JP2006278644A - Cleaning method and cleaning device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning method and a cleaning device which offer cleaning effect by a surfactant and a decomposing/sterilizing effect by ozone, at the same time. <P>SOLUTION: An ozone-containing cleaning solution provided by dissolving ozone into a saturated fatty group surfactant solution that does not have the inter-carbon double bond expressed by general following Formula is used to carry out cleaning by the surfactant and decomposition/sterilization by the ozone in a single process. In the Formula (R)<SB>n</SB>-X, R denotes a hydrophobic group comprising a saturated hydrocarbon or of a saturated halocarbon compound, n denotes an integer of 1, 2, or 3, and X denotes a hydrophilic compound having any one of ether group, hydroxyl group, ester group, carboxyl group, sulfonic group, and amino group, each group not having an inter-carbon double bond and an aromatic group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning method and a cleaning apparatus that can be suitably used, for example, for removing organic substances attached to a substrate surface, and for cleaning and sterilizing various medical tools such as endoscopes and surgical tools used in a medical field.

  In the manufacture of electronic device substrates such as semiconductor wafers and liquid crystal substrates, it is necessary to remove the resist adhering to the substrate surface during the process, and a cleaning process to remove general organic films such as oil films and coating films. It is.

  For example, when a circuit is formed on a compound substrate such as a silicon substrate or a gallium arsenide substrate, and a plurality of colored pixels having different hues are formed in a pattern on a liquid crystal substrate, it corresponds to a circuit pattern to be formed on these. When manufacturing a mask substrate having the mask pattern, a photolithography process is essential. When a circuit is formed on a silicon substrate, a resist is applied on a silicon wafer, an image composed of a resist pattern is formed by a normal photo process, and etching is performed using this as a mask, and then unnecessary resist is removed. Then, in order to form a circuit and form the next circuit, a resist is applied again, and a cycle of image formation-etching-resist removal is repeated.

  In the process of removing the resist that is no longer necessary, conventionally, an RCA cleaning method using an asher (ashing means), sulfuric acid, hydrogen peroxide, or the like is used. However, if an asher is used for resist removal, inorganic impurities cannot be removed. In addition, when removing a resist using a solvent or chemical, it must be replaced with a new chemical every ten or more batches, which requires a large amount of chemical and increases the cost and generates a large amount of waste. For this reason, there is a problem in that the waste liquid treatment is costly and further affects the environment.

  On the other hand, in recent years, an organic substance removal method using ozone has been proposed and put into practical use because it has the oxidizing power next to fluorine in nature, and becomes harmless oxygen immediately after use, so that it has little impact on the environment. (See, for example, Patent Document 1).

  Conventionally, when cleaning and sterilizing medical devices, for example, heat sterilization using steam after cleaning with cleaning water is performed. In the field of cleaning medical devices, sterilization using ozone is performed for the reasons described above. A sterilization method has been proposed and is being put into practical use (for example, see Patent Document 2).

Japanese Patent Laid-Open No. 2003-10895 Japanese Patent Laid-Open No. 11-105834

By the way, in the manufacturing process of the substrate, the resist that is applied on the substrate for circuit formation and becomes unnecessary after the etching and is removed, so that the unmodified resist can be removed by a single treatment with ozone water. is there.
However, in a general substrate manufacturing process, there are resists modified by ion doping, ashing, etching treatment, etc., which are not easily decomposed by ozone water, and complete removal of these resists is difficult by using ozone water alone.
In general resist stripping reagents, a surfactant is added to cope with these modified resists, thereby enhancing the resist stripping effect. However, when ozone is dissolved, only a surfactant having a specific structure that is not decomposed by ozone can be used.

  In addition, human tissue or protein adheres to the surgical tool after use, and ozone treatment alone is insufficient to remove such solid deposits. Therefore, generally, before and after the ozone treatment, washing is performed using a surfactant or the like to remove the solid components, which causes a problem that the process becomes complicated and the washing and sterilization takes time.

  Therefore, the inventors of the present application have considered using a cleaning solution in which ozone is dissolved in a surfactant. However, surfactants usually used for cleaning substrates and cleaning devices such as medical devices are resistant to ozone. It is low, and there is a possibility that it will deteriorate and decompose by reacting with ozone.

