JP2003082392A - Method for controlling detergent solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for controlling a detergent solution in order to keep it in high detergency, good dryability and nonflammability. SOLUTION: The method comprises detecting the level of a dirty component contaminating into a nonflammable detergent or rinse by measuring changes in its property values including electric conductivity, light absorption and refractive index during a cleaning process, wherein the detergent or rinse contains (a) a non-chloric fluoride compound having a vapor pressure of 1.33&times;10<3> Pa at 20 deg.C or more and (b) one or more compound having a vapor pressure of less than 1.33&times;10<3> Pa at 20 deg.C and selected from the group consisting of ether bond- and/or ester bond-having organic compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various processing oils, greases, waxes, and fluxes used for soldering electric and electronic parts, which are used for processing precision machine parts, optical machine parts and the like. The present invention relates to a method for controlling a cleaning liquid containing two or more compounds that are not azeotropic and are suitable for cleaning.

[0002]

2. Description of the Related Art Various processing oils used for processing precision machine parts, optical machine parts, etc., such as cutting oil, press oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, etc., or greases. , Waxes and the like are used, but these must be finally removed as stains, and removal with a solvent is generally performed. Soldering is the most commonly used method of joining electronic circuits, but flux is used to remove and clean oxides on the metal surface to be soldered, to prevent reoxidation, and to improve solder wettability. It is common practice to pretreat the soldering surface. Since this flux residue causes corrosion of the metal and deterioration of the insulating property, it must be sufficiently removed after the soldering is completed.

For cleaning and removing these, 1,1,1-trichloroethane and 1,1,2-trichloro-1,2,2 are used.
-Trifluoroethane (hereinafter referred to as CFC113) or C
Although it was washed with a solvent mixed with FC113 and alcohol, the problem of global environmental pollution such as ozone layer depletion was pointed out, and its production was completely abolished at the end of 1995 in Japan. As an alternative to this CFC113, 3,3-dichloro-
1,1,1,2,2-pentafluoropropane and 1,3
-Hydrochlorofluorocarbons such as a mixture of dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as HCFC225) have been proposed, but these also have ozone layer depletion potential, so in Japan in 2020 Its use will be banned.

Furthermore, in recent years, there has been proposed a nonflammable fluorine-based solvent having no ozone depleting ability such as hydrofluorocarbons (hereinafter referred to as HFC) and hydrofluoroethers (hereinafter referred to as HFE) containing no chlorine atom at all. However, since it does not contain chlorine atoms, it has a low solubility and cannot be used alone as a cleaning agent.
Japanese Patent No. 316598, Japanese Patent Application Laid-Open No. 10-212498, Japanese Patent Application Laid-Open No. 10-251692 and the like disclose a technique of a cleaning agent in which a combustible solvent is combined with HFC or HFE. This cleaner is CFC113 or HCFC2
Unlike the single-component or azeotropic composition detergents such as 25, it is a non-azeotropic detergent composition that is a mixture of volatile HFC or HFE and a high-boiling solvent. Therefore, when this cleaning agent is continuously used, HFC and HFE evaporate and the ratio of the combustible solvent in the cleaning agent increases, which deteriorates the cleaning ability and the drying property, and the appearance of a flash point. H will cause problems
Although it is necessary to appropriately control the composition ratio of FC or HFE to a flammable solvent, there has been no method for effective liquid control until now.

Further, depending on the physical properties used for liquid management in the conventional HCFC, the influence of the contamination component mixed and the compositional change of the cleaning agent on the physical properties are closely correlated, and the concentration of the contaminant component cannot be detected. There are cases. Also,
Japanese Patent No. 3002261 describes the control of composition fluctuation of low-molecular siloxane and fluorocarbon, but it is limited to the low-molecular siloxane having Si-O bond, and also the control of contaminant components mixed in. In addition, stable dirt cannot be maintained due to redeposition of mixed dirt. In this way, a cleaning agent composition or rinse agent that contains a chlorine-free fluorine compound and a flammable solvent and whose composition may change during use has established technology for controlling the cleaning agent composition and the concentration of contaminants mixed in. The current situation is that there are none.

