JP4767002B2 - Pre-cleaning method and cleaning device - Google Patents

Description

  The present invention eliminates all kinds of dirt such as processing oils, greases, waxes used in the machining of mechanical parts, precision machine parts, optical machine parts, etc. The present invention relates to a cleaning method and a cleaning apparatus suitable for cleaning.

  Various processing oils used when processing machine parts, precision machine parts, optical machine parts, etc., such as cutting oils, press oils, drawing oils, heat treatment oils, rust preventive oils, lubricating oils, or greases, Waxes and the like are used, but these stains need to be finally removed, and removal with a solvent is generally performed.

  Soldering is the most commonly used method for joining electronic circuits, but rosin is used for the purpose of removing and cleaning oxides on the metal surface to be soldered, preventing reoxidation, and improving solder wettability. In general, the soldering surface is pre-treated with a flux containing as a main component. Since this flux residue causes corrosion of the metal and deterioration of insulation, it is necessary to remove it sufficiently after the soldering is completed.

  These washing and removal have many characteristics such as nonflammability, low toxicity and excellent solubility, so that 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as “removable”) CFC113) or a mixture of CFC113 and alcohol was used for cleaning, but global environmental pollution problems such as ozone depletion were pointed out, and production was abolished in Japan at the end of 1995. As an alternative to the CFC 113, a mixture of 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as “CFC 113”) Hydrochlorofluorocarbons (such as HCFC225) have been proposed, but these are also expected to be banned in Japan in 2020 due to their ability to destroy the ozone layer.

  Further, in recent years, non-flammable fluorine-based solvents having no ozone layer destructive ability such as hydrofluorocarbons (hereinafter referred to as HFC) and hydrofluoroethers (hereinafter referred to as HFE) containing no chlorine atom have been proposed. Since it does not contain chlorine atoms, its solubility is low and it cannot be used alone as a cleaning agent.

  Patent Literature 1, Patent Literature 2, and Patent Literature 3 disclose a mixed solvent of a non-chlorine fluorine compound such as HFC or HFE and a compound that satisfies a specific condition for the purpose of improving detergency against dirt. Yes. Although these problems are solved by these inventions and a non-flammable cleaning composition having no ozone layer destructive ability and excellent dissolving ability is obtained, it is subject to washing due to an increase in dirt components accumulated in the cleaning agent. There is a problem of shortening the life of the cleaning solution due to the reattachment of the soil component to the surface of the object and the difficulty in separating the soil component and the cleaning agent component. In Patent Document 3 and Patent Document 4, the cleaning agent mixed with the dirt component in the cleaning tank is continuously sent to the dirt separation tank, the dirt component is separated and removed, and the cleaned cleaning agent is supplied to the cleaning tank. A cleaning method and a cleaning apparatus have been proposed to return, but there are problems such as an increase in the size of the apparatus, and a sufficient solution has not been achieved.

  As alternative cleaning agents, non-aqueous cleaning agents using hydrocarbon solvents or alcohol solvents in addition to halogen solvents, and aqueous cleaning agents containing acids, alkalis or surfactants are being developed. However, in these cleaning agents, especially cleaning agents that have a solvent with a high solubility and a relatively high boiling point, similarly, separation and removal of soil components accumulated in the cleaning agent and distillation reuse of the solvent can be used. Difficulties are a problem.

JP 10-36894 A Japanese Patent Laid-Open No. 10-192797 WO 01/092456 pamphlet JP 2000-8095 A

  The present invention has the effect of suppressing the poor cleaning caused by the decrease in detergency and the reattachment of dirt components to the surface of the object to be washed due to the increase in dirt components accumulated in the cleaning agent in the step of washing the article. It is an object of the present invention to provide a cleaning method and a cleaning apparatus that are excellent and dramatically improve the liquid life of the cleaning agent.