As the most classic method for dissolving ozone, there is an aeration method in which ozone gas is dispersed in water and dissolved. However, when ozone gas is aerated in the surfactant solution, bubbles are generated, and there is a problem that it is very difficult to separate the ozone gas and the surfactant solution thereafter.
In addition, an ozone dissolution method using a porous film is used in some fields. In this method, fine pores are opened in the membrane, and the surface pressure of water is used to adjust the water pressure to be about 0.05 MPa higher than the ozone gas pressure. It is supposed to dissolve in. However, when a porous membrane is used, there is a problem that when the surfactant is dissolved in water, the surface tension decreases, and the surfactant solution flows into the ozone gas even with a slight pressure.

The present invention has been made in view of such conventional circumstances, processing is an object of the present invention, the cleaning action of the surfactant, degradation by ozone, it is possible to obtain a bactericidal action simultaneously, specifically, Resist removal on substrates for electronic devices allows simultaneous removal of resist on the substrate by cleaning action with surfactant and decomposition action with ozone. In medical devices, cleaning with surfactants and decomposition and sterilization with ozone are performed. and to provide a novel cleaning method and apparatus Ru can be performed simultaneously.

  In order to achieve the above object, the inventors of the present application have continued intensive research and found that a surfactant having a certain structure is excellent in ozone resistance, and the cleaning action by the surfactant and the decomposition and sterilization by ozone. By using an ozone-containing cleaning solution that also has an action, it has been found that the ozone treatment process and the cleaning process, which have been carried out separately so far, can be shortened to one process, and furthermore, by using a film body having a special structure The inventors have found that ozone can be efficiently dissolved in this specific surfactant, and have completed the present invention.

  That is, the present invention provides a surfactant using an ozone-containing cleaning solution in which ozone is dissolved in a solution of a saturated aliphatic surfactant having no carbon-carbon double bond represented by the following general formula (1). The cleaning method is characterized in that the cleaning by, and the decomposition and sterilization by ozone are performed simultaneously.

(R) _n -X (1)
Wherein R is a hydrophobic group comprising a saturated hydrocarbon or a saturated halogenated carbon compound,
n is an integer of 1 to 3, X is an ether group having no carbon-carbon double bond and an aromatic group,
Any one of hydroxyl group, ester group, carboxyl group, sulfone group and amino group
Represents a hydrophilic group compound having one. )

  The surfactant used in the present invention has a property excellent in ozone resistance. Specifically, the hydrophobic group (R) is composed of a saturated hydrocarbon or a saturated halogenated hydrocarbon, and is an unsaturated hydrocarbon. Or, aromatic hydrocarbons are not included. Although carbon number is not specifically limited, About 10-30 is preferable. Further, a plurality of hydrophobic groups (R) may be present in one molecule. And, as the hydrophilic group (X), a nonionic surfactant having a hydroxyl group or an ether group having no carbon-carbon double bond, or an anionic surfactant of carboxylic acid, sulfonic acid or a salt thereof is used. Can do.

Hereinafter, more specific surfactants that can be used in the present invention are exemplified.
(Nonionic surfactant)
Glycerin series: Glycerin monostearate, glycerin monolaurate and their di- and trialkane compounds Sorbitol series: Sorbitan monostearate, sorbitan monolaurate and their di- and trialkane compounds Mannitol series: Mannitol monostearate, monolaur Rates and their di- and trialkane compounds Hentaerythritol series: Hentaerythritol monostearate, Hentaerythritol monolaurate and their di- and trialkane alkane compounds Other saccharide-based alkane compounds Polyethylene glycol series: Polyethylene glycol 300 monooctyl ether, Polyethylene glycol 600 monooctyl ether, polyethylene glycol 300 monododecyl ether

(Anionic surfactant)
Carboxylic acid and its salt: Lauric acid, stearic acid, etc. and their salts. As the salts, ammonium, sodium, calcium, lithium, and the like that become water-soluble are desirable.
Polybasic acids and salts thereof: Partially esterified products such as citric acid and oxalic acid and salts thereof. As the salts, ammonium, sodium, calium, lithium and the like are desirable.
Sulfonic acid and its salts: lauric acid, stearic acid and their salts. As the salts, ammonium, sodium, calium, lithium and the like are desirable.

