JP2001334104A - Separation method and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To cut down the running cost of a cleaning step by separating dirt mixed in a detergent and a rinse and the detergent component mixed in the rinse to reuse the detergent and the rinse. SOLUTION: A non-chlorinated fluorine compound and an organic compound are added to the dirt component-mixed detergent composition and/or the non- chlorinated fluorine compound is added to the rinse where the detergent component is mixed and the dirt component dissolving and/or dispersing in the detergent is mixed, which are then settled to separate the mixed dirt component and/or detergent component so that the obtained detergent and rinse can be reused.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a variety of processing oils, greases, and the like for processing precision machine parts, optical machine parts, and the like.
The present invention relates to a cleaning agent suitable for cleaning waxes and fluxes used for soldering electric and electronic components, and a method and an apparatus for separating dirt mixed in a rinsing agent and cleaning agent components mixed in the rinsing agent. Things.

[0002]

2. Description of the Related Art Various processing oils, such as cutting oils, press oils, drawing oils, heat treatment oils, rust preventive oils, lubricating oils, etc., or greases, waxes when processing precision machine parts, optical machine parts, etc. Although such stains need to be finally removed, removal with a solvent is generally performed. Soldering is the most commonly used method of joining electronic circuits.However, in order to remove and clean oxides on the metal surface to be soldered, prevent re-oxidation, and improve solder wettability, flux is used. In general, the soldering surface is pre-processed by using the above method. As a method of soldering, after immersing the substrate in a solution-type flux or the like, the flux was attached to the substrate surface, and then a method of supplying molten solder or mixing the flux and solder powder in advance to form a paste. There is a method of heating after supplying the material to the place to be soldered, but in any case, the flux residue causes corrosion of the metal and lowers insulation properties, so it should be sufficiently removed after soldering. There is a need.

[0003] These washing and removal methods have many features such as nonflammability, low toxicity and excellent solubility. For example, 1,1,2-trichloro-1,2,2-trifluoro is preferred. Ethane (hereinafter CFC113) or CFC113
It was washed with a solvent mixed with alcohol. However, CFC113 was pointed out as a problem of global environmental pollution such as depletion of the ozone layer, and its production was completely abolished in Japan at the end of 1995. As an alternative to this CFC 113,
A mixture of dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as HCFC225) or 1,1-dichloro- 1-fluoroethane (hereinafter H
Hydrochlorofluorocarbons such as CFC141b) have been proposed, but their use is scheduled to be banned in 2020 in Japan due to their ability to deplete the ozone layer.

Therefore, in recent years, non-flammable fluorine-based solvents, such as hydrofluorocarbons (hereinafter, referred to as HFC) and hydrofluoroethers (hereinafter, referred to as HFE), which do not contain any chlorine atoms, have no ozone layer destruction ability and have been proposed. ing. However, since the dissolving ability is low and cannot be used alone as a cleaning agent, JP-A-10-36894 describes a cleaning agent using HFC or HFE in combination with an organic compound such as an ester. After washing using this detergent, an organic compound such as an ester dissolving a dirt component adhered to the surface of the object to be washed is washed in a tank containing only HFC or HFE, and the rinse agent is easily cleaned and dried. (Here, HFC or HFE alone), there is also a description of a cleaning method in which a rinsing step is provided. However, if this cleaning method is used continuously for a long time,
Dirt such as flux or oil is mixed in the cleaning agent to deteriorate the detergency, or the rinsing agent is mixed with an organic compound such as an ester in which the dirt component is dissolved. There is.

Therefore, there has been a demand for a method of separating detergent components mixed in these rinsing agents. To solve this problem, Japanese Patent Laid-Open No. 10-202209 discloses a method.
There is a description of an apparatus that uses a hydrocarbon-based solvent as a cleaning agent, cleans with the cleaning agent, and separates the hydrocarbon-based solvent mixed in the fluorine-based solvent in a rinsing step with a fluorine-based solvent. However, in this method, as a cleaning agent,
It is necessary to use a hydrocarbon solvent which is incompatible with the fluorine solvent which is a rinsing agent, and there is a problem in rinsing properties, and there is a risk of ignition because the cleaning agent itself has a flash point.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to recycle a cleaning agent and a rinsing agent by separating dirt components mixed in the cleaning agent and the rinsing agent and cleaning agent components mixed in the rinsing agent. It is an object to reduce the running cost in the process.

