersion, and include a step of wiping the medical devices and the like with sterilized gauze after the immersion or drying with a drier etc. May be. Although the immersion time of the target object in the aqueous solution containing a disinfectant is not particularly limited, for example, it is preferably in the range of 15 seconds to 30 minutes, and more preferably in the range of 30 seconds to 10 minutes.

  Although the method of ultraviolet irradiation is not particularly limited, for example, irradiation may be performed by incorporating an ultraviolet lamp in an automatic washing machine, and the object immersed in the aqueous solution is irradiated with ultraviolet light in an aqueous solution. You may do it. It is also possible to take out the object from the washing machine and irradiate it with ultraviolet rays in the atmosphere. In this case, the ultraviolet irradiation may be performed in a state where the surface of the object is wet or in a dry state.

  The method of the present invention is characterized by combining the treatment with the bactericidal agent and the ultraviolet irradiation, but the order of the combination of the treatment step with the bactericide and the ultraviolet irradiation step, the number of times of combination, and the like are not particularly limited. Can be adopted any number of times, and each process can be applied simultaneously or at different times. For example, the ultraviolet irradiation and the treatment with the bactericide may be performed simultaneously, and the ultraviolet irradiation may be performed as a separate process as a pre-process and / or a post-process of the bactericide. When UV irradiation is performed in a separate process as a pre-process and / or a post-process of treatment with a bactericidal agent, UV irradiation may be performed in the absence or presence of a bactericidal agent. It is also preferable to perform ultraviolet irradiation in the absence. For example, ultraviolet irradiation may be performed in a cleaning solution containing a surfactant or the like in the previous step, and in rinse water in the subsequent step. Further, after the treatment with the bactericidal agent, the ultraviolet irradiation may be performed, and then the treatment with the bactericidal agent may be repeated. You may go.

  Although the kind of disinfectant used for the disinfection or sterilization method of this invention is not specifically limited, It is preferable to use peroxycarboxylic acid as a disinfectant. Hereinafter, the case where the bactericidal agent is peroxycarboxylic acid will be referred to as a preferred embodiment of the present invention, but the bactericidal agent used in the method of the present invention is not limited to peroxycarboxylic acid.

（式中、Ｒ¹は置換若しくは無置換のＣ１−Ｃ１０のアルキル基（ただし、置換基としてヒドロキシ基を有する置換基は除く）、又は置換若しくは無置換のＣ６−Ｃ１０のアリール基を示し、Ｌは置換若しくは無置換のＣ２−Ｃ１２の２価の連結基を示し、Ｒ¹とＬは結合して環を形成してもよい）で表されるペルオキシカルボン酸が好ましい。 The peroxycarboxylic acid is preferably peracetic acid or the following general formula (I):

(Wherein R ¹ represents a substituted or unsubstituted C1-C10 alkyl group (excluding a substituent having a hydroxy group as a substituent) or a substituted or unsubstituted C6-C10 aryl group; Represents a substituted or unsubstituted C2-C12 divalent linking group, and R ¹ and L may combine to form a ring), and a peroxycarboxylic acid represented by

In the general formula (I), examples of the unsubstituted C1-C10 alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include a butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and 2-ethylhexyl group. The C1-C10 alkyl group represented by R ¹ may have a substituent, but a substituent having a hydroxy group as a substituent (such as a hydroxyl group, a carboxy group, a hydroperoxy group, and a hydroperoxycarbonyl group) except. Examples of the substituent in the C1-C10 alkyl group represented by R ¹ include a halogen atom, an alkoxy group, and an alkylsulfonyl group. Examples of the C6-C10 unsubstituted aryl group represented by R ¹ include a phenyl group. The C6-C10 unsubstituted aryl group represented by R ¹ may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a sulfonyl group, a hydroxyl group, and a carboxyl group.

R ¹ is preferably a C1-C4 substituted or unsubstituted alkyl group, more preferably a C1-C4 unsubstituted alkyl group. Examples of the C1-C4 alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. R ¹ is most preferably a methyl group or an ethyl group, but is not limited thereto.

