Composition, kit, method for producing the same, and cleaning method using the same for cleaning object for which aqueous cleaning is avoided

Abstract

To provide a safe and effective cleaning means which does not adversely affect an object for which water-based cleaning is avoided.SOLUTION: The present disclosure provides a composition for cleaning an object for which water-based cleaning is to be avoided, the composition including a first phase including an aqueous solution containing a radical generator and a radical generating catalyst, and a second phase including an organic solvent, wherein the organic solvent is a water-insoluble solvent capable of extracting a radical generated from the radical generator, and the organic solvent containing the radical of the second phase in the composition is applied to cleaning of the object, a method for producing the same, and a kit. A cleaning method using the composition is also provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a composition for cleaning objects that should not be washed with water, a kit, a method for producing the same, and a cleaning method using the same. [Background technology]

[0002] Cultural properties stored in museums and art galleries that should not be washed with water are generally isolated and treated with physical or chemical methods if mold damage is confirmed. Previously, methyl bromide fumigation was widely used to treat mold-damaged objects, but its use is now prohibited due to its danger to workers and potential ozone depletion potential. Organic reagents such as ethylene oxide and propylene oxide are currently commonly used as fumigants, but their high reactivity and explosive nature pose a risk not only to cultural properties but also to workers. Carbon dioxide fumigation is also common, and while effective against insect damage, it is difficult to fundamentally prevent mold damage because mold can grow in a carbon dioxide environment.

[0003] On the other hand, fluorinated solvents, a type of organic solvent, are characterized by non-flammability, high thermal and chemical stability, low viscosity, low latent heat of vaporization, low surface tension, moderate boiling point, and low corrosivity. They are used as refrigerants for electronic devices, fire extinguishing agents, coating agents, and other solvents. Fluorinated solvents are also used as dry-cleaning solvents for everyday items such as clothing that are highly durable in the washing process. However, it is not widely known that they can be used to easily clean cultural heritage materials, which are prone to water-based cleaning and have become fragile due to aging or flooding.

[0004] In recent years, sterilization techniques that utilize radicals and are highly safe for living organisms have been developed. For example, Patent Document 1 discloses a chemical agent that includes a radical-generating catalyst and a radical-generating source, the radical-generating catalyst including at least one of ammonium and its salt, and a substance having at least one of Lewis acidity and Bronsted acidity. However, it is not known at all whether the chemical agent can be used to clean cultural property materials and the like that are averse to aqueous cleaning. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-109978 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a safe and effective cleaning means that does not adversely affect objects that should not be cleaned with water. [Means for solving the problem]

[0007] As a result of investigations to solve the above problems, the present inventors have found that a composition comprising a first phase containing an aqueous solution containing a radical source and a radical-generating catalyst, and a second phase containing an organic solvent, wherein the organic solvent is water-insoluble and capable of extracting radicals generated from the radical source, and the organic solvent containing the radicals in the second phase is used to clean the object, is suitable for cleaning the object for which aqueous cleaning is avoided, and have completed the present invention. That is, the present invention includes the following aspects.

[0008] [1] A composition for cleaning objects that should not be washed with water, comprising: a first phase comprising an aqueous solution containing a radical generating source and a radical generating catalyst; and A second phase containing an organic solvent Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, A composition, characterized in that the organic solvent containing the radicals of the second phase is applied to clean the object. [2] The composition according to item 1, wherein the object contains microbial contamination. [3] The composition according to item 2, wherein the microorganism is a bacterium and / or a fungus. [4] The composition according to any one of items 1 to 3, wherein the object is selected from the group consisting of paper, papyrus, bark cloth, wood, bamboo, animal leather, and cloth. [5] The composition according to any one of items 1 to 4, wherein the organic solvent is a fluorine-containing solvent. [6] The composition according to item 5, wherein the fluorine-based solvent is selected from the group consisting of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and perfluorocompounds. [7] The composition according to any one of items 1 to 6, wherein the radical generating source is at least one selected from the group consisting of a halous acid, a halous acid ion, and a halous acid salt. [8] The composition according to any one of items 1 to 7, wherein the radical generating source is chlorous acid, chlorite ion, or chlorite. [9] The composition according to any one of items 1 to 8, wherein the radical-generating catalyst is an ammonium salt having a Lewis acidity of 0.4 eV or more.

[10] The composition according to item 9, wherein the radical-generating catalyst comprises an ammonium salt represented by the following chemical formula (I): [ka] (In the above chemical formula (I), R 1 , R 2, R 3 and R 4 are the same or different and each represents a hydrogen atom or an alkyl group, and may contain an ether bond, a carbonyl group, an ester bond, an amide bond, or an aromatic ring; X - is an anion.)

[11] The composition according to item 10, wherein the ammonium salt represented by the chemical formula (I) is an ammonium salt represented by the following chemical formula (II): [ka] (In the above chemical formula (II), R 11 is an alkyl group having 5 to 40 carbon atoms, which may contain an ether bond, a carbonyl group, an ester bond, an amide bond, or an aromatic ring; R 2 and X - is the same as the chemical formula (I).

[12] The composition of item 11, wherein the ammonium salt represented by the chemical formula (II) is an ammonium salt represented by the following chemical formula (III): [ka] (In the above chemical formula (III), R 11 and X - is the same as the above chemical formula (II).

[13] The composition according to item 11, wherein the ammonium salt represented by formula (II) is benzethonium chloride and / or benzalkonium chloride.

[0009]

[14] A method for producing a composition for cleaning an object that is avoided from being washed with a water-based solution according to any one of items 1 to 13, comprising: a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst is brought into contact with a second phase containing an organic solvent, and radicals generated from the radical generating source in the first phase are extracted into the second phase; Including, wherein the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source; A manufacturing method, characterized in that the organic solvent containing the radicals of the second phase in the composition is applied to cleaning the object.