As a result of various studies on the cleaning composition, the cleaning method, the soil separation method, and the cleaning device for achieving the above-mentioned problems, the present inventor dissolved the soil before the cleaning in the step of cleaning the article. Poor performance and high specific gravity (a) Pre-cleaning with a composition (b) containing a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more, and stains on the finished cleaning agent Not only can the amount of carry-in be greatly reduced, but it is also possible to continuously and easily separate the dirt components removed from the surface of the object to be washed in the pre-cleaning from the composition (b), greatly increasing the liquid life of the finish cleaning agent. In addition, the pre-cleaning effect is further enhanced by rough cleaning with a hydrocarbon solvent as a pre-treatment for pre-cleaning, and the amount of dirt brought into the finish cleaning agent is further increased. It can solve the previous term problem by reducing the al, and have completed the present invention.
Aspects of the present invention are as described below.

(1) In the step of washing the article, the composition (b) contains 95 % by volume to 100% by volume of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or higher. After pre-cleaning to remove the dirt component adhering to the surface to be washed ,
Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher and 1.33 at 20 ° C. Washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 10 ³ Pa ,
Finishing cleaning containing a stain component adhering to the surface of the object to be cleaned with a rinsing agent which is a condensate obtained by heating the finishing cleaning agent (c) or a rinsing agent having the same composition as the composition (b) A cleaning method comprising rinsing to remove the agent (c) .
(2) The cleaning method according to claim 1, wherein the component (a) contains hydrofluorocarbon (HFC) and / or hydrofluoroether (HFE).
(3) Component (a) is 2H, 2H, 4H, 4H, 4H-pentafluorobutane (HFC365mfc), 2H, 3H-perfluoropentane (HFC43-10mee), methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and These mixtures (HFE7100), ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether and mixtures thereof (HFE7200), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (HFE347pc-f) and 4H, 5H, 5H-heptafluorocyclopentane, or one or a combination of two or more selected from the group consisting of 4H, 5H, 5H-heptafluorocyclopentane, .
(4) The component (d) is any one of the organic compounds having a hydrocarbon, alcohol, ketone, ether bond and / or ester bond, any one of the above (1) to (3) The cleaning method according to 1.
(5) Component (d) is dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, 3-methoxybutanol and 3-methyl-3- The cleaning method according to any one of (1) to (4) above, which is methoxybutanol, butyl lactate, or 3-methyl-3-methoxybutyl acetate.
(6) The cleaning according to any one of (1) to (5) above, wherein pre-cleaning is performed in a state in which the composition (b) is heated and / or in a state where steam is generated by heating. Method.
(7) The above (1) to (6), wherein the pre-cleaning step with the composition (b) is roughly cleaned with one or a combination of two or more selected from hydrocarbons (e). The cleaning method according to any one of the above.
(8) The cleaning method according to (7) above, wherein the hydrocarbon (e) is a C8 to C16 saturated hydrocarbon and / or kerosene.
(9) The cleaning method according to any one of (1) to (8) above, wherein in the pre-cleaning, the soil component is separated by distilling the composition (b) including the soil component. .