In general formula (I), L represents a substituted or unsubstituted divalent linking group having 2 to 12 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy-substituted alkyl group, and a carboxyl group. Further, the linking group may contain a molecule other than carbon such as an oxygen atom and a nitrogen atom. L represents —CH (R ¹¹ ) —L ¹² (R ¹¹ represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group, and L ¹² represents a substituted or unsubstituted C1-C11 divalent linkage. A group) is a preferred example. L ¹² is preferably a substituted or unsubstituted C1-C4 divalent linking group, more preferably a substituted or unsubstituted methylene group, and a methylene group or a methyl group-substituted methylene group (—CH (CH ₃ ) —). More preferred is a methylene group. R ¹ is preferably a substituted or unsubstituted C1-C3 alkyl group, more preferably R ¹ is a methyl group or an ethyl group, and R ¹¹ is more preferably a hydrogen atom.

（式中、Ｒ¹¹は水素原子又はＣ１〜Ｃ４の置換若しくは無置換のアルキル基を示し、Ｌ¹²は置換又は無置換のＣ１−Ｃ１１の２価の連結基を示す）で表されるペルオキシカルボン酸が好ましい。 More specifically, among the peroxycarboxylic acids represented by the general formula (I), the following general formula (I-1):

(Wherein R ¹¹ represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group, and L ¹² represents a substituted or unsubstituted C1-C11 divalent linking group). Acid is preferred.

In this case, L ¹² is preferably a substituted or unsubstituted C1-C4 divalent linking group, more preferably a substituted or unsubstituted methylene group, a methylene group or a methyl group-substituted methylene group (CH (CH ₃ )). Are more preferable, and a methylene group is most preferable. When the linking group represented by L ¹² has a substituent, examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, an alkoxy-substituted alkyl group, and a carboxyl group. Moreover, molecules other than carbon may be included in the linking group, and examples thereof include an oxygen atom and a nitrogen atom.

（式中、Ｒ²、Ｒ³、Ｒ⁴、及びＲ⁵は各々独立に水素、Ｃ１−Ｃ４アルキル基、Ｃ１−Ｃ４のアルコキシ基、又はＣ１−Ｃ４アルコキシ置換Ｃ１−Ｃ４アルキル基を示し、Ｌ²は置換若しくは無置換のＣ１−Ｃ９アルキレン基、又は置換若しくは無置換のＣ６−Ｃ９アリーレン基を示し、Ｌ¹は置換若しくは無置換のＣ１−Ｃ１０の２価の連結基を示す）で表されるペルオキシカルボン酸もまた好ましい。 Among the peroxycarboxylic acids represented by the general formula (I), the general formula (II) or (III):

(Wherein R ² , R ³ , R ⁴ , and R ⁵ each independently represent hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy-substituted C1-C4 alkyl group; ² represents a substituted or unsubstituted C1-C9 alkylene group, or a substituted or unsubstituted C6-C9 arylene group, and L ¹ represents a substituted or unsubstituted C1-C10 divalent linking group). Also preferred are peroxycarboxylic acids.

More preferably, as the peroxycarboxylic acid represented by the general formula (II) or (III), L ¹ is —CH (R ¹¹ ) —L ¹² (R ¹¹ is a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl). represents a group, L ¹² peroxycarboxylic acid is a divalent linking group of C1-C9 substituted or unsubstituted) ^{is; R 2, R 3, R} 4, and R ⁵ are each independently hydrogen, C1- A peroxycarboxylic acid that is a C4 alkyl group or a C1-C4 alkoxy-substituted C1-C4 alkyl group, and L ² is a C1-C2 unsubstituted alkylene group; R ² , R ³ , R ⁴ , and R ⁵ are Peroxycarboxylic acid which is hydrogen is mentioned.