[0007]

Means for Achieving the Object The present inventors have conducted intensive studies in order to achieve the above object, and as a result, the cleaning agent containing a non-chlorine fluorine compound has a specific property that the non-chlorine fluorine compound has. Due to the high specific gravity and low compatibility characteristics, it has been found that by allowing to stand under certain conditions, it is possible to easily separate the dirt component mixed in the cleaning agent, and further, the cleaning agent mixed with the dirt component is in any state, for example, It has been found that, even in a uniform or non-uniform state, the soil component can be separated from the cleaning agent by allowing to stand still. Here, “uniform” means that a detergent containing a chlorine-free fluorine compound mixed with a dirt component is shaken or agitated, and then closed in a sealed state.
This means that no two-layer separation is observed when left at 5 ° C. for 5 minutes.

In addition, after cleaning with a cleaning agent containing a non-chlorine fluorine compound, a cleaning component and a dirt component dissolved and / or dispersed in the cleaning agent used for rinsing and / or steam cleaning are mixed. The present inventors have found that a detergent component and a dirt component dissolved and / or dispersed in the detergent can be separated from the rinse agent thus completed, and the present invention has been completed. That is, the first aspect of the invention is that the cleaning composition (a) is (b)
A composition containing a chlorine-free fluorine compound and (c) an organic compound. In the method of cleaning with the cleaning composition (a), the cleaning composition (a) used for cleaning is left standing. A separation method characterized by separating a dirt component mixed in the cleaning composition (a).

A second aspect of the present invention is a method of rinsing compound (b) alone as a rinsing agent and / or steam washing after washing with the detergent composition (a), and using the same for rinsing and / or steam washing. This separation method is characterized in that the rinse agent is allowed to stand and the compound (c) and the dirt component mixed in the rinse agent are separated. The third aspect of the invention is
The rinsing agent has a composition (d) having a compound (b) and (e) having a boiling point of 20 ° C. at 1.013 × 10 ⁵ Pa.
A second separation method according to the invention, which is a composition containing an organic compound at 100 ° C.

A fourth aspect of the invention is the method and apparatus according to the first to third aspects of the invention, wherein the difference in specific gravity between the compound (b) and the compound (c) is at least 0.3 at 25 ° C. A fifth aspect of the invention is the method and the apparatus according to the first to fourth aspects of the invention, wherein the compound (b) is methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture thereof. A sixth aspect of the invention is a separation apparatus for performing the separation method described in the first to fifth aspects of the invention, wherein the separation apparatus uses a separation tank.

Hereinafter, the present invention will be described in detail. In the present specification, the “cleaning step” refers to a step of using the cleaning composition (a) to remove dirt components adhered to an object to be washed.
Dirt components include processing oils such as cutting oil, press oil, extraction oil, heat treatment oil, flux components such as rosin, chlorides such as amine hydrochloride, polymerized rosin generated during the soldering process, and metal salts of rosin. Can be mentioned.

[0012] The "rinsing step" means that after the "cleaning step", the detergent component adhering to the surface of the object to be washed and the dirt component dissolved and / or dispersed in the detergent are cleaned and dried easily. Refers to the process of replacing components. This clean, easily dried component is called a “rinse agent”. In the present invention, the compound (b) alone or the composition (d) is used as a rinsing agent. Further, the "steam cleaning step" refers to the step of boiling a steam generating tank liquid containing a rinsing agent to form a compound (b) alone or a saturated vapor phase of the composition (d) formed on the upper part of the steam generating tank. After the “washing step” or the “rinsing step”, the object to be washed is allowed to stand, and a liquid composition generated by condensation of the clean compound (b) alone or the vapor of the composition (d) on the surface of the object to be washed Washing and / or rinsing process with an object (including simple substance).