(10) (A) Component (a) To-be-washed with composition (b) containing 90 to 100 volume% of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more (B) a distillation tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, and (C) obtained by condensing the generated vapor. A pre-cleaning device having a water separation tank for removing water from the condensed liquid, and (A) a pre-cleaning tank and (B) a distillation tank being connected by piping;
(H) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher at 20 ° C. Heating to generate steam by heating and / or heating at least one component constituting the finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 1.33 × 10 ³ Pa A finish washing tank having a mechanism;
(I) a steam zone for steam cleaning with steam generated from the finish cleaning tank (H);
(J) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam;
(K) The cleaning method according to any one of (1) to (9) above, characterized in that it has a rinsing tank for immersion rinsing with a condensate from which water has been removed in a water separation tank. cleaning apparatus for.
(11) (D) Component (a) The composition to be washed with a composition (b) containing 90% by volume to 100% by volume of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more (E) a heating tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, (F) generated from the heating tank (E) A steam zone for steam cleaning with steam, (G) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam, (D) pre-cleaning tank and (E) heating A pre-cleaning device in which the tank is connected by piping;
(H) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher at 20 ° C. Heating to generate steam by heating and / or heating at least one component constituting the finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 1.33 × 10 ³ Pa A finish washing tank having a mechanism;
(I) a steam zone for steam cleaning with steam generated from the finish cleaning tank (H);
(J) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam;
(K) The cleaning method according to any one of (1) to (9) above, characterized in that it has a rinsing tank for immersion rinsing with a condensate from which water has been removed in a water separation tank. cleaning apparatus for.
(12) (A) Component (a) The composition to be washed with a composition (b) containing 90% by volume to 100% by volume of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more (B) a distillation tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, and (C) obtained by condensing the generated vapor. A pre-cleaning device having a water separation tank for removing water from the condensed liquid, and (A) a pre-cleaning tank and (B) a distillation tank being connected by piping;
(L) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) the vapor pressure at 20 ° C. of 13.3 Pa or higher. A finish washing tank for washing an object to be washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component of less than 1.33 × 10 ³ Pa;
(M) an immersion rinse bath for immersion rinse with a rinse agent having the same composition as component (a) or composition (b) ;
(N) a heating tank having a heating mechanism for generating vapor of a rinse agent having the same composition as component (a) or composition (b) ;
(O) a steam zone for steam cleaning with steam generated from the heating tank (N);
(P) The cleaning according to any one of (1) to (9) above, further comprising a water separation tank for removing water from the condensate obtained by condensing the generated steam. Cleaning device for carrying out the method .
(13) (D) Component (a) To-be-washed object by the composition (b) containing 90% by volume or more and 100% by volume or less of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more (E) a heating tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, (F) generated from the heating tank (E) A steam zone for steam cleaning with steam, (G) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam, (D) pre-cleaning tank and (E) heating A pre-cleaning device in which the tank is connected by piping;
(L) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) the vapor pressure at 20 ° C. of 13.3 Pa or higher. A finish washing tank for washing an object to be washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component of less than 1.33 × 10 ³ Pa;
(M) an immersion rinse bath for immersion rinse with a rinse agent having the same composition as component (a) or composition (b) ;
(N) a heating tank having a heating mechanism for generating vapor of a rinse agent having the same composition as component (a) or composition (b) ;
(O) a steam zone for steam cleaning with steam generated from the heating tank (N);
(P) The cleaning according to any one of (1) to (9) above, further comprising a water separation tank for removing water from the condensate obtained by condensing the generated steam. Cleaning device for carrying out the method .
(14) The cleaning device according to any one of (10) to (13) , wherein the pre-cleaning device has a mechanism for discharging the dirt component separated from the composition (b) out of the system.

  The present invention uses, as a pre-cleaning agent, a composition (b) containing a component (a) having a low ability to dissolve dirt and having a large specific gravity for pre-cleaning as a pretreatment for finishing cleaning in the step of cleaning an article. Thus, the specific gravity difference separation of the soil component from the composition (b) becomes extremely easy. Further, by distilling the soiled pre-cleaning liquid to separate the soil component and the composition (b), (b) maintaining a high pre-cleanability for a composition (b) having a high cleanliness for a long period of time. Can do. With the pre-cleaning effect of this composition (b), a significant reduction in the amount of dirt components brought into the finishing cleaning process is achieved, and the liquid life is dramatically improved by reducing the load on the finishing cleaning agent, Precision cleaning requiring a higher cleaning level is possible than when the finish cleaning agent is used alone.