[0006]

The chlorine-free fluorine compound (a) having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and the vapor pressure of 1.33 × 10 ³ P at 20 ° C.
Dirt mixed in a cleaning agent or rinse agent having no flash point, containing one or more compounds (b) selected from the group consisting of organic compounds having an ether bond and / or an ester bond, which are components less than a. It is an object to maintain stable detergency, dryability and non-flammability by proposing a concentration control of components and a liquid control method of the detergent or rinse agent.

[0007]

Means for achieving the object of the present invention have, in order to achieve the above object, intensive result of extensive investigations, soil components are mixed, the vapor pressure at 20 ° C. is 1.33 × 10 ³ Pa or more non One or more compounds selected from the group consisting of a chlorine-based fluorine compound (a) and a component having a vapor pressure at 20 ° C. of less than 1.33 × 10 ³ Pa and having an ether bond and / or an ester bond. It was found that the concentration of the soil component mixed in the cleaning agent or the rinse agent can be detected by measuring the change in the physical properties of the cleaning agent or the rinse agent containing (b). It was also found that the composition of the cleaning agent or the rinsing agent can be detected by measuring the change in the physical property or the capacity of the cleaning agent or the rinsing agent caused by the variation in the composition.

Further, among the physical properties of the cleaning liquid, the physical property value of the cleaning liquid in which one of the measured values is dependent on the concentration of the stain component or the liquid composition is significantly smaller than the other, and the other physical property values different from the physical property are measured. It was found that by doing so, the composition and the concentration of the soil component can be detected more accurately. Hereinafter, the present invention will be described in detail. As used herein, the term "dirt component" refers to a component that is desired to be removed from the object to be washed. For example, processing oil attached to precision parts, flux residue attached to a printed circuit board, liquid crystal remaining in the gap of a liquid crystal cell, and the like, and a rinse agent also represents a cleaning agent component.

The term "composition fluctuation" means that the chlorine-free fluorine compound (a) having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. and the vapor pressure of 1.33 × 10 ^{3 at} 20 ° C.
Volatilization in a non-flash point cleaning agent or rinse agent containing one or more compounds (b) selected from the group consisting of organic compounds having an ether bond and / or an ester bond and having a component of less than ³ Pa. Compounds (a) and (b) are removed by evaporation of highly reactive components.
It means that the compounding ratio of is changed.

By carrying out the following liquid control method, the non-chlorine fluorine compound (a) having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. and the vapor pressure of 1.33 × 10 ³ at 20 ° C. It is possible to detect the composition of the cleaning agent or rinse agent containing the component (b) of less than ³ Pa and the concentration of the dirt component mixed in them, and it is possible to manage to maintain a stable cleaning level. Becomes The concentration of the soil component mixed in the cleaning agent or the rinse agent can be detected by measuring the change in the physical properties of the cleaning agent and / or the rinse agent caused by the mixing. Examples of physical properties include conductivity, refractive index, specific gravity, boiling point, condensation point, acidity, viscosity, and absorbance.

The electrical conductivity is an index showing the ease with which an electric current flows in a conductor. Conventionally, it is generally used to measure a contaminant component mixed in an aqueous cleaning agent, while a non-chlorine type is used. It was thought that it could not be used for non-aqueous detergents based on fluorine compounds. However, in the non-aqueous detergent or rinse agent containing the compound (a) and the compound (b) measured by the liquid management method of the present invention, since the compound (b) is contained in the non-aqueous detergent or rinsing agent, the non-aqueous detergent has hitherto been used. It was found that it is possible to detect the density of stains containing a conductive component, which could not be measured in. Examples of stains containing a conductive component include RMA type and RA type fluxes containing an active component, and processing oil containing a large amount of extreme pressure additives and the like. To measure the dirt concentration by conductivity,
Compound (a) and compound (b) such as specific gravity, boiling point and refractive index
As compared with the measuring method which is affected by the compositional fluctuation of the cleaning liquid containing, the compositional fluctuation has less influence on the conductivity, and therefore the stain concentration can be easily detected, which is preferable.