[15] The manufacturing method according to Item 14, wherein the object contains microbial contamination.

[16] The method according to Item 15, wherein the microorganism is a bacterium and / or a fungus.

[17] The manufacturing method according to any one of items 14 to 16, wherein the object is selected from the group consisting of paper, papyrus, bark cloth, wood, bamboo, animal leather, and cloth.

[18] The method according to any one of items 14 to 17, wherein the organic solvent is a fluorine-containing solvent.

[19] The production method according to item 18, wherein the fluorine-based solvent is selected from the group consisting of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and perfluorocompounds.

[20] The method according to any one of items 14 to 19, wherein the radical source is at least one selected from the group consisting of a halous acid, a halous acid ion, and a halous acid salt.

[21] The method according to any one of items 14 to 20, wherein the radical source is chlorous acid, chlorite ions, or chlorite.

[22] The composition according to any one of items 14 to 21, wherein the radical-generating catalyst is an ammonium salt having a Lewis acidity of 0.4 eV or more.

[23] The method according to item 22, wherein the radical-generating catalyst comprises an ammonium salt represented by the following chemical formula (I): [ka] (In the above chemical formula (I), R 1 , R 2 , R 3 and R 4are the same or different and each represents a hydrogen atom or an alkyl group, and may contain an ether bond, a carbonyl group, an ester bond, an amide bond, or an aromatic ring; X - is an anion.)

[24] The method according to item 23, wherein the ammonium salt represented by the chemical formula (I) is an ammonium salt represented by the following chemical formula (II): [ka] (In the above chemical formula (II), R 11 is an alkyl group having 5 to 40 carbon atoms, which may contain an ether bond, a carbonyl group, an ester bond, an amide bond, or an aromatic ring; R 2 and X - is the same as the chemical formula (I).

[25] The method of producing according to Item 24, wherein the ammonium salt represented by the chemical formula (II) is an ammonium salt represented by the following chemical formula (III): [ka] (In the above chemical formula (III), R 11 and X - is the same as the above chemical formula (II).

[26] The method according to Item 24, wherein the ammonium salt represented by the chemical formula (II) is benzethonium chloride and / or benzalkonium chloride.

[0010]

[27] A kit for producing a composition for cleaning an object against which water-based cleaning is avoided according to any one of items 1 to 13, comprising: a first phase including an aqueous solution containing a radical generating source and a radical generating catalyst; a second phase containing an organic solvent; Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, contacting the first phase with the second phase to form a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst, and a second phase containing an organic solvent; extracting radicals generated from the radical generating source in the first phase into the second phase; A kit, characterized in that the organic solvent containing the radicals of the second phase is applied to wash the object.

[0011]

[28] A method for cleaning an object for which water-based cleaning is avoided, comprising: In the composition according to any one of Items 1 to 13, the composition obtained by the production method according to any one of Items 14 to 26, or the composition produced from the kit according to Item 27, the organic solvent containing the radicals in the second phase is brought into contact with the object to be washed. A cleaning method comprising:

[0012]

[29] A method for cleaning an object for which water-based cleaning is avoided, comprising: (1) Cleaning the object by bringing an aqueous solution containing a radical generating source and a radical generating catalyst into contact with the object. (2) contacting the object of step (1) with an organic solvent to remove water impregnated in the object; Including, wherein the organic solvent is non-aqueous. [Effects of the Invention]

[0013] The present disclosure provides a composition, a kit, and a method for producing the same that solve the above-mentioned problems. Furthermore, by using the composition of the present disclosure, it is possible to easily clean objects that should not be cleaned with aqueous cleaning, without causing substantial physical or chemical deterioration. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 shows water-soaked paper after it has been air-dried (left) or after it has been treated with a fluorine-based solvent to remove water (right). [Figure 2]FIG. 2 shows a schematic diagram illustrating the method of the present invention in one embodiment. [Figure 3] Figure 3 shows the compressibility of wet paper after air drying (left) or after water removal treatment using a fluorine-based solvent (right). The compressibility is shown when the area of ​​the wet paper is set to "1" (N=10). ***: p<0.01 [Figure 4] FIG. 4 shows the results of comparing the cleaning effects of water and fluorinated solvents on pieces of paper to which Streptomyces flavus (NBRC3359) and Eurotium herbariorum (alias Aspergillus glaucus: NBRC33235) had been attached. [Figure 5] Figure 5 shows a scanning electron microscope image of a paper sample that was treated with a first phase (first phase solution) containing an aqueous solution containing a radical source and a radical-generating catalyst, and then subjected to a dewatering treatment using a fluorine-based solvent. DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, one embodiment of the present invention will be described with reference to the drawings, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are described for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0016] In one embodiment, the present invention provides A composition for cleaning objects that are reluctant to be washed with water, comprising: a first phase comprising an aqueous solution containing a radical generating source and a radical generating catalyst; and A second phase containing an organic solvent Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, The present invention provides a composition, characterized in that the organic solvent containing the radicals of the second phase is applied to wash the object.

[0017] In one embodiment, the present invention also provides a method for producing the above composition, comprising the steps of: a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst is brought into contact with a second phase containing an organic solvent, and radicals generated from the radical generating source in the first phase are extracted into the second phase; Including, wherein the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source; The present invention provides a production method, characterized in that the organic solvent containing the radicals of the second phase in the composition is applied to wash the object.

[0018] In one embodiment, the present invention also provides a kit for preparing a composition for cleaning an object where water-based cleaning is avoided, comprising: a first phase including an aqueous solution containing a radical generating source and a radical generating catalyst; a second phase containing an organic solvent; Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, contacting the first phase with the second phase to form a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst, and a second phase containing an organic solvent; extracting radicals generated from the radical generating source in the first phase into the second phase; The kit is characterized in that the organic solvent containing the radicals of the second phase is applied to the cleaning of the object. In the kit, the first phase and the second phase may be provided in the same package or in separate packages. Furthermore, the kit may further include an instruction manual describing how to use the kit.