The ozone-containing cleaning liquid used in the present invention is preferably a solution of the saturated aliphatic surfactant obtained by dissolving ozone using a non-porous film that allows gas to permeate but not liquid.
When a porous membrane is used, the gas dissolves in the liquid through the liquid soaked in the pores, so the ozone gas pressure must be strictly adjusted to be lower than the liquid pressure in order to soak the liquid in the pores. . On the other hand, in the non-porous film, it is not necessary to make the ozone gas pressure lower than the liquid pressure, and ozone can be efficiently dissolved using the pressure of the ozone gas.

  Non-porous membranes include synthetic resin materials having excellent ozone resistance and ozone gas permeability, such as fluorine-based resins such as polytetrafluoroethylene copolymer (PTFE) and perfluoroalkoxy resin (PFA), Those formed into a flat membrane shape, a hollow fiber shape (tube shape) or the like with a silicon-based resin such as dimethylsiloxane or methyl silicone rubber can be preferably used. The hollow fiber-shaped material is preferably used as a bundled hollow fiber-shaped gas permeable membrane by bundling a plurality of the fibers and heat-sealing or bonding the end portions thereof.

  If the ozone-containing cleaning solution exceeds pH 8, dissolved ozone may be decomposed, which is not preferable. Therefore, the ozone-containing cleaning liquid used in the present invention preferably has a pH of 8 or less.

More preferably, it is in the range of pH 5 to pH 7. In this range, the cleaning ability by the surfactant and the decomposition and sterilization action by ozone are exhibited in a well-balanced manner, and the organic substance removal from the substrate surface and the cleaning / sterilization of the medical device are performed. It can use suitably for.
Moreover, the solvent (for example, acetone, t-butyl alcohol) etc. which are not decomposed | disassembled by ozone with the solution used for this invention can be mixed in arbitrary ratios.

  The cleaning method according to the present invention uses an ozone-containing cleaning solution in which ozone is dissolved in a solution of a saturated aliphatic surfactant having no carbon-carbon double bond represented by the general formula (1). It can be easily carried out by a cleaning device configured to perform cleaning with an activator and decomposition and sterilization with ozone at the same time.

When applying the cleaning method according to the present invention the organic removal adhering to the substrate surface, such as a semi-conductor wafer or a liquid crystal substrate, at least, include a washing step of supplying a cleaning liquid to the substrate accommodated in the reaction vessel, wherein the cleaning liquid , An ozone-containing cleaning solution in which ozone is dissolved in a saturated aliphatic surfactant solution having no carbon-carbon double bond represented by the general formula (1), and is formed on the substrate surface in the cleaning step. resist removal can be preferably used at the same time the line dividing organic substance removing method to degradation by cleaning with ozone by the surfactant.

This organic substance removal method is an apparatus for removing organic substances adhering to the surface of a substrate such as a semiconductor wafer or a liquid crystal substrate, and includes at least a reaction tank that accommodates the substrate, and a cleaning liquid supply that supplies an ozone-containing cleaning liquid to the reaction tank The cleaning liquid supply means includes a surfactant solution supply path, an ozone gas supply path, and a non-porous film that allows gas to pass through but does not pass through liquid. Ozone in the ozone gas supplied from the ozone gas supply path is dissolved in the surfactant solution supplied from the surfactant solution supply path, and the obtained ozone-containing cleaning liquid is supplied into the reaction vessel; at the reaction vessel, and washing with detergent, the configuration organics removal apparatus to perform the decomposition by ozone at the same time, can be easily performed.

When the cleaning method according to the present invention is applied to cleaning and sterilization of medical devices such as endoscopes and surgical tools, at least a cleaning step using a cleaning solution is included, and the cleaning solution is represented by the general formula (1). This is an ozone-containing cleaning solution in which ozone is dissolved in a saturated aliphatic surfactant solution having no carbon-carbon double bond. In the cleaning step, cleaning with a surfactant, decomposition and sterilization with ozone are performed simultaneously. The cleaning / sterilization method for the medical device to be performed can be preferably used.

This cleaning and sterilization method is an apparatus for cleaning and sterilizing medical tools such as endoscopes and surgical tools, and includes at least an ozone-containing cleaning liquid generator and a cleaning tank for storing an object to be cleaned. A surfactant solution supply path, an ozone gas supply path, and a non-porous film that allows gas to pass through but does not transmit liquid, and is supplied from the ozone gas supply path through the non-porous film. The ozone in the ozone gas is dissolved in the surfactant solution supplied from the surfactant solution supply path, and the obtained ozone-containing cleaning liquid is supplied to the cleaning tank. This can be easily performed by a cleaning / sterilization apparatus for medical devices configured to simultaneously perform cleaning and sterilization with ozone.
Moreover, according to this washing | cleaning sterilization apparatus, since the production | generation part of the ozone containing washing | cleaning liquid and the washing tank of the to-be-washed | cleaned object are provided, the above-mentioned effect can be acquired, setting it as a compact apparatus structure.