（式中、Ｒ²、Ｒ³、Ｒ⁴、及びＲ⁵は各々独立に水素、Ｃ１−Ｃ４のアルキル基、Ｃ１−Ｃ４のアルコキシ基、又はＣ１−Ｃ４アルコキシ置換Ｃ１−Ｃ４アルキル基を示し、Ｌ²は置換若しくは無置換のＣ１〜Ｃ９のアルキレン基、又は置換若しくは無置換のＣ６〜Ｃ９のアリーレン基を示す）で表されるペルオキシカルボン酸もまた好ましい。 Further, among the peroxycarboxylic acids represented by the general formula (I), the general formula (IV) or (V):

(Wherein R ² , R ³ , R ⁴ , and R ⁵ each independently represent hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, or a C1-C4 alkoxy-substituted C1-C4 alkyl group, L ² is a substituted or unsubstituted alkylene group C1 to C9, or peroxycarboxylic acids represented by substituted or indicating the unsubstituted arylene group C6 to C9) are also preferred.

More preferably, as the peroxycarboxylic acid represented by the general formula (IV) or (V), R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, a C1-C4 alkyl group, or C1- A peroxycarboxylic acid which is a C4 alkoxy-substituted C1-C4 alkyl group and L ² is an unsubstituted C1-C3 alkylene group; a peroxycarboxylic acid in which R ² is hydrogen; R ² , R ³ , and R ⁴ are hydrogen A peroxycarboxylic acid in which R ⁵ is a methyl group; a peroxycarboxylic acid in which L ² is a methylene group; a peroxycarboxylic acid in which R ² , R ³ , R ⁴ , and R ⁵ are hydrogen; L ² A peroxycarboxylic acid in which R ⁴ is a C1-C4 alkoxy-substituted methyl group; and a peroxycarboxylic acid in which R ⁵ is a methyl group. .

  Peroxycarboxylic acid may have one or two asymmetric carbons depending on the type of substituent. Any optically pure optical isomer based on one or two asymmetric carbons, any mixture of the above optical isomers, racemic, two diastereoisomers based on two asymmetric carbons, Bactericides including any mixture of stereoisomers and the like can be preferably used. Moreover, although peroxycarboxylic acid may exist as a hydrate or a solvate, the bactericidal agent containing these substances can also be used preferably.

Specific examples of peroxycarboxylic acid are shown below, but are not limited to the following.

  The above peroxycarboxylic acid can be synthesized by known peroxycarboxylic acid synthesis methods described in Organic peroxides, vol. I, pp 313-474 (Daniel Swern, John Wiley & Sons, Inc., New York, 1970). It can be synthesized accordingly. Specifically, for example, it can be synthesized by a reaction between a corresponding carboxylic acid and hydrogen peroxide. In the reaction between the corresponding carboxylic acid and hydrogen peroxide, it is effective to use a strong acid as a catalyst for the reaction. As the strong acid, sulfuric acid or phosphoric acid can be used, but a strongly acidic ion exchange resin having a sulfonic acid group or a solid acid catalyst such as Nafion can also be used.

  As the corresponding carboxylic acid used in the synthesis of the peroxycarboxylic acid, a commercially available carboxylic acid can be used, but a carboxylic acid synthesized by a known method can also be used. For example, 3-alkoxypropionic acid can be obtained by reacting β-propiolactone with an alcohol as described in J. Am. Chem. Soc., 70, 1004 (1948), or by using J. Am. Chem. Soc. 69, 2967 (1947), J. Am. Chem. Soc., 77, 754 (1955), the hydrolysis of 3-alkoxypropionic acid ester obtained by the reaction of acrylic acid ester with alkoxide. It can be synthesized by decomposition. Carboxylic acids substituted with alkoxy at a position far from the carbonyl group from the 3-position are synthesized by reaction of β or δ-lactone with alcohol as described in J. Org. Chem., 59, 2253 (1994). Is possible.

  Peroxycarboxylic acid may be used alone or in combination of two or more. The concentration of peroxycarboxylic acid in the aqueous solution containing peroxycarboxylic acid is 0.1 mmol / l or more and 2000 mmol / l or less, preferably 1 mmol / l or more and 200 mmol / l or less, more preferably 40 mmol / l or more. What is necessary is just 120 mmol / l or less.