The rinsing agent includes the compound (b) alone or the composition (d). In the rinsing tank, the compound (c) and the dirt component are immersed in the rinsing agent of the rinsing bath by immersing the object to which the detergent component and the dirt component dissolved and / or dispersed in the detergent are attached. Stored. When performing the steam cleaning step after the rinsing step, the cleaning agent and the rinsing agent mixed with the dirt component dissolved and / or dispersed in the cleaning agent overflow from the rinsing tank and are taken into the steam generating tank. The compound (c) and the dirt component accumulate in the rinsing agent in the steam generating tank.

In the case where the steam cleaning step is performed without going through the rinsing step after the cleaning step, the cleaning component adhering to the object to be cleaned and the dirt component dissolved / or dispersed in the cleaning agent are removed.
The liquid clean compound (b) generated by condensation is replaced with a simple substance or the composition (d). The replaced detergent component and the soil component dissolved / and / or dispersed in the detergent are collected in the steam generating tank and accumulated in the rinsing agent in the tank. As a separation method of the present invention, when separating a dirt component from the cleaning composition (a) mixed with the dirt component used in the above-mentioned cleaning step, the cleaning composition (a) is allowed to stand still. is necessary. Due to the high specific gravity and low compatibility characteristics of non-chlorine fluorine compounds, convection or diffusion of each component in the liquid is less likely to occur by standing, and some of the detergent components are selected from the liquid level As a result, the cleaning composition (a) containing the contaminated dirt component is separated. By concentrating the dirt component in the separated upper layer, the detergent composition (a)
It is possible to remove the dirt component mixed into the cleaning tank outside. This phenomenon is due to the high compatibility of CFC113 and HCFC
It is not found in a cleaning agent containing a chlorine-based compound such as 225, and may occur specifically in a cleaning agent containing a low-compatible non-chlorine-based fluorine compound.

The term "stationary" as used herein means, in principle, a state in which there is no convection in the detergent composition (a) placed in a container. For example, stirring at about 30 rpm, etc. Shall belong. Further, in a method of separating a detergent component and a dirt component dissolved / and / or dispersed in the detergent, which has been mixed in the rinse agent, when the rinse agent is allowed to stand still, the liquid surface is removed regardless of the liquid temperature. A part of the rinsing agent component mixed with the detergent component and the soil component dissolved / and / or dispersed in the detergent selectively evaporates,
Also, convection or diffusion of each component in the liquid is unlikely to occur, so that phase separation occurs in the rinsing agent. By concentrating the compound (c) and the dirt component in the separated upper layer, the compound (c) and the dirt component mixed in the rinsing agent can also be removed outside the rinsing tank and / or the steam generating tank. Become.

The liquid temperature at the time of the separation may be any temperature, but when heated, when heated, the detergent composition (a) containing the contaminant component, or the detergent component and the detergent component dissolved in the detergent / This is preferable because the rinsing agent component in which the dispersed dirt component is mixed promotes evaporation and the separation is accelerated. The heating temperature is not particularly limited, but is preferably equal to or lower than the boiling point of the non-chlorine fluorine compound mentioned as the compound (b). As a heating method, any method such as continuous heating at a certain temperature or intermittent heating may be used.

Further, the state in which the vapor of the cleaning composition (a) mixed with the dirt component or the rinsing agent mixed with the dirt component dissolved and / or dispersed in the cleaning component and the cleaning agent can be diffused is as follows. This is preferred because it promotes evaporation and accelerates separation. For example, the entire surface or a part of the upper part of the container containing the detergent composition (a) mixed with the dirt component or the rinsing agent mixed with the dirt component dissolved and / or dispersed in the detergent component and the detergent is removed. Examples include a state where the container is open, and a state where the space volume in the container is twice or more the liquid volume even when the container is closed.