Hereinafter, the present invention will be described in detail.
First, terms used in this specification will be described.
In the present specification, “pre-cleaning” refers to an intermediate cleaning that removes the soil components adhering to the surface of the object to be cleaned with the composition (b) containing the component (a) having a poor solubility in soil and high specific gravity. And requires final cleaning in a later process.
“Finishing cleaning” refers to final cleaning that completes cleaning by finally removing the soil components remaining on the pre-cleaned object surface with various cleaning agents.
Further, “rough cleaning” represents preliminary cleaning for removing the soil component adhering to the surface of the object to be cleaned by the hydrocarbons (e) having an excellent ability to dissolve the soil component as a pre-cleaning step.
The “dirt component” represents a component that is desired to be removed from the article to be washed. For example, processing oil adhering to precision parts, flux residue adhering to the printed circuit board, liquid crystal remaining between the gaps of the liquid crystal cell, and the like, and in the rinsing step, a finishing detergent component is also represented.

The cleaning method in the present invention comprises a pre-cleaning step and a pre-cleaning step using a composition (b) containing a component (a) having a low vapor solubility and a high specific gravity as a preceding cleaning step and a preceding step.
The performance required for the component (a) is as follows: 1) specific gravity is large to facilitate specific gravity difference separation (1.0 or more), and 2) vapor pressure is high to facilitate separation by distillation ( The vapor pressure at 20 ° C. is 1.33 × 10 ³ Pa or more) and 3) the soil solubility is low in order to facilitate separation of the soil.
The specific gravity of the component (a) is preferably 1.0 or more, more preferably 1.1 or more, and still more preferably 1.2 or more in separating the specific gravity difference from the soil component.
The pre-cleaning step essential for the cleaning method according to the present invention is a pretreatment step of the finish cleaning step by removing dirt components adhering to the object to be cleaned from the surface of the object to be cleaned by 50% or more, preferably 75% or more. Pre-cleaning is a process for reducing the occurrence of poor cleaning due to accumulation of dirt components in the subsequent final cleaning process and reducing the load of liquid replacement work, and obtaining a high cleanliness finish that cannot be obtained by finishing cleaning alone. Mainly pre-cleaning with the composition (b) stored in the tank, and if necessary, a pre-cleaning process comprising a step of steam cleaning with steam obtained by heating the composition (b) and a composition in use (b). This is a process that can be used in combination with a process of transferring the cleaning agent to a still and separating various soil components by continuous distillation or the like.

  As a specific pre-cleaning step, a pre-cleaning tank for pre-cleaning, a heating tank or a distillation tank having a heating mechanism for generating steam by heating the pre-cleaning agent comprising the composition (b), generation It consists of a water separation tank for removing water from the condensate obtained by condensing the steam. Steam generated by heating by the heater of the heating tank or distillation tank is condensed by the cooling pipe, and the condensed liquid overflows in the order of the pre-cleaning tank, heating tank or distillation tank after separating the water in the water separation tank. As necessary, a steam cleaning process using steam generated by heating by a heater or distillation tank heater, a pump, a filter, and a specific gravity difference for separating dirt components accumulated in the heating tank or distillation tank were used. Any mechanism such as a stationary tank can be installed.

  Furthermore, the cleaning method according to the present invention enables a cleaning method corresponding to precision cleaning that requires high cleaning performance that is difficult with a finish cleaning agent, by combining a pre-cleaning step and a subsequent cleaning step. By reducing the amount of dirt brought into the finish cleaning agent, the life of the liquid is dramatically increased, and the work efficiency at the cleaning site can be greatly improved.

  The final cleaning process is a process that removes dirt components remaining in the object that has been pre-cleaned in the pre-cleaning process and completes cleaning, and is mainly required for final cleaning with various finishing cleaning agents stored in the final cleaning tank. Depending on the surface of the object to be cleaned, the cleaning agent containing the dirt component attached to the surface of the object to be cleaned is replaced with a solvent that does not contain the dirt component. It is a process including a mechanism for steam cleaning that removes a slightly contaminated component on the surface with a liquid condensed on the surface of the object to be cleaned due to a temperature difference between the object to be cleaned and steam.