Further, the conductivity measurement can be performed with an inexpensive instrument as compared with an expensive analysis instrument such as a gas chromatograph, and can be easily measured, so that it can be used at a site where cleaning is actually performed. It is preferable because it is possible. The device for measuring the conductivity may be an in-line type installed in the cleaning device, a handy type, a desktop type, or any device capable of measuring the conductivity. When performing an accurate analysis, the measurement temperature is an error factor.Therefore, use a device with a temperature correction function, or create a calibration curve of the contamination concentration and conductivity at several temperatures, and make it appropriate depending on the measurement temperature. The concentration may be detected using a simple calibration curve. The refractive index utilizes the phenomenon that the refraction of light differs depending on the solute concentration in the solution. When the dirt component is mixed in the cleaning agent, the refractive index of the dirt component also changes, so that the dirt concentration can be detected. Also for the refractive index measurement, since it can be easily measured with an inexpensive device, it can be used at a site where cleaning is actually performed, which is preferable. As a device for measuring the refractive index, there are hand-held refractometers, saccharimeters, etc., which may be either in-line measurement type or sampling type, but there is little influence of cleaning agent volatilization at the time of measurement. Those are preferable. Regarding the refractive index as well, when performing accurate analysis, use a device with a temperature correction function or create a calibration curve for the concentration of contaminants and refractive index at several temperatures, and then set the appropriate calibration curve according to the measurement temperature. It is also possible to detect the concentration by utilizing it.

The specific gravity can be detected by changing the specific gravity by mixing a stain component having a low specific gravity into a cleaning agent containing the compound (a) having a high specific gravity, thereby making it possible to detect the stain concentration, which is commercially available. Measure with a meter, float balance, etc. Regarding the boiling point, as compared with the detergent containing the compound (a) and the compound (b), the contamination component generally having a high boiling point causes the boiling point to rise proportionally, and the concentration can be detected.

Further, the "condensation point" represents the temperature of the gas phase portion in the boiling state in the cleaning agent having a non-azeotropic composition, and like the boiling point described above, the concentration of the mixed contaminant component can be detected. . The acidity is obtained by adding an indicator to the solution to be measured, titrating the solution with an alkaline solution, and measuring the amount of acidic substance contained in the solution by the color change point. When the mixed dirt component contains an acidic substance, the titration amount and the quantity of the mixed dirt component are in a proportional relationship, and the concentration can be detected.

Absorbance is an amount indicating the degree to which a cleaning agent or a rinse agent absorbs light. In many cases, for example, processing oil and other contaminants mixed in have an absorption band of 320 nm to 70 nm.
0 nm, while compound (a) or compound (b)
Of the absorption band of 190 nm to 300 nm is used, 320 nm to 70
It was found that by measuring the absorbance at 0 nm, the concentration of the mixed stain component can be detected accurately. The wavelength region used for detecting the dirt component is preferably 320 nm to 600 nm where absorption appears more significantly. Moreover, the measurement in the visible light region of 400 nm to 700 nm is
A colorimeter can be used, and measurement at the washing site is possible, which is preferable.

Further, when the composition of the cleaning liquid for which the concentration of the mixed dirt is to be detected is fluctuated, the cleaning liquid before the composition change is added to suppress the influence of the composition fluctuation, and then the change of the physical property value is measured to obtain a higher accuracy. It was found that the stain density can be detected well. This method is preferably carried out by adding a small amount of liquid from a tank containing the cleaning liquid. If the stain component concentration detected by the above method exceeds the upper limit of the stain component concentration that can maintain the required cleaning level, the liquid is replaced and a new liquid is renewed, or a new liquid is replenished. By keeping the concentration of the dirt component in the tank within the control upper limit value, it becomes possible to maintain a stable cleaning level.

As a method of detecting the composition, the composition of the cleaning agent can be detected by using an analytical instrument such as a gas chromatograph or a gas chromatograph mass spectrometer, but at the actual cleaning site, However, there is a need for a low-cost and simple detection method. In the present invention, the composition control of the detergent or rinse agent containing the compounds (a) and (b) can also be detected by measuring the change in the physical properties of the detergent or rinse agent caused by the composition variation. I found that. Examples of the physical properties include refractive index, specific gravity, boiling point, condensation point, viscosity, and absorbance. Depending on the detected composition, the cleaning liquid or the components that evaporate from the cleaning liquid are appropriately replenished and managed to obtain a high cleaning property, which is a characteristic of this cleaning liquid.
It has been found that excellent dryness and non-flammability can be maintained.