When the separation apparatus used in the separation method of the present invention performs the separation while performing each of the washing step, the rinsing step, and the steam washing step, the separation is performed within a range of a condition capable of maintaining “stationary”. , By any method such as pumping,
Cleaning, rinsing, and vapor generation From at least one of the respective tanks, and after performing separation, the liquid from which the dirt component has been removed is returned to a predetermined tank, and one or more separation tanks Installation. The flow rate of the pump can be set to an arbitrary flow rate within a range of conditions that can maintain “stationary”. Here, the separation tank is a separation tank for separating dirt components mixed in the cleaning agent sent from the washing tank, and a cleaning agent mixed in the rinsing agent sent from the rinsing tank and / or the steam generation tank. It is preferable to separately install the separation tank for separating the dirt component dissolved and / or dispersed in the agent. Further, it is preferable that the inlet of the liquid sent from each tank into the separation tank is below the liquid level in the separation tank. By allowing this to stand in this separation tank, the dirt component mixed in the cleaning agent, and the dirt component mixed in the rinsing agent and the dirt component dissolved and / or dispersed in the cleaning agent can be separated into an upper layer. . The lower layer clean cleaning agent or rinsing agent may be sent by a pump or by overflowing after providing a partition plate so that separated dirt components etc. are not brought into the liquid sending section to each tank. The liquid can be sent from the separation tank to each tank by the method. In the separation tank, the effect of convection in the separation tank generated when the liquid is sent to the separation tank is reduced, the separation of the mixed dirt components is promoted, and the separated dirt components etc. A partition plate for the purpose of preventing carry-in may be provided. By performing this circulation, the cleanliness in each of the washing tank, the rinsing tank, and the steam generating tank can be maintained.

Further, if it is possible to secure time during which the respective steps of the cleaning step, the rinsing step, and the steam generating step are not performed,
Separation is possible by standing still in any of the washing tank, the rinsing tank and the steam generating tank as well as the separating tank. When the solution is allowed to stand and separated in each tank, a heating device such as a heater for heating may be installed to promote the separation as the liquid temperature. In each tank, by installing a float and an electric valve for detecting the interface, the separated dirt component or the dirt component dissolved and / or dispersed in the cleaning agent and the cleaning agent are automatically discharged out of the system. You can also.

As an apparatus for carrying out the separation method of the present invention, as a specific example of the separation apparatus, the washing and separation apparatus shown in FIG. 1 can be mentioned. Hereinafter, the washing and separating apparatus of the present invention will be specifically described with reference to the accompanying drawings. However, aspects of the washing and separating apparatus according to the present invention are not limited to this example. The cleaning and separating apparatus shown in FIG. 1 has a cleaning tank 1 for storing a cleaning composition as a main structure,
A rinsing tank 2 and a steam generating tank 3 for storing the rinsing agent, a steam zone 4 filled with the rinsing agent vapor, the evaporated rinsing agent being condensed by the cooling pipe 9, and the condensed liquid and water adhering to the cooling pipe are allowed to stand. It comprises a water separator 5 for separation, and a separation tank 19 for separating the compound (c) mixed in the steam generation tank and a dirt component.

First, a cleaning device will be described with reference to the accompanying drawings. In actual cleaning, the object to be cleaned is placed in a dedicated jig or basket, and the cleaning is completed while passing through the cleaning device in the order of the cleaning tank 1, the immersion rinsing tank 2, and the steam zone 4. In the cleaning tank 1, the cleaning composition (a) is heated and heated by the heater 7, and the dirt component adhering to the object to be cleaned is cleaned and removed by cavitation generated by the ultrasonic vibrator 8 while controlling the temperature to a constant temperature. . At this time, as the physical force, other than the ultrasonic wave, any method employed in the conventional cleaning machine such as rocking or jetting of a cleaning agent into a liquid may be used. In the present cleaning apparatus, when moving from the cleaning tank 1 to the rinsing tank 2, since the detergent component adheres to the surface of the object to be washed, it prevents the contamination of the dirt component due to drying on the surface of the object to be washed. It is possible to move to the rinsing tank 2.

In the rinsing tank 2, the detergent component adhering to the article to be washed and the dirt component dissolved / dispersed in the detergent are rinsed with the rinse agent. The rinsing agent enters the steam generating tank 3 from the rinsing tank 2 through the overflow pipes 11, 16 and 12, is heated and boiled by the heater 6 of the steam generating tank 3, becomes steam, and fills the steam zone as indicated by arrow 13. After being condensed in the cooling pipe 9, the water is collected from the pipe 14 to the water separator 5 and separated from water, and then returns to the rinsing tank 2 through the pipe 15.