  As described above, since the present invention uses an ozone-containing cleaning solution in which ozone is dissolved in a predetermined surfactant solution, it is possible to simultaneously obtain a cleaning action by a surfactant and a decomposition and sterilization action by ozone. Therefore, compared with the prior art in which it is necessary to separately perform a treatment process using ozone water and a cleaning process using a surfactant or the like, the surface treatment of an object to be processed can be performed in a shorter time, for example, a semiconductor wafer, It can be suitably used for removal of organic substances from a liquid crystal substrate and other substrates, and cleaning and sterilization of endoscopes, surgical tools, and other medical tools.

Embodiments of a cleaning method according to the present invention will be described below with reference to the drawings.
FIG. 1 shows an example in which the present invention is implemented as a resist removal apparatus for an electronic device substrate. This organic substance removal apparatus A includes a cleaning liquid supply means 1 for supplying an ozone-containing cleaning liquid, a semiconductor wafer, a liquid crystal substrate, and the like. The reaction tank 2 containing the substrate (hereinafter referred to as “object to be cleaned”) is provided, and the object to be cleaned in the reaction tank 2 is cleaned with the ozone-containing cleaning liquid supplied from the cleaning liquid supply means 1 and is oxidized by ozone. The decomposition process is performed simultaneously.

  The cleaning liquid supply means 1 includes an ozone gas generator 3, a liquid feed pump 4 for sending a surfactant, a liquid feed pump 5 for sending raw material water (pure water), an ozone dissolution module 6, ozone detectors 7 and 8, and the like. ing. Then, the secondary side of the liquid feed pump 4 is connected to the secondary side of the liquid feed pump 5 in the pure water supply line 9, and the surfactant solution having a predetermined concentration is supplied to the ozone dissolution module 6. The solution supply path 10 is formed, and the ozone gas generated by the ozone gas generator 3 is supplied to the ozone dissolution module 6 through the ozone gas supply path 11, and in the ozone dissolution module 6, the solution is supplied into the surfactant solution. It is designed to dissolve ozone.

  As shown in FIG. 2 (a), the ozone dissolution module 6 is divided into a plurality of baffle plates 13 partially provided with through holes or notches, and the center where the baffle plates 13 are connected. A bundle of hollow fiber gas permeable membranes 15 wound around an axis 14 and supplied to each hollow fiber (tube-like) gas permeable membrane 16 constituting the bundle of hollow fiber gas permeable membranes 15. The ozone in 17 is dissolved in the surfactant solution 18 supplied into the case 12 through a bundle of hollow fiber gas permeable membranes 15 to generate an ozone-containing cleaning liquid 19.

  The hollow fiber-shaped gas permeable membrane 16 is excellent in ozone resistance and is a synthetic resin material that transmits gas but does not transmit liquid, for example, fluorine resin such as polytetrafluoroethylene copolymer (PTFE), polydimethylsiloxane, etc. A hollow fiber-shaped gas permeable membrane (non-porous membrane) 15 is formed by bundling a plurality of silicon-based resins into a hollow fiber shape (tube shape) and heat-sealing or bonding the ends thereof. It is composed.

The ozone-containing cleaning liquid 19 generated by the ozone dissolution module 6 is supplied to the reaction tank 2 through the ozone detector 8 through the cleaning liquid supply line 20.
Excess ozone gas 21 discharged from the ozone dissolution module 6 is discharged to the ozone treatment tower 23 via the discharge pipe 22 and reduced to oxygen.

  As shown in FIG. 2 (b), the ozone dissolution module 6 may be a module in which a bundle of hollow fiber gas permeable membranes 15 is arranged in a straight line at the axial center in the case 12 '.

  The ozone detectors 7 and 8 detect and measure the ozone concentration in the ozone-containing cleaning liquid 19 supplied from the ozone dissolution module 6, and based on the result, the ozone gas supply amount from the ozone gas generator 3 or the surface activity. The amount of the surfactant supplied by the liquid feed pump 4 for sending the agent is appropriately adjusted to obtain an ozone-containing cleaning liquid 19 having a predetermined concentration (pH 8 or lower).

