JP2005306790A - Radical-containing disinfectant material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a disinfectant material for effectively carrying out disinfection of microorganisms, viruses, etc. <P>SOLUTION: The disinfectant material comprises a radical derived from formaldehyde. Heating formaldehyde generates the radical in the disinfectant material. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gaseous or liquid bactericidal material containing radicals. The present invention also relates to a method for easily generating radicals.

Conventionally, ethylene oxide gas (EOG), ozone, etc. are known as gas used for sterilization of medical devices (Patent Documents 1 to 3),
Moreover, sodium hypochlorite solution etc. are used as a liquid disinfectant.
EOG is highly toxic and has a problem of remaining on the sterilized material. Ozone has not only a surface sterilization due to its poor permeability, but also has a strong corrosive defect.
Further, sodium hypochlorite is a halogen-based disinfectant, and has problems such as generation of trihalomethane and generation of hydrogen chloride under acidic conditions.

A sterilization system using radical gas (methanol radical: MR) generated by catalytic reaction from methanol has a strong sterilizing power higher than EOG and has been confirmed to have no persistence and corrosivity (non-non-toxic). Patent Document 1).
However, since methanol radicals are generated in a relatively small amount, it is desirable to use a sterilization system that easily generates radicals.
JP 2001-212217 A Japanese Patent Laid-Open No. 11-226094 JP2002-17830 Kyoko Takada, Yoshiaki Fukuda, Kazumichi Kojima, Tokunori Koike, Eiji Sano, Eiichi Minaya, Akio Futaki "Verification of bactericidal power in MR gas sterilization system" The 81st Annual Meeting of the Chemical Society of Japan, 2002.3

An object of this invention is to provide the bactericidal material which can perform disinfection of microorganisms, a virus, etc. effectively with a smaller amount of bactericides.

As a result of intensive studies, the present inventors have found that radicals are generated simply by heating a formaldehyde solution (for example, an aqueous solution), and microorganisms can be effectively sterilized, thereby completing the present invention.
The present invention provides the following inventions.
1. Bactericidal material containing radicals derived from formaldehyde.
2. Item 2. The disinfectant material according to Item 1, wherein the radical is generated by heating formaldehyde.
3. Item 4. The material according to any one of Items 1 to 3, further comprising at least one selected from the group consisting of hydrogen peroxide, methanol, and ethanol.
4). A method for generating radicals derived from formaldehyde, comprising heating formaldehyde or an aqueous solution thereof in a gaseous or liquid state.
5). A method for producing a bactericide containing radicals derived from formaldehyde, characterized in that formaldehyde or an aqueous solution thereof is heated in a gaseous or liquid form.
6). A method for sterilizing an article to be sterilized, comprising bringing a sterilizing material containing a formaldehyde-derived radical into contact with the article to be sterilized in liquid or gaseous form.
7). The method according to claim 6, wherein the article to be sterilized is a bacterium.

Hereinafter, the present invention will be described in detail.
The present invention is based on a completely new finding that formaldehyde-derived radicals (hereinafter sometimes referred to as “formaldehyde radicals”) are generated by simply heating formaldehyde in the absence of a catalyst.
For example, in the case of an aqueous formaldehyde solution, the heating conditions can be obtained by heating at a temperature of about 50 to 100 ° C. and evaporating the solution. The concentration of formaldehyde is not particularly limited, but is, for example, about 0.001 to 99% by weight, preferably about 0.01 to 90% by weight, and more preferably about 0.1 to 50% by weight. When the concentration of formaldehyde is too low, the amount of radical generation is reduced, and when the concentration is too high, the amount of formaldehyde monomer (HCHO) is reduced and the generation efficiency of radicals is reduced.
Formaldehyde radicals exist stably even in gaseous form, and exist stably even in solution form. Further, even if gaseous formaldehyde radicals are condensed on the surface of the substance and become liquid, the radicals can exist stably.
When the aqueous formaldehyde solution is heated to 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 80 ° C. or higher, formaldehyde radicals can be generated even in the aqueous solution state.
A gas containing formaldehyde radicals is preferable because it has sufficient radical stability at a temperature of about 0 ° C to 100 ° C, preferably about 10 ° C to 80 ° C. The gaseous formaldehyde radical can exist stably at a relative humidity of about 20 to 90%.
Although the formaldehyde radical of the present invention can be obtained by heating liquid formaldehyde, the amount of radicals can be increased by heating gaseous formaldehyde vapor evaporated at a low temperature under normal pressure or reduced pressure. It is.
The disinfectant of the present invention is characterized by containing a radical together with formaldehyde. Formaldehyde may exist in a liquid state such as an aqueous solution or a hydrous alcohol solution, or may be gaseous. Gaseous formaldehyde may be prepared, for example, by volatilizing the formaldehyde solution under reduced pressure, or by heating and evaporating the formaldehyde solution.
In order to allow liquid formaldehyde to coexist with radicals, for example, a radical generation source may be added to a formaldehyde solution, and the radical generation source may be decomposed to generate radicals. , X-rays, γ-rays) to generate radicals. Further, it may be generated by condensing wet steam containing gaseous formaldehyde (a high humidity mixture of gaseous water vapor and formaldehyde).
Radical generation sources include AIPH, AIBN, t-butyl hydroperoxide, di-t-butyl peroxide, peroxydicarbonate (eg, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxycarbonate, di-n-propyl Peroxycarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, etc.) and diacyl peroxide (octanonyl peroxide, succinic acid peroxide, benzoyl peroxide, etc.).
When radicals are generated by ultrasonic waves, ultrasonic irradiation can be carried out under conditions of a normal frequency of 10 kHz to 10 MHz and an output of 1 W or more. Although irradiation time is not specifically limited as long as sterilization is realizable, about 0.1 to 100 minutes can be mentioned.
When radicals are generated by ultraviolet rays, examples of the ultraviolet ray generation source include metal halide lamps, high-pressure mercury lamps, xenon lamps, low-pressure mercury lamps, medium-pressure mercury lamps, and deuterium lamps. The irradiation amount of ultraviolet rays is, for example, 5 to 50 W · hr · / m ³ per 1 mg / L of formaldehyde solution concentration.
The bactericidal material of the present invention includes formaldehyde. The formaldehyde content is about 0.001 to 99% by weight in the case of liquid, preferably about 0.01 to 90% by weight, more preferably about 0.1 to 50% by weight. It is about 10000 ppm, Preferably it is about 10-5000 ppm.
Gaseous formaldehyde radicals can be generated simply by heating an aqueous formaldehyde solution, but the amount of radicals generated can be increased by contacting with a catalyst.
Catalysts for generating radicals include catalysts such as silica, zirconia, alumina, diatomaceous earth, and noble metal (Pt, Ni, Pd, Cu, etc.) supported catalysts. These catalysts and formaldehyde are reacted in the gas phase to generate radicals. The amount can be increased. The temperature for generating radicals by reacting with the catalyst is from room temperature to about 100 ° C, preferably from about 40 ° C to 90 ° C.
You may mix | blend at least 1 sort (s) chosen from the group which consists of hydrogen peroxide, methanol, and ethanol with the bactericidal material containing the formaldehyde radical of this invention with formaldehyde. For example, when formaldehyde and formaldehyde radical coexist in a gaseous state, the sterilizing action of formaldehyde can be further enhanced by further blending these volatile solvents.
In one of the preferred embodiments, the sterilizing material containing formaldehyde of the present invention is heated and vaporized, and brought into contact with the catalyst in a gaseous state as necessary to form a processing gas containing radicals, and a sealed containing an object to be sterilized. Supplied to the space.
Examples of organisms sterilized with the bactericidal material of the present invention include bacteria (for example, pathogenic bacteria, multidrug resistant bacteria, genetically modified bacteria, etc.), viruses (influenza virus, SARS, HIV, herpes virus, cytomegalovirus, hepatitis). Examples include viruses (A type, B type, C type, etc.), fungi, molds and the like.
The object to be sterilized is not particularly limited, but includes medical facilities such as hospitals, medical instruments, rooms (floors, walls, wallpaper, ceilings), lab coats, sheets, beds, etc., or facilities that handle microorganisms or genetic modification. Examples include experimental facilities and instruments.