By circulating the rinsing agent while changing the state of the rinsing agent into a liquid or a gas in the cleaning device and overflowing the liquid from the rinsing tank 2 to the steam generating tank 3, not only the steam cleaning in the steam zone 4 but also The cleaning component and the dirt component dissolved and / or dispersed in the cleaning agent brought into the rinsing tank 2 are continuously removed from the steam generating tank 3.
And the cleanliness of the rinsing tank 2 can be maintained. The steam cleaning performed in the steam zone 4 filled with the steam generated in the steam generating tank 3 is effective as the final cleaning at the end of the cleaning process because the liquid condensed on the surface of the object to be cleaned does not contain any dirt components. . Further, in order to enhance the cleaning effect, the temperature of the rinsing agent is kept low in the cooling pipe 10 of the rinsing tank 2 and the temperature of the object to be immersed is kept low, so that the temperature difference from the steam temperature is widened and the amount of condensate is increased. It is effective to increase the number.

In the cleaning apparatus of the present invention, the cleaning composition (a) and the rinsing agent have two independent immersion tank structures to use the two liquids. When used in common, the evaporation loss of (b) the chlorine-free fluorine compound from the cleaning agent is suppressed, and as a result, the composition fluctuation of the cleaning agent is reduced, and the cleaning agent can be used for a long time. Next, an apparatus for separating a rinsing agent containing a detergent component and a dirt component dissolved and / or dispersed in the detergent will be described with reference to FIG. The cleaning agent and the rinsing agent in the steam generating tank mixed with the dirt component dissolved and / or dispersed in the cleaning agent are sent to the separation tank 19 through the pipe 18 by the pump 17. Here, the separation tank 19 needs to be left still. FIG.
Then, the upper surface of the separation tank 19 is opened in order to promote the evaporation of the cleaning agent component and the rinsing agent component mixed with the dirt component dissolved and / or dispersed in the cleaning agent and accelerate the separation. 20 for heating.

In FIG. 1, by providing a partition plate 21 whose upper part is open, the influence of convection generated at the time of liquid sending using the pump 17 is reduced, and the cleaning agent sent into the separation tank 19 is removed. The rinsing agent mixed with the dirt component dissolved and / or dispersed in the component and the cleaning agent forms the separation tank 19.
By passing through the upper portion of the inner liquid, the separation of the mixed detergent component and the dirt component dissolved and / or dispersed in the detergent is promoted. Also, FIG.
A partition plate 22 having an open lower portion is provided on the side away from the partition plate 21 from the inlet of the rinsing agent mixed with the detergent component and the dirt component dissolved and / or dispersed in the detergent. A clean rinsing agent is brought into the liquid feed pipe 25 side separated by the partition plate 22, and an arrow 2
It overflows as in 3 and returns to the steam generation tank 3 through the liquid feed pipe 25. By this circulation, the cleanliness of the rinsing agent in the steam generating tank 3 can be maintained.

In FIG. 1, the compound (C) separated at the top of the separation tank is provided by providing a float 24 for detecting an interface.
The soil component dissolved and / or dispersed in the cleaning agent is discarded out of the system after being accumulated in a certain amount. In FIG. 1, it is possible to perform a continuous operation of separating the cleaning agent component and the dirt component dissolved / and / or dispersed in the cleaning agent mixed in the steam generating tank while performing the cleaning.

Next, each compound will be described. The above-mentioned (b) non-chlorine fluorine compound is a fluorine compound in which part of the hydrogen atoms of hydrocarbons or ethers is replaced only by fluorine atoms and does not contain chlorine atoms. For example, the following general formula (1) A) a cyclic HFC specified by (2), a chain HFC specified by (2), or a HFE specified by (3), which does not contain a chlorine atom and comprises a carbon atom, a hydrogen atom, an oxygen atom, and a fluorine atom. , And 2 selected from these
Combinations of more than one compound and the like can be mentioned.