  Furthermore, in the cleaning method according to the present invention, as a pre-process of the pre-cleaning process, a rough cleaning process using hydrocarbons (e) having excellent solubility for the soil component is combined to bring the dirty component into the pre-cleaning process. By reducing the amount and substituting with a rough cleaning agent, by slightly imparting the ability to dissolve the soil component of the composition (b) containing the component (a) having poor solubility and high specific gravity in the pre-cleaning step, The pre-cleaning effect can be enhanced by improving the separation / removability of the dirt component from the surface of the object to be cleaned.

  The rough cleaning process is a process of reducing the amount of a large amount of dirt components adhering to the object to be cleaned in the previous process of the pre-cleaning process and replacing it with a rough cleaning agent, and is based on hydrocarbons (e) stored in the rough cleaning tank. It is a process that includes immersion rough cleaning as a main subject, and includes rocking, vibration, submerged jets, showers and ultrasonic waves or a combination of these physical forces in a rough cleaning tank as necessary.

The (a) non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. used in the pre-cleaning agent comprising the composition (b) of the present invention has a vapor pressure of 1.33 × at 20 ° C. The type is not particularly limited as long as it is 10 ³ Pa or more. For example, the cyclic HFC specified by the following general formula (1), the chain HFC specified by the following general formula (2), or the following general formula (3) Specific examples of the HFE that does not include a chlorine atom, a compound composed of a carbon atom, a hydrogen atom, an oxygen atom, and a fluorine atom, and combinations of two or more compounds selected from these compounds can be given.
C _n H _2n-m F _m (1)
(In the formula, integers of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1 are shown)
C _x H _{2x + 2-y} F _y (2)
(In the formula, an integer of 4 ≦ x ≦ 6, 5 ≦ y ≦ 12 is shown)
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 include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane (for example, Zeolora H (trade name)), 5H, 6H, 6H-perfluorocyclohexane, and the like. Can do. Specific examples of the chain HFC include 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H-perfluorobutane, 1H, 1H, 3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 1H, 2H, 3H-perfluorobutane, 1H, 2H, 3H, 4H-perfluorobutane, 2H, 2H, 4H, 4H, 4H-perfluorobutane (HFC365mfc), 1H , 2H-perfluoropentane, 1H, 4H-perfluoropentane, 2H, 3H-perfluoropentane (HFC43-10mee), 2H, 4H-perfluoropentane, 2H, 5H-perfluoropentane, 1H, 2H, 3H- Perfluoropentane, 1H, 3H, 5H-perfluoropentane, 1H, H, 5H-perfluoropentane, 2H, 2H, 4H-perfluoropentane, 1H, 2H, 4H, 5H-perfluoropentane, 1H, 4H, 5H, 5H, 5H-perfluoropentane, 1H, 2H-perfluoro Examples include hexane, 2H, 3H-perfluorohexane, 2H, 4H-perfluorohexane, 2H, 5H-perfluorohexane, 3H, 4H-perfluorohexane, and the like. Specific examples of HFE include methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and mixtures thereof (HFE7100), methyl perfluoropentyl ether, methyl perfluorocyclohexyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether and mixtures thereof. (HFE7200), ethyl perfluoropentyl ether, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (HFE347pc-f), and the like.
One or two or more compounds selected from these (a) non-chlorine fluorine compounds can be used in combination, preferably HFC or HFE having a low global warming potential. More preferably, HFC365mfc, 4H, 5H, 5H-perfluorocyclopentane (for example, Zeolora H (trade name)), methyl perfluorobutyl ether and methyl perfluoroisobutyl ether and HFE7100, ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether, and HFE7200, HFE347pc-f can be mentioned. More preferably, mention may be made of methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, HFE7100 and HFC365mfc having a soil dissolving ability suitable as a pre-cleaning agent, which are excellent in flash point suppression effect. In particular, in order to make the composition (b) and the finish cleaning agent non-flammable, it is necessary to contain a non-chlorine fluorine compound as the component (a).