It is also possible to detect the composition of the cleaning liquid by measuring the volume change of the amount of the solution in the tank containing the cleaning liquid, which is measured by the liquid management method of the present invention. When the liquid level at the time of building bath is out of the range that maintains the high cleaning properties, excellent drying properties, and non-flammability, which are the characteristics of this cleaning liquid, it is stabilized by supplementing the vaporized volatile components. Can be managed. The liquid level management may be any one such as automatic measurement and manual measurement as long as the liquid level can be detected. As the cleaning device, any device capable of cleaning the object to be cleaned may be used, and the device for managing the liquid is not limited, but a device for specifically managing the liquid level is specifically described with reference to the accompanying drawings. To do. The cleaning apparatus shown in FIG. 1 has a heating mechanism 5 for heating or / and boiling at least one component constituting a cleaning agent as a main structure.
Cleaning tank (A) 1, a steam zone (B) 3 for steam cleaning with steam 7 generated from the cleaning tank (A) 1, the evaporated cleaning agent is condensed by a cooling pipe 6, and the condensed liquid and cooling From a water separation tank (C) 4 for statically separating water attached to the pipe, and a rinse tank (D) 2 for immersion rinsing with the condensed liquid from which water has been removed in the water separation tank (C) 4. Become.

After the condensate is collected in the water separation tank (C) 4, it enters the rinse tank (D) 2 through the pipe 9, overflows, and returns to the cleaning tank (A) 1 as shown by an arrow 10, and the heater After heating and boiling at 5, a part or all of the composition becomes vapor and is condensed in the cooling pipe 6 as shown by arrow 7, and then returns from the pipe 8 to the water separation tank (C) 4. The procedure as one example of the method for detecting the composition in the change of the capacity in the present invention is shown below. In the cleaning tank (A) 1, when the cleaning tank (A) 1 is heated or / and boiled to generate steam, and the condensed liquid overflows and returns to the cleaning tank (A) 1, measurement of the cleaning tank liquid level And use this as the reference plane. During continuous cleaning, the steam generated by heating or / and boiling the cleaning liquid partially evaporates into the atmosphere, and the liquid level in the cleaning tank (A) 1 lowers. At this time, by supplementing the vaporized components and maintaining the liquid level range that maintains the high cleaning properties, excellent drying properties, and low flammability that are characteristic of this cleaning liquid, safe cleaning and stable cleaning properties can be achieved. Can be maintained. Here, as a liquid replenishment method, a liquid surface float is used, and when the value is below the control lower limit value,
A device for automatic supply may be provided. Here, the rinse agent composition is more preferable because the composition variation of the cleaning liquid can be suppressed by making the cleaning liquid the same composition as the condensate obtained by heating or / and boiling the cleaning liquid.

In a cleaning device in which a condensate of vapor obtained by heating or / and boiling the cleaning liquid circulates,
An apparatus having only one tank whose capacity changes is preferable because it can detect a liquid level change with high accuracy. Further, regarding the cleaning liquid in which dirt is mixed and the composition is changed, one of the physical property values that is less affected by either the composition change or the mixed dirt component concentration,
It has been found that the composition and the concentration of the stain component can be detected more accurately by measuring one of the physical property values for detecting the composition different from the physical property or the concentration of the stain component mixed therein.

The physical properties for detecting the concentration of the dirt component, which is less affected by the composition of the cleaning liquid, are conductivity and 320 nm to 700 n.
Absorbance at m. In addition, the one that detects the cleaning liquid composition, which is less affected by the mixed dirt concentration, is 190n.
The absorbance at m to 300 nm and the change in the volume of the solution in the cleaning liquid tank are included. For example, the composition of the cleaning liquid based on the refractive index can be accurately detected by performing the absorbance measurement and the refractive index measurement, obtaining the concentration of the contamination component mixed by the change of the absorbance, and correcting the influence of the contamination component concentration.