C _n H _2n-m F _m (1) (in the formula, an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n-1) C _x H _{2x + 2-y} F _y (2) ( (In the formula, an integer of 4 ≦ x ≦ 6, 6 ≦ y ≦ 2x + 1 is indicated.) C _s F _{2s + 1} OR (3) (where 4 ≦ s ≦ 6, R is an alkyl group having 1 to 3 carbon atoms) Specific examples of the cyclic HFC include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, 5H, 6H, 6H-nonafluorocyclohexane and the like.

Specific examples of chain HFCs include 1H, 2
H, 3H, 4H-perfluorobutane, 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane,
2H, 3H-perfluorobutane, 4H, 4H-perfluorobutane, 1H, 1H, 3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 1H, 2
H, 3H-perfluorobutane, 1H, 2H-perfluoropentane, 1H, 4H-perfluoropentane, 2
H, 3H-perfluoropentane, 2H, 4H-perfluoropentane, 2H, 5H-perfluoropentane,
1H, 2H, 3H-perfluoropentane, 1H, 3
H, 5H-perfluoropentane, 1H, 5H, 5H-
Perfluoropentane, 2H, 2H, 4H-perfluoropentane, 1H, 2H, 4H, 5H-perfluoropentane, 1H, 4H, 5H, 5H, 5H-perfluoropentane, 1H, 2H-perfluorohexane, 2H,
3H-perfluorohexane, 2H, 4H-perfluorohexane, 2H, 5H-perfluorohexane, 3
H, 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, ethyl perfluoropentyl ether and the like. Can be mentioned.

The detergent used in the present invention comprises these (b)
One or two or more compounds selected from non-chlorine fluorine compounds can be used in combination, but are preferably soluble in highly polar solvents such as alcohols, ketones, esters, and glycol ethers. Cyclic HFC or HFE having a high global warming potential and a low global warming potential. More preferably, 4H, 5H, 5H-perfluorocyclopentane, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, or a mixture thereof can be mentioned. More preferably, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether or a mixture thereof (trade name: HFE7100, manufactured by Sumitomo 3M Limited), ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether or a mixture thereof (trade name: HFE7200) And Sumitomo 3M Ltd.). Still more preferably, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether or a mixture thereof (trade name: HFE7100, manufactured by Sumitomo 3M Ltd.) can be mentioned.

The detergent used in the present invention must contain (c) an organic compound for the purpose of improving the detergency of a wide variety of stains. The cleaning composition (a) used in the present invention is a composition containing the compounds (b) and (c). The detergent composition (a) is preferably composed of a homogeneous solution containing the compound (b) and the compound (c) as one component. Further, the detergent composition (a) is preferably a composition having no flash point, which does not require equipment such as a washing machine to have an explosion-proof structure. Here, "no flash point"
Means that the cleaning agent is recognized as having no flash point by a general flash point evaluation test such as JIS K 2265.

(C) Examples of the organic compound include glycol ethers, glycol ether acetates, and hydroxycarboxylic acid esters. These organic compounds can be used alone or in combination of two or more. Glycol ethers as used herein refers to an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms, wherein any of the two hydroxyl groups is either a hydrocarbon or a hydrocarbon. It is a compound substituted with a residue or a hydrocarbon residue containing an ether bond.
For example, glycol ethers specified by the following general formula (4) can be mentioned.

[0034]

Embedded image

(Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms;
Alkenyl group or cycloalkyl group, R ² , R ³ , R
⁴ is hydrogen or a methyl group, R ⁵ is hydrogen or a carbon number of 1 to
6, an alkyl group, an alkenyl group, or a cycloalkyl group, and a represents an integer of 0 to 1. b represents an integer of 1 to 4. )

Specific examples of glycol ethers include:
Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-
n-butyl ether, dipropylene glycol dimethyl ether, 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 Non-n-propyl ether, dipropylene glycol mono-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 and the like can be mentioned.