  The aqueous solution containing a peroxycarboxylic acid may contain a carboxylic acid corresponding to the peroxycarboxylic acid and / or hydrogen peroxide in addition to the above-mentioned peroxycarboxylic acid. In the present specification, the carboxylic acid corresponding to the peroxycarboxylic acid means a compound in which the peroxycarboxyl group of the peroxycarboxylic acid is a carboxyl group. In this case, the concentration of the carboxylic acid corresponding to the peroxycarboxylic acid in the aqueous composition is 0.1 mmol / l or more and 2000 mmol / l or less, preferably 1 mmol / l or more and 200 mmol / l or less, more preferably What is necessary is just 40 mmol / l or more and 200 mmol / l or less. The concentration of hydrogen peroxide is 3 mmol / l or more and 6000 mmol / l or less, preferably 10 mmol / l or more and 1000 mmol / l or less, more preferably 30 mmol / l or more and 600 mmol / l or less. I just need it. The aqueous composition containing peroxycarboxylic acid preferably has a peroxycarboxylic acid concentration of 1 mmol / l or more and 200 mmol / l or less, and a hydrogen peroxide concentration of 10 mmol / l or more and 1000 mmol / l or less. .

  An aqueous composition containing a carboxylic acid corresponding to the peroxycarboxylic acid and / or hydrogen peroxide together with the peroxycarboxylic acid is used so that, for example, each component such as the peroxycarboxylic acid has the above-mentioned concentration during use. May be prepared. The production of peroxycarboxylic acids from hydrogen peroxide and carboxylic acids has long been known. This reaction proceeds as an equilibrium reaction with carboxylic acid, hydrogen peroxide, peroxycarboxylic acid, and water, and a higher concentration of peroxycarboxylic acid is generated as the concentration of hydrogen peroxide or carboxylic acid is increased. For example, when 90% hydrogen peroxide is mixed with 1.5 times the molar amount of acetic acid, acetic acid is 45% by mass peracetic acid, 35% by mass acetic acid, 6% by mass hydrogen peroxide, and 14% by mass water. (Kirk-Othmer Encyclopedia of Chem. Tech. Inst, Suppl. P662 (1957)). Therefore, the aqueous composition containing peroxycarboxylic acid can be prepared by mixing an aqueous solution containing carboxylic acid corresponding to peroxycarboxylic acid and an aqueous solution containing hydrogen peroxide, which are prepared and provided separately. If necessary, an aqueous composition containing these mixtures can be used after diluting with water. In addition, peroxycarboxylic acid and the following additives may be provided in a dry form and dissolved in an aqueous solvent when used.

  The aqueous solution containing a bactericidal agent may further contain one or more additives in addition to the bactericidal agent. As described above, the aqueous solution containing a peroxycarboxylic acid may contain a carboxylic acid corresponding to the peroxycarboxylic acid and / or hydrogen peroxide, and in that case also contains one or more additives. You may go out. Examples of additives include, but are not limited to, corrosion inhibitors, solubilizers, pH adjusters, sequestering agents, stabilizers, surfactants, and anti-redeposition agents. .

  What is necessary is just to select the thing suitable for the material of disinfection or sterilization, for example, a medical device, as a corrosion inhibitor, and more specifically, 1,2,3-benzotriazole, lower alkyl benzotriazole, Hydroxybenzotriazole, lower alkylhydroxybenzotriazole, carboxybenzotriazole, lower alkylcarboxybenzotriazole, benzimidazole, lower alkylbenzimidazole, hydroxybenzimidazole, lower alkylhydroxybenzimidazole, carboxybenzimidazole, lower alkylcarboxybenzimidazole, mercaptobenzo Thiazole, lower alkyl mercaptobenzothiazole, hydroxymercaptobenzothiazole, lower alkylhydroxymercaptobenzothiazole, cap Boxymercaptobenzothiazole, lower alkyl carboxymercaptobenzothiazole, sodium gluconate, sodium benzoate, butyl benzoate, monoethanolamine, triethanolamine, morpholine, sorbitol, erythritol, sodium phosphate, sodium tripolyphosphate, tetrapyrophosphate tetra Examples include corrosion inhibitors in combination with one or more compounds selected from sodium, sodium molybdate, sodium nitrite, sodium bisulfite, sodium metabisulfite, chromate, and borate. However, it is not limited to these. In the present specification, the term “lower alkyl” means a straight or branched saturated hydrocarbon group having 1 to 6 carbon atoms, and the lower alkyl group includes one or two lower alkyl groups. You may have the above unsaturated bond.