  The surfactant supplied by the feed pump 4 for delivering the surfactant is a saturated aliphatic surfactant having no carbon-carbon double bond represented by the following general formula (1). Can use the nonionic surfactant or the anionic surfactant described above.

(R) _n -X (1)
Wherein R is a hydrophobic group comprising a saturated hydrocarbon or a saturated halogenated carbon compound,
n is an integer of 1 to 3, X is an ether group having no carbon-carbon double bond and an aromatic group,
Any one of hydroxyl group, ester group, carboxyl group, sulfone group and amino group
Represents a hydrophilic group compound having one. )

A cleaning liquid supply pipe 20 is connected to the reaction tank 2 so that an ozone-containing cleaning liquid 19 is supplied. With the ozone-containing cleaning liquid, cleaning with a surfactant solution and oxidation and decomposition treatment with ozone are performed. While performing simultaneously, each process, such as subsequent drainage and washing | cleaning (rinsing), is comprised so that it may be automatically performed as needed.
Excess ozone gas discharged from the reaction tank 2 is discharged to the ozone treatment tower 25 through the discharge pipe 24 and reduced to oxygen.

  According to the organic substance removing apparatus A of the present example having the above configuration, since the ozone-containing cleaning liquid 19 in which ozone is dissolved in a predetermined surfactant is used, cleaning with the surfactant and oxidation / decomposition treatment with ozone are performed together. Simultaneously in the process, the resist and other organic substances on the substrate surface can be removed efficiently in a shorter time.

  FIG. 3 shows an example in which the present invention is implemented as a medical instrument cleaning and sterilizing apparatus. This cleaning and sterilizing apparatus A ′ includes an ozone-containing cleaning liquid generator 30, an endoscope, a surgical tool, and other medical tools ( A cleaning unit 32 containing a cleaning tank 31 for storing the object to be cleaned (hereinafter referred to as “object to be cleaned”) is provided, and cleaning and sterilization of the object to be cleaned in the cleaning tank 31 are simultaneously performed by the ozone-containing cleaning liquid supplied from the generation unit 30. Is configured to do.

  The ozone-containing cleaning liquid generation unit 30 includes an ozone gas generator 33, a surfactant filler 34, a liquid feed pump 35, an ozone dissolution module 36, an ozone concentration meter 37, a heater 38, and the like. Then, a surfactant filling device 34 is disposed in the middle of the supply line 39 of pure water supplied from the water supply source, and a predetermined amount of surfactant is supplied to the supply line 39 so that an interface with a predetermined concentration is provided. The activator solution is supplied to the ozone dissolution module 36 via the liquid feed pump 35, and the ozone gas generated by the ozone gas generator 33 is supplied to the ozone dissolution module 36 via the gas pipe 40. Thus, ozone is dissolved in the surfactant solution.

  The ozone dissolution module 36 has the same configuration as that shown in FIG. 2A or 2B described above, and the ozone in the ozone gas 17 supplied to each hollow fiber-like (tube-like) gas permeable membrane 16 is transferred into the case 12. Is dissolved in the surfactant solution 18 supplied via the bundle of hollow fiber gas permeable membranes 15 to generate an ozone-containing cleaning liquid 19.

The ozone-containing cleaning liquid generated by the ozone dissolution module 36 is supplied to the cleaning tank 31 through the ozone concentration meter 37 through the cleaning liquid supply line 41. A heater (heating means) 38 is disposed in the middle of the cleaning liquid supply pipe 41, and the ozone-containing cleaning liquid is heated to an appropriate temperature by the heater 38 and supplied to the cleaning tank 31.
Excess ozone gas discharged from the ozone dissolution module 36 is discharged to the outside through the discharge pipe 42 and reduced to oxygen.

  The ozone concentration meter 37 measures the ozone concentration in the ozone-containing cleaning liquid supplied from the ozone dissolution module 36, and based on the result, the ozone gas supply amount from the ozone gas generator 33 or the surfactant filler 34. The surfactant filling amount is appropriately adjusted to obtain an ozone-containing cleaning liquid having a predetermined concentration (pH 8 or less).

  The surfactant supplied from the surfactant filler 34 is a saturated aliphatic surfactant having no carbon-carbon double bond represented by the general formula (1).