The glycol ether acetates used in the detergent of the present invention are compounds obtained by converting glycol ether monoalkyl ethers into acetate. As used herein, glycol ether monoalkyl ethers are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, and any one of the two hydroxyl groups is used. It is a compound in which the hydrogen of a hydroxyl group is substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond. For example, glycol ether acetates specified by the following general formula (5) can be mentioned.

[0038]

Embedded image

(Wherein R ⁶ is an alkyl group having 1 to ⁶ carbon atoms;
Alkenyl group or cycloalkyl group, R ⁷ , R ⁸ , R
⁹ is a hydrogen or methyl group, c is an integer of 0 to 1, d is 1 to
Represents an integer of 4. )

Specific examples of glycol ether acetates include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
Acetate of monoalkyl ether corresponding to dipropylene glycol and tripropylene glycol, 3
-Methoxy-1-butyl acetate, 3-methoxy-3
-Methyl-1-butyl acetate and the like.

The hydroxycarboxylic acid esters used in the detergent of the present invention are ester compounds having a hydroxyl group, such as lactic acid ester, malic acid ester, tartaric acid ester, citric acid ester, glycol monoester, glycerin monoester. Esters, glycerin diesters, ricinoleic esters, castor oil and the like can be mentioned. Particularly preferred hydroxycarboxylic acid esters include lactic acid esters specified by the following general formula (6).

[0042]

Embedded image

(In the formula, R ¹⁰ represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms.)

Specific examples of the lactic acid esters include methyl lactate, ethyl lactate, butyl lactate and pentyl lactate. Here, the vapor pressure of the organic compound (c) is not particularly limited, but is preferably in a range where the detergent composition (a) has no flash point, and more preferably the vapor pressure at 20 ° C. is 1.013. It is less than × 10 ³ Pa, more preferably 6.66 × 10 ² Pa or less, and even more preferably 1.013 × 10 ² Pa or less.

When the specific gravity difference between the compound (c) and the compound (b) is large, the specific gravity is generally higher than that of the compound (c), and the volatile compound (b) is difficult to diffuse into the upper layer. Thus, the separation is accelerated. When the specific gravity difference between the compound (b) and the compound (c) is 0.3 or more at 25 ° C., good separation properties can be realized. To achieve better separation properties, the difference in specific gravity between compound (b) and compound (c) is 2
At 5 ° C., it is preferably 0.5 or more.

In order to improve the rinsing properties of the rinsing agent,
Instead of the compound (b) alone, the composition (d) to be used as the composition (d) and the compound (e) are rinsed with a composition containing an organic compound having a boiling point of 20 ° C. to 100 ° C. at 1.013 × 10 ⁵ Pa. It may be used as an agent. Further, the composition (d)
Is preferably a composition having no flash point, which does not require equipment such as a washing machine to have an explosion-proof structure. Here, the compound (e) is a compound different from the compounds (b) and (c).

The compound (e) can be exemplified, for example, for each type of solvent shown below. Examples of the hydrocarbons include n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n-heptane, 2-methylhexane,
-Methylhexane, 2,4-dimethylpentane, isooctane and the like.

Examples of alcohols include methanol, ethanol, n-propanol, isopropanol and the like. Ketones include acetone and methyl ethyl ketone. Examples of the esters include ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and the like.

The compound (e) was 1.013 × 10 ⁵ Pa
Or a combination of two or more selected from organic compounds having a boiling point of from 20 ° C to 100 ° C. Compound (e) has a boiling point at 1.013 × 10 ⁵ Pa of 20 ° C. to 100 ° C., and is used together to reduce composition fluctuations during use. It is preferably within a range of 40 ° C, more preferably ± 30 ° C.

The compound (e) is preferably an azeotropic composition with the non-chlorine fluorine compound (b) used together or an azeotropic composition having a composition similar thereto.