  When using the disinfection or sterilization method of the present invention to treat equipment containing copper, brass, bronze, or multimetal systems, 1,2,3-benzotriazole and one or more lower alkyl benzoates Preferably used are corrosion inhibitors including triazole, hydroxybenzotriazole, lower alkylhydroxybenzotriazole, sodium molybdate, sodium nitrite, sodium bisulfite, sodium metabisulfite, chromate, borate, and mixtures thereof. It is done. A corrosion inhibitor containing 1,2,3-benzotriazole, sodium molybdate, and sodium nitrite is particularly preferably used. When the disinfection or sterilization method of the present invention is used to treat equipment containing carbon steel and stainless steel, for example, a corrosion inhibitor containing sodium benzoate, sodium nitrite, sodium molybdate and the like is preferable. Used. When the disinfection or sterilization method of the present invention is used for treating equipment containing carbon steel and / or stainless steel, for example, a corrosion inhibitor containing sodium nitrate and / or sodium molybdate is preferably used. When the corrosion inhibitor is added to an aqueous solution containing a disinfectant, the total amount of the corrosion inhibitor is not particularly limited, but is typically 0.1% to about 30% by mass with respect to the total mass of the aqueous solution. is there. The amount of 1,2,3-benzotriazole is preferably 0.1% to about 3.0% by weight, more preferably 0.5% to about 2.0% by weight.

  If the corrosion inhibitor is sparingly soluble in an aqueous solution containing a bactericide, the aqueous solution may further contain a solubilizing agent such as an alkylene glycol. As used herein, the term “alkylene glycol” refers to, for example, ethylene glycol, propylene glycol, dialkylene glycol (eg, diethylene glycol), trialkylene glycol (eg, triethylene glycol), or the corresponding mono- and dialkyl thereof. Means glycol such as ether. The alkyl ether is a lower alkyl ether having 1 to 6 carbon atoms (eg, methyl ether, ethyl ether, or propyl ether). Particularly preferably, when the aqueous solution contains propylene glycol as a solubilizer, it is preferable that propylene glycol is contained at a concentration of about 3 to 10 times that of the corrosion inhibitor. For example, it is preferable that propylene glycol is contained in the aqueous solution at a ratio of about 3.5% to 6.5% by mass with respect to 1,2,3-benzotriazole contained in the aqueous solution at about 1% by mass.

  As the pH adjuster, for example, an acid or base that is compatible with an aqueous solution containing a bactericide and compatible with the environment can be used. For example, citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, organic acids such as adipic acid and salts thereof, inorganic acids such as phosphoric acid and sulfuric acid and salts thereof, ammonium hydroxide or A base such as an alkali metal hydroxide can be used. But the pH adjuster which can be added to the aqueous solution containing a disinfectant is not limited to these. The concentration of the pH adjusting agent in the aqueous solution is not particularly limited, but is preferably 20% by mass or less, particularly preferably 0.1% by mass to 10% by mass with respect to the total mass of the aqueous solution.

  It is preferable that the aqueous solution containing a disinfectant contains a heavy metal ion sequestering agent as an optional component. In the present specification, the heavy metal ion sequestering agent means a substance having the property of sequestering (chelating) heavy metal ions, and when these components have the ability to chelate calcium and magnesium, iron, manganese, And a substance having the property of binding more selectively to heavy metal ions such as copper. The heavy metal ion sequestering agent is generally 0.005% by mass to 20% by mass, preferably 0.1% by mass to 10% by mass, and more preferably 0.25% by mass with respect to the total mass of the composition in the aqueous solution containing the bactericide. % To 7.5% by mass, and most preferably 0.5% to 5% by mass. Examples of heavy metal sequestering agents include organic phosphonates such as aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxydiphosphonates, nitrilotrimethylene phosphonates, and the like. Of these, diethylenetriaminepenta (methylenephosphonic acid), ethylenediaminetri (methylenephosphonate) hexamethylenediaminetetra (methylenephosphonic acid), and hydroxy-ethylene 1,1 diphosphonate are preferred.