The cleaning agent used in the liquid control method of the present invention will be described below. The chlorine-free fluorine compound (a) having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more contained in the cleaning agent and / or rinsing agent used in the liquid control method of the present invention is a hydrocarbon. A fluorine compound in which a part of hydrogen atoms of ethers and ethers are replaced only by fluorine atoms and does not contain a chlorine atom, for example, a cyclic HFC specified by the following general formula (1) or a chain specified by (2) HFC, or HFE specified in (3), containing no chlorine atom,
The compound which consists of a carbon atom, a hydrogen atom, an oxygen atom, a fluorine atom, the combination of 2 or more types of compounds chosen from these, etc. are mentioned. C _n H _2n-m F _m (1) (in the formula, represents an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1) C _x H _{2x + 2-y} F _y (2) (wherein, 4 ≦ x ≦ 6, 6 ≦ y ≦ 2x + 1 is an integer) C _s F _{2s + 1} OR (3) (wherein 4 ≦ s ≦ 6, R is an alkyl group having 1 to 3 carbon atoms)

Specific examples of the cyclic HFC are 3H, 4H,
4H-perfluorocyclobutane, 4H, 5H, 5H-
Perfluorocyclopentane, 5H, 6H, 6H-nonafluorocyclohexane etc. can be mentioned. Specific examples of the chain HFC are 1H, 2H, 3H, 4H-perfluorobutane, 1H, 2H-perfluorobutane, 1
H, 3H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H-perfluorobutane, 1H,
1H, 3H-perfluorobutane, 1H, 1H, 4H-
Perfluorobutane, 1H, 2H, 3H-perfluorobutane, 1H, 2H-perfluoropentane, 1H, 4
H-perfluoropentane, 2H, 3H-perfluoropentane, 2H, 4H-perfluoropentane, 2H,
5H-perfluoropentane, 1H, 2H, 3H-perfluoropentane, 1H, 3H, 5H-perfluoropentane, 1H, 5H, 5H-perfluoropentane, 2
H, 2H, 4H-perfluoropentane, 1H, 2H,
4H, 5H-perfluoropentane, 1H, 4H, 5
H, 5H, 5H-perfluoropentane, 1H, 2H-
Perfluorohexane, 2H, 3H-perfluorohexane, 2H, 4H-perfluorohexane, 2H, 5H
-Perfluorohexane, 3H, 4H-perfluorohexane and the like can be mentioned.

Specific examples of HFE include methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, methyl perfluorocyclohexyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether and ethyl perfluoropentyl ether. Can be mentioned.

The cleaning agent and / or rinsing agent of the present invention
The vapor pressure at 20 ° C is 1.33 x 10
³Selected from chlorine-free fluorine compounds (a) with Pa or more
One or two or more compounds used in combination
You can In the cleaning agent of the present invention, any dirt
For the purpose of improving the detergency of the compound (a),
Vapor pressure at 20 ℃ is 1.33 × 10³Less than Pa
And an ether bond and / or an ester bond
One or more selected from the group consisting of organic compounds having
One or more compounds selected from the compound (b)
The above can be used together. The compound (b) is, for example,
Various esters, glycol ethers, various stains
Has good detergency against steam and vapor at 20 ℃
Pressure is 1.33 × 10 ³It is a compound of less than Pa. Compound
When the vapor pressure of (b) is in this range, the present invention is concerned.
A cleaning agent with excellent cleaning properties can be obtained. Preferably 20
6.66 × 10 at ℃³Pa or less, more favorable
1.33 × 10 is better²Pa or less.

The compound (b) is exemplified below for each type of solvent. Among the esters, n-butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, methyl acetoacetate,
Ethyl acetoacetate, methyl lactate, ethyl lactate, butyl lactate, γ-butyl lactone, dimethyl succinate, dimethyl glutarate, dimethyl adipate, 3-methyl-3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monobutyl ether. Examples thereof include acetate.

Among glycol ethers, ethylene glycol mono-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol. Mono-i-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether, dipropylene glycol monomethyl ether , Dipropylene glycol mono-n-propyl ether Le, dipropylene glycol monomethyl -i- propyl ether, dipropylene glycol mono -n- butyl ether, dipropylene glycol mono -
i-butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-
3-methoxybutanol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
Diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether, etc. can be mentioned.