  The cleaning section 32 is connected with a pipe 41 for supplying an ozone-containing cleaning liquid, a water supply pipe 43 for rinsing water, and a drain pipe 44 in a cleaning tank 31 incorporated therein, and cleaning with ozone-containing cleaning liquid and disinfection with ozone. The sterilization is performed at the same time, and the subsequent processes such as draining, washing (rinsing), and drying are automatically performed as necessary.

  According to the cleaning and sterilizing apparatus A ′ configured as described above, since an ozone-containing cleaning solution in which ozone is dissolved in a predetermined surfactant is used, cleaning with a surfactant and disinfection and sterilization with ozone are performed in one step. At the same time, the medical device can be efficiently cleaned and sterilized in a shorter time. In addition, since the ozone-containing cleaning liquid generation unit 30 and the cleaning tank 31 for the object to be cleaned are provided, the above-described effects can be obtained while having a compact device configuration, and of course, the use in a large-scale hospital is small. It can also be suitably used in large scale hospitals and clinics.

Next, test results for confirming the cleaning action, decomposition, and sterilization action of the ozone-containing cleaning liquid used in the present invention will be described.
Example 1
As a surfactant, 5 L of a 0.1% aqueous solution of sorbitan monostearate (a nonionic surfactant “trade name: Tween 60” manufactured by Kanto Chemical Co., Inc.) that can be used in the present invention is used. When high-concentration ozone water production device “TO-R100S type” manufactured by Sekisui Chemical Co., Ltd. is used, and circulates at a liquid flow rate of 1 L / min. Similarly, an ozone-containing cleaning solution having an ozone concentration of 55 ppm and a pH of 5.1 was obtained, and foaming peculiar to the surfactant solution was also observed, confirming that ozone and the surfactant did not react.
This ozone-containing cleaning liquid was sprayed toward the surface of the sample substrate at a flow rate of 1 L / min with a spray nozzle to perform cleaning and decomposition treatment. As a sample substrate, a phosphorus ion implantation amount of 1.00E + 15, an I-line ion-doped silicon wafer (a positive resist (trade name: THMR IP1800 18cp, manufactured by Tokyo Applied Chemical Co., Ltd.) is spin-coated on a 6-inch silicon wafer, and a resist film A substrate having a thickness of 21500 angstroms) was used.
When the sample substrate after the treatment was observed with a microscope, all resists were peeled from a fine pattern with a width of 1 μm to a resist with a width of 100 μm in the resist film.

(Comparative Example 1)
Ozone water having an ozone concentration of 60 ppm was obtained by the same apparatus as in Example 1 except that ion-exchanged water was used instead of the surfactant solution. When surface treatment was performed with this ozone water under the same conditions using the same sample substrate as in Example 1, the fine pattern portion of 1 μm in the resist film was peeled off, but the wide pattern portion of 10 μm or more was completely peeled off. It wasn't.

(Example 2)
As a surfactant, a polyethylene glycol dodecyl ether (non-ionic surfactant “trade name: Bridge 35” manufactured by Kanto Chemical Co., Inc.) that can be used in the present invention was used. An ozone-containing cleaning liquid having an ozone concentration of 41 ppm and a pH of 7 or less was obtained. In this cleaning liquid, foaming peculiar to the surfactant solution was also observed, and it was confirmed that ozone and the surfactant did not react.
To this ozone-containing cleaning solution, orange II manufactured by Kanto Chemical Co., Inc. was added as a pigment at a rate of 0.03% by weight, and the orange color disappeared after 5 minutes. From this, it was confirmed that the ozone decomposition ability (oxidation and sterilization ability) was not lost even in the presence of the surfactant. Further, when this ozone-containing cleaning solution was used to perform the cleaning and decomposition treatment of the sample substrate in the same manner as in Example 1, the same results as in Example 1 were obtained, and the cleaning ability by the surfactant was not lost. I was able to confirm.

(Example 3)
Example: An anionic surfactant (sodium n-dodecyl sulfate manufactured by Kanto Chemical Co., Inc.) usable in the present invention was used as the surfactant, and the pH was adjusted to 6.5 with acetic acid. In the same manner as in 1, ozone was dissolved. As a result of measuring the ozone concentration after about 20 minutes, an ozone-containing cleaning solution having an ozone concentration of 44 ppm and a pH of 7 or less was obtained as in the case of using pure water, and foaming peculiar to the surfactant solution was also observed. It was confirmed that the activator did not react. It was also confirmed that the same cleaning and decomposition treatment as in Example 1 was performed.