  The composition (b) used in the pre-cleaning of the present invention comprises the component (a) as an essential component, but in a range not impairing its characteristics, a small amount of the component (d), antioxidant, or ultraviolet ray as necessary. An inhibitor or the like may be contained. The proportion of the component (a) in the composition (b) is not particularly limited as long as it does not impair the ability to dissolve dirt, the specific gravity, volatility, and nonflammability, which are features of the pre-cleaning agent of the present invention. Preferably they are 90 volume% or more and 100 volume% or less of the whole composition, More preferably, it is 95-100 volume%, More preferably, it is 98-100 volume%. In this range, sufficient soil separation, drying and non-flammability can be obtained.

The pre-cleaning method of the present invention may be cleaned by any method capable of pre-cleaning the object to be cleaned, and is not limited to the pre-cleaning method, but by the composition (b) containing the component (a), It is an essential requirement to pre-clean the article. By combining physical methods such as immersion, rocking, vibration, submerged jet, and ultrasonic waves for the purpose of improving the pre-cleanability in the pre-cleaning step, effective pre-cleaning becomes possible. In the heating or distillation step, the composition (b) is continuously circulated while changing the state of the composition (b) into a liquid or gas in the cleaning device by a heating mechanism for separating the composition (b) and the soil component. Therefore, pre-cleaning with a highly clean composition (b) is possible.
The pre-cleaning method of the present invention removes the soil components on the surface of the object to be cleaned with the composition (b) and continuously separates the removed soil components from the composition (b), thereby effecting a final cleaning effect in the subsequent step. It can be said that it is the most suitable cleaning method for increasing

A specific pre-cleaning method and pre-cleaning apparatus will be described with reference to the accompanying drawings.
FIG. 1 is an example of the pre-cleaning apparatus according to the aspect (10) of the present invention. A pre-cleaning tank (A) 1 for immersing an object to be cleaned by the composition (b) as a main structure, a distillation having a heating mechanism for generating vapor of at least one component or compound constituting the composition It has a tank (B) 2, a steam zone 3 filled with the vapor of the composition, and a water separation tank (C) 4 for removing moisture from the condensate obtained by condensing the generated steam. In actual pre-cleaning, the object to be cleaned is put in a dedicated jig or basket and passed through the pre-cleaning tank (A) 1 in the cleaning device to complete the pre-cleaning. On the other hand, the dirt removed from the surface of the object to be cleaned overflows continuously from the pre-cleaning tank (A) 1 together with the vapor condensate generated by heating the composition (b) and is distilled as indicated by the arrow 6. Since it enters tank (B) 2, it becomes possible to always maintain the cleanliness of composition (b) in pre-cleaning tank (A) 1 high.

  In the pre-cleaning tank (A) 1, the object to be cleaned is immersed in the composition (b), and the dirt adhered to the surface of the object to be cleaned by the ultrasonic wave generated by the ultrasonic vibrator 5 as a physical force. Peel from the surface. In the pre-washing with the composition (b), the physical force is effective because the dirt adhering to the surface of the object to be washed is not dissolved and removed but physically removed from the surface of the object to be washed. As the physical force, for example, ultrasonic waves, rocking, stirring, spraying the composition (b) in the liquid and brushing, or a combination thereof, the physical force employed in the conventional washing machine is used. Any method can be used as long as it is forceful. Further, the vapor of the composition (b) generated in the pre-cleaning tank (A) 1 is condensed by the cooling pipe 14, collected in the water separation tank (C) 4 through the pipe 15, and then cooled by the cooling pipe 12. Thus, the condensate and the water adhering to the cooling pipe 14 are allowed to stand and be separated and returned from the pipe 13 to the pre-cleaning tank (A) 1.

  In the distillation tank (B) 2, the steam generated by heating the composition (b) with the heater 8 is condensed in the cooling pipe 10 as shown by the arrow 9, and the condensate passes through the pipe 11 to form the water separation tank (C). 4, after the temperature is lowered by the cooling pipe 12, the condensate and the water adhering to the cooling pipe 10 are separated from each other and sent from the pipe 13 to the pre-cleaning tank (A) 1, overflowing, and the arrow 6 Return to the distillation tank (B) 2 through the pipe 7 as shown in FIG. The cooling pipes 10 and 14 can condense moisture in the air, prevent the moisture from being brought into the washing machine, and suppress the evaporation loss of the composition (b) due to vapor diffusion. In this immersion pre-cleaning, the amount of dirt components adhering to the object to be cleaned can be greatly reduced by using these physical forces in combination.