The cleaning agent and / or rinsing agent used in the liquid control method of the present invention has a boiling point of 20 ° C. to 100 ° C. at 1.013 × 10 ⁵ Pa and is referred to as compound (a) or compound (b). Addition of different compounds as detergency improvers, stabilizers, melting point depressants, etc. to suppress the amount of compound (b) added, improve detergency, improve metal stability in the vapor phase during vapor cleaning. It is also possible to prevent coagulation of the cleaning agent during cooling. Further, for the purpose of preventing oxidative deterioration of the detergent and / or rinse agent, a phenol-based antioxidant, an amine-based antioxidant, and a phosphorus-based antioxidant can be used. The cleaning agent or rinsing agent of the present invention, if necessary, various auxiliary agents, for example, a surfactant, a stabilizer, a defoaming agent,
You may add a ultraviolet absorber etc. as needed.

The rinse agent used in the liquid control method of the present invention may have any composition as long as it contains the compound (a) and the compound (b). A vapor composition containing a compound (a) obtained by heating or / and generating at least one component constituting the contained cleaning agent and a compound (b) slightly contained,
It is preferable to use it as a rinse agent because it can be used as a replenisher for the cleaning agent.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples. Create the cleaning or rinsing agent in Table 1,
Used in the examples shown below.

[0031]

[Example 1] Pellets prepared by heating flux (trade name: JS64-ND, manufactured by Hiroki Co., Ltd.) to the cleaning agent represented by 1 in Table 1 to evaporate and dry the compound components such as isopropanol , 1% by weight, 2% by weight, 3% by weight
Conductivity meter (trade name: E
S-12, manufactured by Horiba Ltd.) was used to measure the electrical conductivity.
As a result, as shown in FIG. 2, it was revealed that there is a correlation between the amount of mixed flux and the electrical conductivity.

[0032]

Example 2 Processing oil (trade name: Unicut Terrami AM30, manufactured by Nisseki Mitsubishi Corp.) was added to each of the cleaning agents 2 in Table 1 in an amount of 1% by weight, 3% by weight, 5% by weight, and 7% by weight. Digital sugar content meter (product name: palette 10
0, manufactured by Atago Co., Ltd., the refractive index was measured at room temperature (28 ° C.). As a result, as shown in FIG. 3, it was revealed that there is a correlation between the amount of mixed processing oil and the refractive index.

[0033]

Example 3 The spectrophotometer (trade name: UV) of 3 in Table 1 and 3 of the cleaning agent of Table 1 to which 3% by weight of cutting oil (Unicut Terrami AM30, manufactured by Mitsubishi Nisseki Co., Ltd.) was added -240, manufactured by Shimadzu Corporation) was used to measure the absorption spectrum at a wavelength of 190 to 700 nm. As a result, 3 in Table 1 in which dirt was mixed
In the absorption spectrum of No. 3, the absorption of the stain component not found in the absorption spectrum of No. 3 in Table 1 is 350 nm to 6 nm.
It was found in the range of 00 nm. Further, the absorbance at a wavelength of 420 nm of each solution prepared by mixing 1, 3, 5% by weight of this cutting oil with the cleaning agent of 5 in Table 1 was measured. As a result, as shown in FIG. 4, it was clarified that there is a correlation between the contamination component mixed and the absorbance, and the concentration of the contamination component can be detected by measuring the absorbance.

[0034]

[Example 4] When the refractive index of the cleaning agents having the compositions of 3 to 5 in Table 1 was measured, it was revealed that the fluorine-based solvent concentration in the cleaning agent and the refractive index had a correlation as shown in Fig. 5. became. In addition, regarding the cleaning agents 3 to 5 in Table 1, processing oils (trade name: Unicut Terrami AM30, Mitsubishi Nisseki Co., Ltd.)
(Made by Japan) was added at 1% by weight, 3% by weight, and 5% by weight, and the refractive index was measured. As a result, when mixing each processing oil,
It became clear that the concentration of the fluorine-based solvent and the refractive index have a correlation.

[0035]

[Embodiment 5] In the cleaning apparatus of FIG. 1, the cleaning tank (A) 1
(Cleaning tank container: Dimensions 24.7 cm vertical x 15.5 c horizontal
The cleaning agent of 1 in Table 1 was put in m), and the rinse agent of 6 in Table 1 was put in the rinse tank (D) 2 and the water separation tank (C) 4. When the washing tank (A) 1 was boiled and continuously operated,
A decrease in the liquid level was observed due to the evaporation of steam. The rinse agent of 6 in Table 1 was newly added to the cleaning tank (A) 1 to keep the liquid level at the original height. The cleaning tank liquid was sampled every 15 hours of operation and gas chromatographic analysis was performed to confirm the composition. As a result, it became clear that stable composition can be controlled by keeping the capacity within a certain range. The results are shown in Table 2.