[0019] The inventors of the present invention have discovered that radicals generated from a first phase containing an aqueous solution containing a radical source and a radical-generating catalyst can be extracted into a second phase containing an organic solvent. Even when only the organic solvent containing the radicals in the second phase is used to clean the object, the radicals can still act to provide cleaning, deodorizing, sterilizing, and other effects. This has enabled the removal and / or reduction of microbial contamination without substantial physical or chemical deterioration, even for objects that are averse to aqueous cleaning, such as valuable cultural properties. Furthermore, after using the second phase of the composition, the used second phase can be re-contacted with the original first phase, allowing the environmentally hazardous second phase to be reused (recycled). The first phase may be further added to the composition, or the first phase may be replaced with a new one. The amount of radicals extracted into the second phase can be adjusted by adjusting the amount of the radical source contained in the first phase. Furthermore, when the second phase is reused (recycled), the second phase after use in cleaning object A (here, to explain that the objects being cleaned are different, they will be referred to as "object A" and "object B") may be reused (recycled) as is for cleaning object B. Alternatively, the second phase after use in cleaning object A may be contacted with the first phase, and radicals generated from the first phase may be extracted, and the resulting second phase may be reused (recycled) for cleaning object B. Alternatively, the first phase may be recycled, and the organic solvent used as the second phase may be the same or a different type of organic solvent.

[0020] In one embodiment, the present invention provides a method for cleaning an object that should not be cleaned with water, using the composition or the composition obtained by the production method described above. Specifically, the cleaning method includes contacting the organic solvent containing the radicals of the second phase of the composition with the object to clean it.

[0021] In this specification, an object that should not be washed with water refers to an object made of a material that will wrinkle or shrink during the drying process of the wet object, and examples thereof include objects made of materials containing natural fibers, such as paper, papyrus, bark cloth, wood, bamboo, animal leather, and cloth. Objects that should not be washed with water may be, for example, clothing or writing materials.

[0022] In this specification, "writing material" refers to a medium, primarily having a two-dimensional surface, used to record and / or draw information such as letters, symbols, and / or pictures (e.g., paintings). Writing materials contain information from the era in which they were used, recorded as letters, symbols, or pictures, and are highly valuable as historical documents and cultural assets, and therefore need to be preserved stably for a long period of time.

[0023] Writing materials are sometimes damaged by flooding due to natural disasters such as tsunamis and extreme weather events, or by water used to extinguish fires. Water-damaged writing materials often suffer subsequent microbial contamination, particularly mold damage, and therefore require prompt and appropriate cleaning and drying processes. Many writing materials, such as historical documents and cultural assets, are unique, making restoration difficult if they are damaged. Traditionally, cultural assets that have suffered such damage have been treated using large facilities such as fumigation chambers. Furthermore, the drying process for water-soaked objects has been problematic, as they are prone to physical and chemical damage, such as creasing and shrinkage. In one embodiment, the present invention provides a method for cleaning water-damaged writing materials while preventing creasing and shrinkage and without substantial physical or chemical degradation. By applying this invention, large facilities such as the fumigation cabinets that have been used in the past are not required, and it can be applied, for example, at disaster sites, and can also contribute to emergency treatment of objects that have suffered flood damage.

[0024] The writing material to which the present invention can be applied is not limited, and may be, for example, a material containing natural fibers, such as paper, papyrus, bark cloth, wood, bamboo, animal hide, or cloth. In one embodiment, the present invention is preferably used with a wet writing material, and the present invention allows the writing material to be dried while preventing curling and shrinkage and without substantial physical or chemical deterioration.

[0025] In one embodiment, the present invention may include a step of washing a hydrated object with a second-phase organic solvent while contacting the object with a water-absorbent material, such as a sponge or a water-absorbent polymer (e.g., sodium polyacrylate copolymer). For example, by sandwiching the hydrated object between water-absorbent materials from above and below and applying the second-phase organic solvent to the object, water can be transferred from the object to the water-absorbent material, thereby shortening the drying time. Furthermore, sandwiching the object between water-absorbent materials can reduce the occurrence of wrinkles and shrinkage.

[0026] In one embodiment, the object to be avoided from being washed with a water-based system may be one containing microbial contamination. The microorganism may be bacteria and / or fungi, particularly mold-forming fungi. Examples of bacteria as contaminants include, but are not limited to, gram-negative bacteria such as Escherichia genus (e.g., Escherichia coli), Methylobacterium genus (e.g., Methylobacterium mesophilicum), Pseudomonas genus (e.g., Pseudomonas aeruginosa), Serratia genus (e.g., Serratia marcescens), Staphylococcus genus (e.g., Staphylococcus aureus), Bacillus genus (e.g., Bacillus subtilis, Bacillus cereus), and gram-positive bacteria such as lactic acid bacteria. Furthermore, fungi as contaminants include, but are not limited to, the genus Cladosporium such as Cladosporium cladosporioides, the genus Penicillium such as Penicillium citrinum, the genus Aspergillus such as Aspergillus brasiliensis, the genus Alternaria such as Alternaria alternata, the genus Fusarium such as Fusarium solani, the genus Eurotium such as Eurotium herbariorum, the genus Streptomyces such as Streptomyces flavus, the genus Rhodotorula, Examples of yeasts that can be used include red yeasts such as Aureobasidium and Exophiala, black yeasts such as Phoma, Candida, and Saccharomyces.

[0027] In one embodiment, by applying the present invention to an object where aqueous cleaning is avoided, it is possible to remove and / or reduce microbial contamination without substantially accompanying physical and chemical deterioration. Also, in another embodiment, by applying the present invention to an object where aqueous cleaning is avoided, it is possible to inhibit the growth of microorganisms on the object.