(Comparative Example 2)
As the surfactant, ozone was used in the same manner as in Example 1 except that sorbitan monooleate (non-ionic surfactant “trade name: Tween 80” manufactured by Kanto Chemical Co., Ltd.), which is not subject to the present invention, was used. Was dissolved. As a result of measuring the concentration after about 20 minutes, the ozone concentration was 0 ppm, the foaming peculiar to the surfactant solution disappeared, and ozone and the surfactant clearly reacted to obtain the ozone-containing cleaning liquid according to the present invention. It was confirmed that it was not possible.

(Comparative Example 3)
Other than using an anionic surfactant (n-dodecylbenzenesulfonic acid manufactured by Kanto Kagaku Co., Ltd.) that is outside the scope of the present invention as the surfactant and adjusting the pH to 6.5 with sodium hydroxide. As a result of dissolving ozone in the same manner as in Example 1, foaming peculiar to the surfactant solution was not observed after about 20 minutes, and it was clearly confirmed that the surfactant was decomposed by ozone.

  From the above results, ozone can be dissolved in the surfactant that can be used in the present invention, and by using this ozone-containing cleaning solution, the cleaning action by the surfactant and the oxidizing and decomposing actions by ozone can be obtained simultaneously. As a result, the superiority of the present invention could be confirmed.

Example 4
Using the ozone-containing cleaning liquid according to Examples 1 to 3, after cleaning medical devices such as endoscopes and surgical tools after use, no solid deposits were seen in the cleaned medical devices, and the surfactant was used. It was confirmed that the cleaning ability was not lost.
Thus, it was found that by using the ozone-containing cleaning liquid according to the present invention, the cleaning action by the surfactant and the sterilization and disinfection action by the ozone can be obtained at the same time, and the superiority of the present invention could be confirmed.

The schematic diagram of the organic substance removal apparatus which concerns on an example of embodiment of this invention. The simplification figure which shows the example of the non-porous film formation used by this invention. The schematic diagram of the washing | cleaning sterilization apparatus of the medical device which concerns on an example of embodiment of this invention.

Explanation of symbols

A: Organic substance removal device 1: Cleaning liquid supply means 2: Reaction tank 3: Ozone gas generator 4: Liquid feed pump for delivering surfactant 6: Ozone dissolution module 15: Bundled hollow fiber gas permeable membrane (non-porous membrane) )
A ': Cleaning sterilizer 30: Ozone-containing cleaning liquid generation unit 31: Cleaning tank 32: Cleaning unit 33: Ozone gas generator 34: Surfactant filler 36: Ozone dissolution module

Claims (4)

Using a ozone-containing cleaning solution in which ozone is dissolved in a saturated aliphatic surfactant solution having no carbon-carbon double bond represented by the following general formula, cleaning with a surfactant, and decomposition and sterilization with ozone And a cleaning method characterized in that
(R) _n -X
Wherein R is a hydrophobic group comprising a saturated hydrocarbon or a saturated halogenated carbon compound,
n is an integer of 1 to 3, X is an ether group having no carbon-carbon double bond and an aromatic group,
Any one of hydroxyl group, ester group, carboxyl group, sulfone group and amino group
Represents a hydrophilic group compound having one. )   The cleaning method according to claim 1, wherein the ozone-containing cleaning liquid is obtained by dissolving ozone in the saturated aliphatic surfactant solution through a non-porous film that allows gas to permeate but not liquid. .   The cleaning method according to claim 1 or 2, wherein the ozone-containing cleaning liquid has a pH of 8 or less. Using a ozone-containing cleaning solution in which ozone is dissolved in a saturated aliphatic surfactant solution having no carbon-carbon double bond represented by the following general formula, cleaning with a surfactant, and decomposition and sterilization with ozone The cleaning apparatus is configured to perform the above simultaneously.
(R) _n -X
Wherein R is a hydrophobic group comprising a saturated hydrocarbon or a saturated halogenated carbon compound,
n is an integer of 1 to 3, X is an ether group having no carbon-carbon double bond and an aromatic group,
Any one of hydroxyl group, ester group, carboxyl group, sulfone group and amino group
Represents a hydrophilic group compound having one. )

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