[0036]

Example 6 The cleaning composition of 3 in Table 1 was added with 3, 5
Weight% processing oil (trade name: Unicut Terrami AM30,
After adding each of the products manufactured by Nisseki Mitsubishi Co., Ltd., the absorbance and the refractive index of each oil-mixed solution were measured, and the contamination concentration was calculated from the measured absorbance values as shown in FIG. It was clarified that the cleaning agent composition can be detected accurately by using the calibration curve in consideration of the influence of each soil concentration in. The results are shown in Table 3.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

EFFECT OF THE INVENTION The liquid control method for a detergent according to the present invention measures changes in physical properties of a non-azeotropic detergent containing a non-chlorine fluorine compound and an organic compound having an ether bond and / or an ester bond. However, by detecting and controlling the concentration and / or composition of the contaminant components mixed in, it is possible to carry out cleaning without impairing the characteristics of this cleaning agent or rinse agent such as high cleaning property, good drying property and non-flammability. Is possible.

Further, by combining the measurement of the physical property for detecting the concentration of the mixed contaminant component and the measurement of the physical property for detecting the composition different from the physical property, the concentration of the contaminant component and the composition can be detected more accurately.

[Brief description of drawings]

FIG. 1 is an example of a cleaning apparatus of the present invention (schematic diagram)

[Fig. 2] Dependence of the measured values of the conductivity of the cleaning liquid on the soil component concentration under a constant cleaning liquid composition

[Fig. 3] Dependence of the measured values of the refractive index of the cleaning liquid on the concentration of the dirt component under a constant cleaning liquid composition

[Fig. 4] Dependence of the measured values of the absorbance of the cleaning solution on the concentration of the soil component under a constant cleaning solution composition

FIG. 5 Dependence of cleaning liquid composition on the measured refractive index of cleaning liquid in cleaning liquids with different soil component concentrations

[Explanation of symbols]

1 cleaning tank 2 rinse tanks 3 steam zones 4 water separation tank 5 heater 6 cooling tubes 7 Cleaning solution vapor 8 piping 9 piping 10 Condensate

Claims (6)

[Claims] 1. The vapor pressure at 20 ° C. is 1.33 × 10.
Selected from the group consisting of a chlorine-free fluorine compound (a) of ³ Pa or more and an organic compound having a vapor pressure at 20 ° C. of less than 1.33 × 10 ³ Pa and having an ether bond and / or an ester bond. The concentration of the dirt component mixed in the cleaning agent or rinsing agent having no flash point and containing one or more compounds (b) (hereinafter, collectively referred to as a cleaning solution, if necessary) is A cleaning liquid management method characterized by detecting by measuring a change in the physical properties of the cleaning liquid. 2. A cleaning liquid management method, which comprises detecting the composition of the cleaning or rinsing agent according to claim 1 by measuring a change in the physical properties of the cleaning liquid in the cleaning step. 3. The cleaning liquid management method according to claim 1, wherein a liquid before composition change of the cleaning liquid to be measured is added to the cleaning liquid to be measured. 4. A cleaning liquid management method, which comprises detecting the composition of the cleaning agent or rinsing agent according to claim 1 by measuring a change in volume of the cleaning liquid tank content liquid in the cleaning step. 5. Measurement of one item selected from the group consisting of conductivity, absorbance and volume change of the amount of solution in the cleaning liquid tank in the cleaning step, and selected from the group consisting of refractive index, specific gravity, boiling point, condensation point and viscosity. A method of managing a cleaning liquid, which comprises detecting the concentration and composition of a stain component in the cleaning liquid by measuring one item. 6. The concentration and composition of stain components in the cleaning liquid are detected by measuring two items selected from the group consisting of conductivity, absorbance and volume change of the amount of solution in the cleaning liquid tank in the cleaning step. Cleaning liquid management method.