[0028] In one embodiment, the organic solvent applicable to the present invention may be a single organic solvent or a mixture of two or more organic solvents. Also, in one embodiment, the organic solvent applicable to the present invention may be a fluorine-based solvent. Also, in one embodiment, the fluorine-based solvent may be a "fluorous solvent" that is highly fluorinated. A fluorous solvent is a solvent that is immiscible with an aqueous phase or another organic solvent phase and forms a new phase called a fluorous phase. In one embodiment, among the fluorine-based solvents, a fluorous solvent that is immiscible with a first phase containing an aqueous solution containing a radical source and a radical-generating catalyst and a second phase containing an organic solvent and forms a fluorous phase (third phase) may be used. By using a fluorous solvent, contaminant components incorporated into the fluorous solvent can be extracted into an organic phase in the subsequent liquid treatment process, allowing the fluorous solvent to be recycled.

[0029] In one embodiment, the fluorinated solvent may also be a fluorous / organic amphiphilic solvent.

[0030] Fluorinated solvents are solvents characterized by non-flammability, high thermal and chemical stability, low viscosity, low latent heat of vaporization, low surface tension, a moderate boiling point, and low corrosiveness, and currently, environmentally friendly fluorinated solvents with low ozone depletion potential (ODP) and global warming potential (GWP) have been developed and are on the market. In one embodiment, the fluorinated solvent applicable to the present invention may be selected from the group consisting of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and perfluorocompounds.

[0031] Examples of hydrochlorofluorocarbons (HCFCs) include those represented by the chemical formulas CF3CF2CHCl2 and CClF2CF2CHClF (for example, ASAHIKLIN (registered trademark) AK-225 manufactured by AGC Corporation).

[0032] Examples of hydrofluorocarbons (HFCs) include those of the chemical formula: CF3CF2CF2CF2CF2CF2H (e.g., ASAHIKLIN (registered trademark) AC-2000 manufactured by AGC Corporation), those of the chemical formula: CF3CF2CF2CF2CF2CF2CF2CF2CH3 (e.g., ASAHIKLIN (registered trademark) AC-6000 manufactured by AGC Corporation), and CF3CH2CHF2 (e.g., HFC-245fa manufactured by Central Glass Co., Ltd.).

[0033] Examples of hydrofluoroethers (HFEs) include those represented by the chemical formula: CHF2CF2OCH2CF3 (e.g., ASAHIKLIN (registered trademark) AE-3000 manufactured by AGC Corporation), CF3CF2CF2OCH3 (e.g., Novec (registered trademark) 7000 manufactured by 3M Corporation), CF3CF2CF2CF2OCH3 (e.g., Novec (registered trademark) 7100 manufactured by 3M Corporation), CF3CF2CF2CF2OCH2CH3 (e.g., Novec (registered trademark) 7200 manufactured by 3M Corporation), and CF3CF2CF(OCH3)CF(CF3)2 (e.g., Novec (registered trademark) 7300 manufactured by 3M Corporation).

[0034] Examples of hydrofluoroolefins (HFOs) include those having the chemical formula: CFCF=CH (e.g., AMOLEA (registered trademark) 1234yf manufactured by AGC Inc.), CFCH=CHCl (e.g., CELEFIN (registered trademark) 1223Z (HFO-1233zd(Z)) manufactured by Central Glass Co., Ltd.), and CFCH=CHF (e.g., ZEM-SCREEN (registered trademark) (HFO-1234ze(E)) manufactured by Central Glass Co., Ltd.).

[0035] Examples of hydrochlorofluoroolefins (HCFOs) include those represented by the chemical formula: CHF2=CHCl (for example, AMOLEA (registered trademark) AS-300 manufactured by AGC Corporation).

[0036] Examples of perfluoro compounds include perfluoro compounds having carbon numbers of C5 to C18 or mixtures thereof, such as Fluorinert (trademark) manufactured by 3M Corporation (e.g., F-43, FC-72, FC-770, FC-3283, etc.).

[0037] The radical generating source applicable to the present invention may be at least one selected from the group consisting of halous acid, halous acid ions, and halous acid salts, and preferably at least one selected from the group consisting of chlorous acid, chlorous acid ions, and chlorous acid salts. Specifically, the radical generating source may be sodium chlorite.

[0038] In the composition of the present invention, the content of the radical source contained in the first phase may be, for example, 1 to 20,000 ppm by mass, preferably 10 to 3,000 ppm by mass, more preferably 10 to 1,500 ppm by mass, and even more preferably 100 to 1,500 ppm by mass. If the concentration of the radical source in the composition is too low, the amount of radicals generated may be too small, and cleaning (particularly sterilizing) effects may not be achieved. Furthermore, the higher the concentration of the radical source, the better the cleaning (particularly sterilizing) effects, but from the perspective of ensuring safety, it is preferably 20,000 ppm by mass or less. Furthermore, in order to further reduce the survival or persistence of microorganisms at levels not visible to the naked eye on the target object, the higher the concentration of the radical source contained in the first phase, the greater the effect, and therefore the concentration may be preferably 10 to 3,000 ppm by mass, more preferably 100 to 1,500 ppm by mass.

[0039] In one embodiment, the aqueous solution containing a radical-generating source applicable to the present invention may further contain a radical-generating catalyst.

[0040] The radical-generating catalyst that can be included in the first phase of the present invention (hereinafter sometimes referred to as "the radical-generating catalyst of the present invention") is not particularly limited as long as it catalyzes the generation of radicals from a radical-generating source, and known compounds can be used. The radical-generating catalyst may be used alone or in combination of two or more.