  Other preferred heavy metal sequestering agents that can be added to an aqueous solution containing a disinfectant include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutar Acid, 2-hydroxypropylenediamine disuccinic acid, or any salt thereof. Particularly preferred is ethylenediamine-N, N′-disuccinic acid (EDDS) or an alkali metal salt, alkaline earth metal salt, ammonium salt or substituted ammonium salt thereof, or a mixture thereof.

  Other preferable heavy metal ion sequestering agents that can be added to an aqueous solution containing a bactericide are described in, for example, European Patent Publication No. 317,542 and European Patent Publication No. 399,133. -Iminodiacetic acid derivatives such as hydroxyethyldiacetic acid or glyceryliminodiacetic acid, iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxyl described in EP 516,102 Methyl N-2-hydroxypropyl-3-sulfonic acid sequestering agent, and β-alanine-N, N′-diacetic acid, aspartic acid-N, N′- described in European Patent Publication No. 509,382 Examples include diacetic acid, aspartic acid-N-monoacetic acid, and iminodisuccinic acid sequestering agent. EP-A 476,257 describes preferred blocking agents having amino groups. EP-A 510,331 describes preferred blocking agents derived from collagen, keratin or casein. EP 528,859 describes preferred alkyliminodiacetic acid sequestering agents. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Also suitable are glycinamide-N, N'-disuccinic acid (GADS), ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (HPDDS). is there. But the preferable heavy metal ion sequestering agent which can be added to the aqueous solution containing a disinfectant is not limited to what was illustrated above.

  As the stabilizer, a known stabilizer can be used, and examples thereof include phosphate, 8-hydroxyquinoline, stannic acid, sulfolene, sulfolane, sulfoxide, sulfone, and sulfonic acid. Phosphate can be used as a preferred stabilizer in an aqueous solution containing a bactericide. Preferably, from about 0.001% to about 0.5% by weight phosphate based on the total weight of the aqueous solution. The phosphate is selected from the group consisting of sodium orthophosphate, potassium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium polyphosphate, potassium polyphosphate, and combinations thereof.

  The aqueous solution containing a disinfectant may contain a surfactant up to about 30% by mass based on the total mass of the aqueous solution, if necessary. As the surfactant, for example, a surfactant that is stable against oxidation and / or decomposition in the presence of peroxycarboxylic acid and hydrogen peroxide in an acidic aqueous medium can be used, and the surfactant is easily oxidized. Should be avoided. Preferred surfactants can be selected from nonionic, anionic, amphoteric or cationic surfactants. As a preferable surfactant that can be added to an aqueous solution containing a bactericide, for example, a nonionic surfactant can be exemplified. More specifically, examples include polyethylene / polypropylene block polymer type surfactants, polyoxyethylene alkylphenyl ether type surfactants, polyoxyethylene ether type surfactants, and polyoxyethylene sorbitan type surfactants. The surfactant that can be added to the aqueous solution is not limited to these.