  In the pre-cleaning tank (A) 1, the composition (b) has a low ability to dissolve soil, so that a part of the soil component dissolves in the composition (b), but most does not dissolve and the composition (b) Due to the difference in specific gravity of the composition (b), the composition (b) exists in a floating state. The composition (b) in the pre-cleaning tank (A) 1 and the suspended dirt component are continuously fed from the water separation tank (C) 4 to the pre-cleaning tank (A) 1 (b). The condensate overflows from the pre-cleaning tank (A) 1, passes through the pipe 7 as indicated by an arrow 6, and moves to the distillation tank (B) 2.

  The dirt component slightly dissolved in the composition (b) transferred to the distillation tank (B) 2 and the dirt component floating not dissolved in the composition (b) are not evaporated by heating by the heater 8 and are not distilled. ) Accumulated and concentrated in 2. The dirt component accumulated and concentrated in the distillation tank (B) 2 is discharged out of the system from the distillation tank (B) 2 as necessary. Any method that has been used so far may be used for discharging, for example, after separating and floating dirt components by pump circulation to discharge out of the system, and then continuously using an oil skimmer and filter. And a method of adsorbing with an oil mat or scooping with a container or the like when a certain amount is accumulated in the tank. Furthermore, it becomes possible to accelerate the separation of the soil components more effectively by lowering the liquid temperature of the composition (b).

  In the pre-cleaning method and the pre-cleaning apparatus of the present invention, the composition (b) having a low ability to dissolve soil components is used, and the soil components are not dissolved but physically removed from the surface of the object to be cleaned. In addition to improving the separation between b) and the soil component and facilitating the discharge of the soil component to the outside of the system, the amount of the soil component brought into the finish cleaning agent in the subsequent process can be greatly reduced. In particular, it is effective as a pretreatment step for a finish cleaning agent in which the dirt components brought into the finish cleaning agent cannot be easily separated by a method such as distillation.

FIG. 2 is an example of the pre-cleaning apparatus according to the aspect (11) of the present invention. Pre-cleaning tank (D) 16 for cleaning the object to be cleaned with the composition (b) as a main structure, (b) a heating mechanism for generating vapor of at least one component or compound constituting the composition A heating tank (E) 17 having steam, a steam zone (F) 18 for steam cleaning with steam generated from the heating tank (E), and for removing moisture from the condensate obtained by condensing the generated steam. A water separation tank (G) 19 is provided.
In actual pre-cleaning, the object to be cleaned is put in a dedicated jig or basket and passed through the pre-cleaning tank (D) 16 and the steam zone (F) 18 in the cleaning device to complete the pre-cleaning. On the other hand, the dirt removed from the surface of the object to be cleaned overflows continuously from the pre-cleaning tank (D) 16 together with the vapor condensate generated by heating the composition (b) and is heated as indicated by an arrow 21. It becomes possible to enter the tank (B) 17 and maintain the cleanliness of the composition (b) in the pre-cleaning tank (D) 16 at a high level.

  In the pre-cleaning tank (D) 16, the object to be cleaned is immersed in the composition (b), and the dirt attached to the surface of the object to be cleaned is cleaned by the ultrasonic wave 20 generated by the ultrasonic vibrator 5 as a physical force. Peel from the surface of the object. In the pre-washing with the composition (b), the physical force is effective because the dirt adhering to the surface of the object to be washed is not dissolved and removed but physically removed from the surface of the object to be washed. As physical force, for example, physical force that has been employed in conventional washing machines such as ultrasonic waves, rocking, stirring, spraying the composition (b) in liquid and brushing, or a combination thereof. Any method can be used.