[0041] In the present invention, a Lewis acid is preferably used as the radical generating catalyst, and a Lewis acid having a Lewis acidity of 0.4 eV or more is more preferred. The upper limit of the Lewis acidity is not particularly limited, but is preferably 20 eV or less. The Lewis acidity can be measured, for example, by the method described in Ohkubo, K.; Fukuzumi, S. Chem. Eur.J., 2000, 6, 453-2, J. AM. CHEM.SOC.2002, 124, 10270-10271, or J. Org.Chem. 2003, 68, 4720-4726, and specifically, by the following method.

[0042] (Method for measuring Lewis acidity) In the following reaction scheme (A), cobalt tetraphenylporphyrin (CoTPP), saturated O2, and the object to be measured for Lewis acidity (e.g., a cation of a metal, etc., are shown. In the following reaction scheme (A), M n+ The change in the UV-visible absorption spectrum of acetonitrile (MeCN) containing the reaction product (represented by k cat ) can be used to calculate the ΔE value (eV), which is an index of Lewis acidity. cat The higher the value, the stronger the Lewis acidity. The Lewis acidity of an organic compound can also be estimated from the energy level of the lowest unoccupied molecular orbital (LUMO), calculated by quantum chemical calculations. The higher the positive value, the stronger the Lewis acidity.

[0043] [ka]

[0044] The following shows an example of the reaction rate constant between CoTPP and oxygen in the presence of a Lewis acid, which serves as an index of Lewis acidity measured (calculated) by the above-mentioned measurement method. cat ,M -2 s -1The value represented by " is the energy level of CoTPP and oxygen in the presence of a Lewis acid. The value represented by "LUMO, eV" is the energy level of the LUMO.

[0045] [Table 1]

[0046] The radical-generating catalyst contained in the first phase of the present invention is preferably an ammonium or a salt thereof having Lewis acid properties, such as a quaternary ammonium, or a tertiary, secondary, primary, or zeroth ammonium.

[0047] Examples of ammonium and its salts include cationic surfactants, and among these, quaternary ammonium type cationic surfactants are preferred.

[0048] Examples of quaternary ammonium type cationic surfactants include benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, hexadecyltrimethylammonium bromide, dequalinium chloride, edrophonium, didecyldimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride, oxitropium, carbachol, glycopyrronium, safranine, sinapine, tetraethylammonium bromide, and hexadecyl bromide. Examples of suitable anti-inflammatory agents include trimethylammonium, suxamethonium, sphingomyelin, denatonium, trigonelline, neostigmine, paraquat, pyridostigmine, phellodendrine, pralidoxime methyl iodide, betaine, betanin, bethanechol, betalain, lecithin, and cholines (choline chlorides such as benzoylcholine chloride and lauroylcholine chloride hydrate, phosphocholine, acetylcholine, choline, dipalmitoylphosphatidylcholine, and choline bitartrate). These may be used alone or in combination of two or more.

[0049] However, in the present invention, the quaternary ammonium is not limited to surfactants.

[0050] In the radical-generating catalyst included in the first phase of the present invention, the ammonium may be, for example, ammonium represented by the following chemical formula (I).

[0051] [ka]

[0052] In the above chemical formula (I), R 1 , R 2 , R 3 and R 4 are the same or different and each is a hydrogen atom or an alkyl group, which may contain an ether bond, a ketone (carbonyl group), an ester bond, an amide bond, or an aromatic ring, and X- is an anion. The alkyl group is preferably a linear or branched alkyl group having 1 to 40 carbon atoms.

[0053] The ammonium represented by the chemical formula (I) is preferably ammonium represented by the following chemical formula (II).

[0054] [ka]

[0055] In the above chemical formula (II), R 11 is an alkyl group having 5 to 40 carbon atoms, which may contain an ether bond, a ketone (carbonyl group), an ester bond, an amide bond, or an aromatic ring; R 2 and X - is the same as the above chemical formula (I).

[0056] In the above chemical formula (II), R 2is preferably a methyl group or a benzyl group, and the benzyl group may or may not have one or more hydrogen atoms on the benzene ring substituted with an optional substituent, and the optional substituent may be, for example, an alkyl group, an unsaturated aliphatic hydrocarbon group, an aryl group, a heteroaryl group, a halogen, a hydroxy group (-OH), a mercapto group (-SH), or an alkylthio group (-SR, where R is an alkyl group).

[0057] The ammonium represented by the chemical formula (II) is preferably ammonium represented by the following chemical formula (III).

[0058] [ka]

[0059] In the above chemical formula (III), R 11 and X - is the same as the above chemical formula (II).

[0060] Specific examples of the ammonium represented by the chemical formula (I) include benzethonium chloride, benzalkonium chloride, hexadecyltrimethylammonium chloride, tetramethylammonium chloride, ammonium chloride, and tetrabutylammonium chloride, and at least one selected from the group consisting of these is preferred. Among these, benzethonium chloride represented by the formula (II) is particularly preferred.

[0061] In addition, benzethonium chloride (Bzn + Cl - ) can be represented, for example, by the following chemical formula (IV): In formula (IV), Me is a methyl group; t Bu is a tertiary butyl group. Benzalkonium chloride can be obtained by, for example, 11 is an alkyl group having 8 to 18 carbon atoms, and X - is the chloride ion. [ka]

[0062] In the above chemical formulas (I), (II) and (III), X - is any anion and is not particularly limited. - is not limited to a monovalent anion, but may be an anion of any valence, such as divalent or trivalent. When the anion has multiple charges, such as divalent or trivalent, the number of ammonium (monovalent) molecules in the chemical formulas (I), (II), and (III) is, for example, the number of anion molecules multiplied by the valence of the anion (for example, when the anion is divalent, the number of anion (monovalent) molecules is twice the number of anion molecules). X - Examples of the ions include halogen ions (fluoride ions, chloride ions, bromide ions, iodide ions), acetate ions, nitrate ions, and sulfate ions.