According to the present invention, the sterilization / sterilization effect of formaldehyde can be greatly enhanced by the combined use of radicals, and a bactericidal material having an excellent sterilization effect can be obtained using a small amount of formaldehyde.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples.
Materials and methods Cells: Human T lymphoma Jurkat cells are used. RPMI-1640 medium containing 10% bovine serum was used for cell culture and reaction.
Measuring the number of living cells; Measure mitochondrial dehydrogenase activity in living cells and measure the relative cell volume.
MTT (yellow) → MTT formazan (purple; 570nm)
MTT is 3- (4,5-dimethylthiazol-2-yl-2,5-diphenyl tetrazolium bromide.
experimental method:
According to the following protocol, the effect of the bactericidal material of the present invention on cell viability was examined.
Jurkat cell (5x105 cells / ml)
↓ Bactericidal material (gaseous) 1hr (40 ℃)
↓ Exhaust, 20min (room temperature)
↓ MTT Assay, 2hr (37 ° C)
MTT formazan (A570)
Example 1
Using a radical initiator (AIPH), HCHO, and Trolox at the concentrations shown in FIG. 1, cell viability was measured according to the above protocol. The results are shown in FIGS.

Example 2
In a solution (benzene: acetonitrile = 2: 1), 33 mM spin labeling agent MDN (methyl-N-durylnitrone) was reacted with 100 mM HCHO or 0 mM HCHO at 37 ° C. for 2 hours. After the reaction, ESR analysis was performed. . The results of ESR analysis are shown in FIG. 3 (0 mM HCHO; 100 mM HCHO).
In the control (0 mM HCHO), no significant ESR signal was detected between the left and right Mn-derived peaks. In addition, if a radical is generated in the solution and reacts with MDN, six peaks appear in the center. On the other hand, when reacted with 100 mM HCHO for 2 hours, six peaks were detected as shown in FIG. That is, it shows that radicals are generated only by heating HCHO in solution.

Effects of radicals and formaldehyde on cell viability Effects of radicals and formaldehyde on cell viability The ESR measurement result of 0 mM HCHO and 100 mM HCHO is shown.

Claims (7)

Bactericidal material containing radicals derived from formaldehyde. The bactericidal material according to claim 1, wherein the radical is generated by heating formaldehyde. Furthermore, the material in any one of Claims 1-3 containing at least 1 sort (s) chosen from the group which consists of hydrogen peroxide, methanol, and ethanol. A method for generating radicals derived from formaldehyde, comprising heating formaldehyde or an aqueous solution thereof in a gaseous or liquid form. A method for producing a bactericide containing radicals derived from formaldehyde, characterized by heating formaldehyde or an aqueous solution thereof in a gaseous or liquid form. A method for sterilizing an article to be sterilized, comprising bringing a sterilizing material containing a formaldehyde-derived radical into contact with the article to be sterilized in liquid or gaseous form. The method according to claim 6, wherein the article to be sterilized is a bacterium.

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