  As the anti-reattachment agent, those having a function of keeping dirt or the like detached from an object to be sterilized or sterilized such as a medical device suspended in a liquid can be used. For example, organic water-soluble colloids (eg starch, gelatin, or starch ether carboxylic acid or ether sulfonic acid salt, cellulose, cellulose ether, or cellulose ether carboxylic acid or ether sulfonic acid salt, or cellulose or starch And the like, and the like. Water-soluble polyamides containing acidic groups can also be suitably used. Furthermore, starch derivatives other than those described above, such as aldehyde starch, can be used as an anti-redeposition agent. However, the anti-redeposition agent that can be added to the aqueous solution containing the bactericide is not limited to those exemplified above. As the anti-redeposition agent, for example, one or more selected from the group consisting of the above-described substances exemplified as the anti-redeposition agent can be used. When the aqueous solution containing the bactericidal agent contains the anti-redeposition agent, the concentration of the anti-redeposition agent is not particularly limited, but is preferably 5% by mass or less, particularly preferably 2% by mass or less, based on the total mass of the aqueous solution.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
Example 1: Evaluation of antimicrobial activity Antimicrobial activity against spores was evaluated. The Bacillus subtilis spore solution (Eiken Equipment Co., Ltd.) was adjusted to 1.0 × 10 ⁷ cfu / mL and subjected to the following antimicrobial activity evaluation. The activity was evaluated according to the method of Sakagami et al. (J. Antibact. Antifung. Agents., 26, 605-601, 1998). Specifically, 2 mL of the Bacillus subtilis spore solution is added to 18 ml of an aqueous composition containing Compound 2 (40 mmol / m) and hydrogen peroxide (120 mmol / l) (spore concentration after mixing; 1.0 × 10 6 ⁶ cfu / ml), an ultraviolet lamp (30 W, submerged ultraviolet sterilizer (Funatech Co., Ltd.)) was immediately inserted, and ultraviolet irradiation was performed at room temperature for a certain period of time. 2 μL was sampled at regular intervals, added to 2 mL of SCDLP medium (Nissui Pharmaceutical), and cultured at 160 rpm and 37 ° C. for 48 hours to examine the presence or absence of bacterial growth. As a control, the same experiment was conducted for the case without ultraviolet irradiation. The results are shown in Table 1. In the table, + indicates that cell growth in liquid culture was observed, and-indicates that cell growth in liquid culture was not observed.

Example 2: Evaluation of antimicrobial activity The antimicrobial activity was evaluated in the same manner as in Example 1. Specifically, 2 mL of the Bacillus subtilis spore solution was added to 18 ml of sterilized water (spore concentration after mixing; 1.0 × 10 ⁶ cfu / ml), and immediately an ultraviolet lamp (30 W, submerged ultraviolet sterilizer (Funatech Corporation) ))) Was placed, and ultraviolet irradiation was performed at room temperature for a certain time. Thereafter, 23 μL of an aqueous solution containing Compound 3 (1830 mM) was added (concentration after mixing: 40 mM), 2 μL was sampled at regular intervals, and antimicrobial activity was evaluated in the same manner as in Example 1. Further, as a control, the same experiment was carried out in the case of no ultraviolet irradiation and in the case of no addition of compound 3. The results are shown in Table 2.

  From these results, the treatment combining the ultraviolet irradiation and the aqueous solution containing the peroxycarboxylic acid, synergistically compared to the case of using the aqueous solution containing the peroxycarboxylic acid alone and the case of the treatment with the ultraviolet irradiation alone. It has been shown that strong antimicrobial activity has been achieved and spores can be disinfected or sterilized in a very short time.

Claims (10)

A disinfection or sterilization method comprising a combination of disinfectant treatment and ultraviolet irradiation. The method according to claim 1, wherein ultraviolet irradiation using ultraviolet rays having a wavelength of 300 nm or less is performed. The method according to claim 1 or 2, wherein the ultraviolet irradiation is performed for a time of 5 seconds or more and 10 minutes or less. The method according to any one of claims 1 to 3, wherein the object to be disinfected or sterilized is a medical device. The method according to claim 4, wherein the object to be disinfected or sterilized is an endoscope. The method according to any one of claims 1 to 5, wherein the disinfectant is a peroxycarboxylic acid. Peroxycarboxylic acid is peracetic acid or general formula (I):

(Wherein R ¹ represents a substituted or unsubstituted C1-C10 alkyl group (excluding a substituent having a hydroxy group as a substituent) or a substituted or unsubstituted C6-C10 aryl group; 7 represents a substituted or unsubstituted C2-C12 divalent linking group, and R ¹ and L may be combined to form a ring). . L represents —CH (R ¹¹ ) —L ¹² (wherein R ¹¹ represents a hydrogen atom or a C1-C4 substituted or unsubstituted alkyl group, and L ¹² represents a substituted or unsubstituted C1-C11 divalent group. The method according to claim 7, wherein the group is a group represented by: The method according to claim 8, wherein L ¹² is a substituted or unsubstituted C1-C4 divalent linking group. The method according to any one of claims 7 to 9, wherein R ¹ is a substituted or unsubstituted C1-C3 alkyl group.