[0063] The ammonium contained in the first phase of the present invention has an ammonium structure (N + Furthermore, the ammonium may form a dimer, a trimer, or the like, by association of a plurality of molecules through π electron interactions, for example.

[0064] In the present invention, when a compound (e.g., the organic ammonium compound) has isomers such as tautomers or stereoisomers (e.g., geometric isomers, conformational isomers, and optical isomers), any of the isomers can be used in the present invention unless otherwise specified.

[0065] Furthermore, when a compound (e.g., the organic ammonium) can form a salt, the salt may be either an acid addition salt or a base addition salt. Furthermore, the acid that forms the acid addition salt may be either an inorganic acid or an organic acid, and the base that forms the base addition salt may be either an inorganic base or an organic base. Examples of inorganic acids include, but are not limited to, sulfuric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, hypofluorite acid, hypochlorous acid, hypobromous acid, hypoiodite acid, fluorite acid, chlorous acid, bromous acid, iodite acid, fluoric acid, chloric acid, bromic acid, iodic acid, perfluoric acid, perchloric acid, perbromic acid, and periodic acid. Examples of organic acids include, but are not limited to, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, p-bromobenzenesulfonic acid, carbonic acid, succinic acid, citric acid, benzoic acid, and acetic acid. The inorganic base is not particularly limited, but examples thereof include ammonium hydroxide, alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, and bicarbonates, and more specifically, examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, calcium hydroxide, and calcium carbonate. The organic base is also not particularly limited, but examples thereof include ethanolamine, triethylamine, and tris(hydroxymethyl)aminomethane. The method for producing these salts is also not particularly limited, and they can be produced, for example, by adding the above-mentioned acid or base to the compound as appropriate using a known method.

[0066] Furthermore, in the present invention, unless otherwise specified, chain substituents (e.g., hydrocarbon groups such as alkyl groups and unsaturated aliphatic hydrocarbon groups) may be linear or branched, and the number of carbon atoms therein is not particularly limited, but is preferably 1 to 40, 1 to 32, 1 to 24, 1 to 18, 1 to 12, 1 to 6, or 1 to 2 (2 or more in the case of unsaturated hydrocarbon groups). Furthermore, in the present invention, the number of ring members (the number of atoms constituting the ring) of cyclic groups (e.g., aryl groups, heteroaryl groups, etc.) is not particularly limited, but is preferably 5 to 32, 5 to 24, 6 to 18, 6 to 12, or 6 to 10, but is not particularly limited. Furthermore, when isomers of substituents, etc. exist, any isomer may be used unless otherwise specified. For example, a simple reference to a "naphthyl group" may refer to either a 1-naphthyl group or a 2-naphthyl group.

[0067] In the first phase of the present invention, the content of the radical-generating catalyst is preferably 0.01 to 1500 ppm by mass. If the concentration of the radical-generating catalyst in the composition is too low, radical generation may be suppressed, and the bactericidal effect may not be obtained. Furthermore, a content of the radical-generating catalyst of 1500 ppm by mass or less is preferable because safety can be ensured. The content of the radical-generating catalyst in the composition is more preferably 0.1 to 1000 ppm by mass, even more preferably 0.1 to 500 ppm by mass, particularly preferably 1 to 200 ppm by mass, and most preferably 1 to 100 ppm by mass. Note that, from the viewpoint of preventing the bactericidal effect from being lost due to micelle formation, the concentration of the radical-generating catalyst is preferably equal to or less than the micelle limit concentration.

[0068] For example, in one embodiment, the first phase may be an aqueous solution containing a radical source and a radical-generating catalyst, such as commercially available MA-T (registered trademark) Concentrated Type 10K (Earth Chemical Co., Ltd.), which contains sodium chlorite as a radical-generating source and further contains a radical-generating catalyst.

[0069] In one embodiment, there is provided a method for cleaning an object that should not be washed with water, the method comprising contacting the object with an organic solvent containing a second-phase radical from the above-described composition, the composition obtained by the above-described production method, or the composition produced from the above-described kit. This method makes it possible to remove and / or reduce microbial contamination from objects that have traditionally been avoided from being washed with water, such as valuable objects such as cultural properties, without causing substantial physical or chemical deterioration.

[0070] In another aspect, a method for cleaning an object that should not be washed with water comprises the steps of: (1) cleaning the object by bringing an aqueous solution containing a radical source into contact with the object; and (2) contacting the object of step (1) with an organic solvent (wherein the organic solvent is water-insoluble) to remove the water impregnated in the object; Furthermore, the cleaning method of this embodiment may be combined with a cleaning method using the above-mentioned composition.

[0071] In one embodiment, in a method for cleaning an object that should not be cleaned with an aqueous solution using the composition or kit, the cleaning effect can be further enhanced by adjusting the time for which the organic solvent containing the radicals of the second phase is applied to the object for cleaning, for example, the immersion time. For example, the application time can be about 1 minute or more, as long as the cleaning effect (e.g., removal of contaminants, reduction of odor, or the presence or absence or reduction of microbial growth) can be confirmed. There is no upper limit, but the application time may be, for example, about 1 minute, about 3 minutes, about 5 minutes, about 10 minutes, about 30 minutes, about 1 hour, about 2 hours, about 4 hours, about 8 hours, about 24 hours (1 day), about 2 days, about 5 days, about 7 days (about 1 week), about 2 weeks, about 4 weeks (about 1 month), about 2 months, about 3 months, or longer. For example, the cleaning effect on the target object may be observed for any of the above periods, such as 1 minute to 3 months, 1 hour to 3 months, 2 hours to 2 months, 4 hours to 1 month, 1 day to 3 months, 1 week to 3 months, or 1 week to 1 month. The longer the application period, the greater the cleaning effect.