[0051]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. In addition, the performance by each washing method was measured and evaluated as follows. (1) Separability evaluation test A separation evaluation test of the steam generation tank liquid was performed by the method described below. Glass epoxy printed circuit board (70 × 4
8cm) in a flux on one side and air-dried.
A test piece prepared by soldering at ℃ was used. Five test pieces are put in a basket, and ultrasonic cleaning → rinsing → using the apparatus of FIG. 1 and a cleaning agent and a rinsing agent having a predetermined composition.
Cleaning was performed in a steam cleaning process. The capacity of each tank was 8.0 L for the washing tank, 9.5 L for the rinsing tank, and 6.5 for the steam generating tank.
L. The temperature was set to 40 ° C. in the washing tank, and the temperature of the rinsing tank was set to room temperature, and washing was performed for 3 minutes in each step. This was defined as one cycle, and a total of 125 cycles (125 × 5 test pieces) were washed.

Thereafter, the liquid in the steam generating tank was collected, and the residual of the compound (c) and the flux were measured by gas chromatography. The separability was evaluated based on the following criteria. ：: Compound (c) content 5 wt% or less and flux residual amount 1 wt% or less ×: Compound (c) content 5 wt% or more or flux residual amount 1 wt% or more

[0053]

EXAMPLES As the detergent composition (a), (b) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (trade name, HFE7100, manufactured by Sumitomo 3M Ltd.) 50 wt% (c) dipropylene glycol dimethyl ether 20 wt % And 3-methyl-
A product containing 30% by weight of 3-methoxybutanol was prepared. HFE7100 was used as a rinsing agent. Using these compositions, the pump 17 shown in FIG. 1 was operated, and a separation evaluation test was conducted while feeding the vapor generation tank liquid to the separation tank. The heater 20 is used and the separation tank is 50
Set to ° C. As a result, as shown in the table below, it was confirmed that the liquid in the steam generation tank was clean with few compounds (c) and dirt components.

[0054]

COMPARATIVE EXAMPLE The same cleaning composition and rinsing agent as in the example were used. Using these compositions, a separation evaluation test was performed without operating the pump 17 of FIG. 1 and using a separation tank. As a result, as shown in the table below, it was confirmed that the compound (c) and the dirt component were mixed in the steam generation tank liquid.

[0055]

[Table 1]

[0056]

According to the present invention, the cleaning cost can be reused by separating the dirt component mixed in the cleaning agent and the rinsing agent and the cleaning component mixed in the rinsing agent, thereby reducing the running cost in the cleaning process. Can be reduced.

[Brief description of the drawings]

FIG. 1 is an example of an apparatus for performing a separation method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Washing tank 2 Rinse tank 3 Steam generating tank 4 Steam zone 5 Water separator 6 Heater 7 Heater 8 Ultrasonic vibrator 9 Cooling pipe 10 Cooling pipe 11 Overflow pipe 12 Overflow pipe 13 Steam flow 14 Condensation liquid pipe 15 Water separation Piping for condensed liquid 16 Piping for overflow liquid 17 Pump 18 Piping for liquid supply in vapor generation tank 19 Separation tank 20 Heater 21 Partition plate 22 Partition plate 23 Rinse agent liquid flow 24 Float 25 Clean rinsing agent liquid supply pipe

Claims (6)

[Claims] 1. A method for cleaning with a cleaning composition (a), wherein the cleaning composition (a) is a composition containing (b) a chlorine-free fluorine compound and (c) an organic compound. A cleaning method, wherein the cleaning composition (a) used for cleaning is allowed to stand still to separate dirt components mixed in the cleaning composition (a). 2. A method for rinsing compound (b) alone as a rinsing agent after washing with a detergent composition (a) and / or performing steam cleaning, wherein the rinsing agent used for rinsing and / or steam cleaning is used. A separation method characterized by separating the compound (c) and the dirt component mixed in the rinsing agent by standing still. 3. The rinsing agent is a composition containing the compound (b) as the composition (d) and (e) an organic compound having a boiling point of 20 ° C. to 100 ° C. at 1.013 × 10 ⁵ Pa. 3. The method according to claim 2, wherein: 4. The method according to claim 1, wherein the specific gravity difference between the compound (b) and the compound (c) is at least 0.3 at 25 ° C. 5. The method according to claim 1, wherein the compound (b) is methyl perfluorobutyl ether, methyl perfluoroisobutyl ether or a mixture thereof. 6. A separation apparatus for performing the separation method according to claim 1, wherein a separation tank is used.