[0072] In this specification, the term "about" is used to mean a range of ±10%, preferably ±5%, more preferably ±3%, and most preferably ±1% of the numerical value to which it accompanies. [Example]

[0073] Examples of the present invention will be described below. However, the present invention is not limited to the following experimental examples. The first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst used in the following experimental examples was an aqueous solution containing 1.0% sodium chlorite as the radical generating source and 1.0% benzalkonium chloride as the radical generating catalyst, and was adjusted so that the sodium chlorite concentrations were 10 ppm, 100 ppm, and 1000 ppm when diluted and mixed with water (collectively referred to as "first phase solution" in the following experimental examples).

[0074] [Experimental Example 1] When flooded materials or other wet objects are allowed to dry naturally, they can suffer physical changes such as wrinkles and creases (Figure 1). Therefore, we came up with the idea of ​​immersing the objects in a fluorinated solvent while the objects are absorbed by a water-absorbent polymer. This replaces the water-containing portion of the object with the solvent, and then drying the object. This method eliminates the physical drying process and suppresses the degeneration of the objects (Figure 2). We compared the compressibility of paper samples with those dried naturally (Figure 3, n = 10 for each). We found that fluorinated solvents suppress physical degeneration compared to those dried naturally. The fluorinated solvents used in this study were Asahiklin® AE-3000 (manufactured by AGC Corporation) or Novec® 7300 (manufactured by 3M Corporation) (hereinafter collectively referred to as "fluorinated solvents"). Furthermore, no physical degeneration of the paper pieces was observed before or after treatment.

[0075] [Experimental Example 2] We conceived the idea of ​​physically washing away mold cells that may adhere to less durable cultural properties by washing with a fluorinated solvent (ASAHIKLIN® AE-3000, manufactured by AGC Corporation). In this experiment, two species of mold frequently reported to cause mold damage to cultural properties, Streptomyces flavus (NBRC3359) and Eurotium herbariorum (alias Aspergillus glaucus: NBRC33235), were obtained from the National Institute of Technology, Institute of Biotechnology (NBRC) (NBRC). Sterilized 1.0 cm square pieces of paper were then attached to a solution of the fungi suspended at a turbidity of 0.5 McFarland standard solution. The paper pieces were then divided into three groups: untreated, washed with sterile water, and washed with a fluorinated solvent. Each piece was placed in a sterile container containing 1.0 mL of the washing solution (hereafter referred to as "washing solution"), and the paper pieces immersed in sterile water and the fluorinated solvent were further washed with agitation. Next, each piece of paper was placed on potato dextrose agar (PDA) medium and cultured for two days and nights at 30°C. The results confirmed that washing with a fluorinated solvent had the same physical cleaning effect on mold as washing with water (Figure 4). When combined with Experiment 1, this experiment shows that a fluorinated solvent can clean mold cells and other deposits from an object without physically denaturing the object.

[0076] [Experimental Example 3] Next, we considered the use of antifungal agents as a chemical antifungal method. Among commonly used antifungal agents, three were selected: diphenyl, o-phenylphenol, and thiabendazole. (A fluorinated solvent (ASAHIKLIN® AE-3000, manufactured by AGC Corporation) was used as the solvent.) In addition, a first phase (phase 1 solution) containing an aqueous solution containing a radical source and a radical-generating catalyst was used as the cleaning solution. After immersion in each chemical solution for one day and night, the plants were cultured on PDA medium as in Experimental Example 2. As a result, diphenyl, o-phenylphenol, and thiabendazole exhibited antifungal effects at 1,000 ppm, while the antifungal effect was confirmed at 10 ppm or higher for the phase 1 solution (Table 2). [Table 2]

[0077] [Experimental Example 4] After treatment with the first phase solution in the same manner as in Experimental Example 3, the paper pieces were observed under a scanning electron microscope to confirm whether or not there had been any physical alteration to the paper samples that had been subjected to the dewatering treatment with a fluorine-based solvent (ASAHIKLIN (registered trademark) AE-3000 manufactured by AGC Corporation) in the same manner as in Experimental Example 1. No noticeable swelling of the cellulose fibers was observed in the paper samples (Figure 5). These observation results support the fact that there was almost no physical alteration to the paper samples as a result of this treatment, even at a microscopic level.

[0078] [Experimental Example 5] The protection of objects requires speed (elimination of water impregnation) and simplicity (elimination of the need for fumigation equipment, etc.). To achieve this, we conceived the idea of ​​combining a mixture of the first phase solution and a fluorinated solvent (ASAHIKLIN® AE-3000, manufactured by AGC Corporation) to combine the physical cleaning effect of the fluorinated solvent confirmed in Experimental Example 2 with the chemical cleaning effect (antifungal effect) of the first phase solution confirmed in Experimental Example 3. To prepare the first phase solution / fluorinated solvent mixture, the first phase solution and the fluorinated solvent were mixed at a volume ratio of 1:1. After allowing the mixture to stand, the upper water-soluble fraction was removed with a dropper to obtain a fluorinated solvent with the effects of the first phase solution ("fluorinated solvent with first phase effect"). In the same manner as in Experiments 2 and 3, 1.0 cm pieces of each sample (Western paper, Japanese paper, parchment, cowhide, and wood) with mold cells attached were immersed for one day and one night in this fluorinated solvent with a Phase 1 effect, and then cultured for two days and two nights on PDA medium. The results are shown in Table 3 (Streptomyces flavus) and Table 4 (Eurotium herbariorum), confirming the physical and chemical cleaning effects of the fluorinated solvent with a Phase 1 effect on the target objects. [Table 3]

[0079] [Table 4]

[0080] [Experimental Example 6] Before and after the cleaning process in Experimental Example 5, the amount of the fluorine-based solvent itself was unlikely to decrease, but the radical source in the first phase solution was consumed by chemical reactions with the fungal cells. In light of this, in this experimental example, we came up with the idea of ​​extracting the radical source from the consumed first phase solution from a newly prepared first phase solution, and conducted the following experiment. As in Experimental Example 5, 100 ppm of the first phase solution was mixed with a fluorinated solvent (ASAHIKLIN® AE-3000, manufactured by AGC Corporation) at a volume ratio of 1:1. After allowing to stand, the fluorinated solvent alone was collected with a dropper to obtain a fluorinated solvent imparted with the effects of the first phase solution ("first phase effect-imparted fluorinated solvent"). As in Experimental Example 4, 1.0 cm pieces of each sample (Western paper, Japanese paper, parchment, cowhide, and wood) with fungal cells attached were immersed in this first phase effect-imparted fluorinated solvent for one day and overnight, and then cultured on PDA medium for two days and overnight (initial cycle). The first phase effect-imparted fluorinated solvent used in the initial cycle was further mixed with fresh 100 ppm of the first phase solution at a volume ratio of 1:1, and the subsequent procedures were the same as in the initial cycle (first recycling). The fluorinated solvent used in the first recycle was mixed with a fresh 100 ppm first phase solution at a volume ratio of 1:1, and the subsequent procedure was the same as in the initial cycle (second recycle). The results are shown in Table 5 (Streptomyces flavus) and Table 6 (Eurotium herbariorum).

[0081] [Table 5]

[0082] [Table 6]

[0083] [Experimental Example 7] In Experimental Example 6, a new first phase solution was prepared and brought into contact with the fluorinated solvent each time. However, in this Experimental Example, instead of this process, a method of recycling the first phase solution was conceived in which multiple fluorinated solvents were prepared for one first phase solution and brought into contact with it multiple times, and the following experiment was carried out. As in Experiment 5, 100 ppm of the first phase solution was mixed with a fluorinated solvent (ASAHIKLIN AE-3000, manufactured by AGC Corporation) at a volume ratio of 1:1. After allowing to stand, the fluorinated solvent alone was collected to obtain a fluorinated solvent with the effects of the first phase solution ("fluorinated solvent with first phase effect"). As in Experiment 4, 1.0 cm pieces of each sample (western paper, Japanese paper, parchment, cowhide, and wood) with fungal cells attached were immersed in this fluorinated solvent with first phase effect for one day and then cultured on PDA medium for two days and two nights (initial cycle). The first phase solution used in the initial cycle was mixed with fresh fluorinated solvent (ASAHIKLIN AE-3000, manufactured by AGC Corporation) at a volume ratio of 1:1, and the subsequent procedures were the same as in the initial cycle (first recycling of the first phase solution). The first phase solution used in the first recycling was mixed with a new fluorinated solvent (ASAHIKLIN AE-3000 manufactured by AGC Corporation) in a volume ratio of 1:1, and the subsequent procedure was the same as in the initial cycle (second recycling of the first phase solution).The first phase solution used in the second recycling was mixed with a new fluorinated solvent (ASAHIKLIN AE-3000 manufactured by AGC Corporation) in a volume ratio of 1:1, and the subsequent procedure was the same as in the initial cycle (third recycling of the first phase solution).The results are shown in Table 6 (Streptomyces flavus) and Table 7 (Eurotium herbariorum).

[0084] [Table 7]

[0085] [Table 8]

[0086] The results of Experimental Examples 6 and 7 demonstrated the possibility of recycling the fluorinated solvent or the first phase solution multiple times, and showed that the antifungal effect that is reduced by cleaning can be restored by simply performing a simple operation after cleaning.

Claims

1. A composition for cleaning objects that are reluctant to be washed with water, comprising: a first phase comprising an aqueous solution containing a radical-generating source and a radical-generating catalyst; and A second phase containing an organic solvent Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, A composition, characterized in that the organic solvent containing the radicals of the second phase in the composition is applied to clean the object.

2. The composition of claim 1 , wherein the object contains microbial contamination.

3. The composition of claim 2 , wherein the microorganism is a bacterium and / or a fungus.

4. 10. The composition of claim 1, wherein the object is selected from the group consisting of paper, papyrus, bark cloth, wood, bamboo, animal hide, and fabric.

5. The composition according to claim 1 , wherein the organic solvent is a fluorinated solvent.

6. 6. The composition according to claim 5, wherein the fluorine-based solvent is selected from the group consisting of hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs), hydrofluoroolefins (HFOs), hydrochlorofluoroolefins (HCFOs), and perfluorocompounds.

7. 2. The composition according to claim 1, wherein the radical generating source is at least one selected from the group consisting of a haloid acid, a haloid ion, and a haloid salt.

8. 2. The composition according to claim 1, wherein the radical generating source is chlorous acid, chlorite ions, or chlorite salts.

9. 2. A method for producing a composition for cleaning objects that are resistant to water-based cleaning according to claim 1, comprising: contacting a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst with a second phase containing an organic solvent, and extracting radicals generated from the radical generating source in the first phase into the second phase; Including, wherein the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source; A manufacturing method, characterized in that the organic solvent containing the radicals of the second phase in the composition is applied to cleaning the object.

10. A kit for producing a composition for cleaning objects that are resistant to water-based cleaning according to claim 1, comprising: a first phase including an aqueous solution containing a radical generating source and a radical generating catalyst; a second phase comprising an organic solvent; Including, the organic solvent is water-insoluble and capable of extracting radicals generated from the radical generating source, contacting the first phase with the second phase to form a first phase containing an aqueous solution containing a radical generating source and a radical generating catalyst, and a second phase containing an organic solvent; extracting radicals generated from the radical generating source in the first phase into the second phase; The organic solvent containing the radicals of the second phase is applied to wash the object.

11. A method for cleaning an object that should not be cleaned with water, comprising the steps of:

11. A method for cleaning an object by contacting the organic solvent containing the radicals in the second phase with the composition according to claim 1, the composition obtained by the production method according to claim 9, or the composition prepared from the kit according to claim 10. A cleaning method comprising:

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