  In the heating tank (E) 17, the steam generated by heating the composition (b) with the heater 22 is condensed in the cooling pipe 24 as indicated by the arrow 23, and the condensate passes through the pipe 25 to form the water separation tank (C). 19, the condensate and the water adhering to the cooling pipe 26 are left and separated by lowering the temperature through the cooling pipe 26, and sent from the pipe 27 to the pre-cleaning tank (D) 16 and overflowed to the arrow 21. Return to the heating tank (E) 17 as follows. The cooling pipe 24 condenses moisture in the air, prevents moisture from being brought into the washing machine, and suppresses the evaporation loss of the composition (b) due to vapor diffusion.

  In the steam zone (F) 18, the steam of the component (a) having a high vapor pressure and the component (d) slightly contained in the finish cleaning agent (c) generated mainly in the heating tank (E) 17 are used. Use steam cleaning. The steam cleaning performed in the steam zone (F) 18 is effective as a final cleaning at the end of the pre-cleaning process because the dirt component is not included in the liquid formed by the steam condensing on the surface of the object to be cleaned.

  In the cleaning device of the pre-cleaning step, the component (a) having a high vapor pressure and the component (d) slightly included in the finish cleaning agent (c) are changed into a liquid or a gas in the cleaning device. Dirty components that may circulate and remain in the object to be washed are washed in the pre-cleaning tank (D) 16 and the steam zone (F) 18 to greatly increase the amount of dirt brought into the finishing cleaning agent in the subsequent process. Can be reduced. In this cleaning method, since the steam cleaning is performed in the steam zone (F) 18 and the process moves to the finishing cleaning step, it is an effective method and apparatus for further reducing the amount of dirt components brought into the finishing cleaning agent.

  Depending on the precision cleaning required for a higher cleaning level or the type of dirt, as a pre-cleaning step of pre-cleaning with the composition (b) of the present invention, (e) one or more selected from hydrocarbons Rough cleaning is effective in combination. (E) Hydrocarbons used here include hexane, heptane, octane, isooctane, nonane, decane, undecane, dodecane, tridecane, pentadecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4, Examples include 4,6,8,8-heptamethylnonane, kerosene, and light oil. One or two or more compounds selected from these hydrocarbons (e) can be used in combination, and preferred are decane and kerosene having a high flash point and a low viscosity. The cleaning method and cleaning device used for the rough cleaning may be any method and device that can be cleaned. Conventional cleaning methods and cleaning devices that have been used with hydrocarbon-based cleaning agents, or simply immersion cleaning. It is also possible to use a tank for this purpose.

In the final cleaning process, the pre-cleaned object to be cleaned is finally cleaned by removing the dirt components remaining in the object to be cleaned. A conventionally well-known thing is applied to the cleaning agent, the washing | cleaning method, and washing | cleaning apparatus which are used for this finishing washing | cleaning process. In particular, the effect of the pre-cleaning method of the present invention is more prominent in the case where it is difficult to separate the cleaning agent component from the soil component or in the cleaning agent containing a cleaning agent component that is relatively difficult to recover by distillation. . Therefore, although it is not limited, Preferably the finishing cleaning agent (c) used for the washing | cleaning process after pre-cleaning is (d) The vapor pressure in 20 degreeC is 13.3 Pa or more and less than 1.33 * 10 < ³ > Pa It is a finish cleaning agent containing ingredients, especially non-combustible in the final cleaning process, cleaning performance against various types of dirt, rinsing properties, and a final cleaning agent and pre-cleaning agent used for rinsing and steam cleaning in the final cleaning process. Considering that a common solvent can be used, the finish cleaning agent (c) has (a) a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and (d) a vapor pressure at 20 ° C. The most effective cleaning agent becomes possible in the finish cleaning agent containing a component of 13.3 Pa or more and less than 1.33 × 10 ³ Pa.

Here, (d) a component having a vapor pressure at 20 ° C. of 13.3 Pa or more and less than 1.33 × 10 ³ Pa is an organic compound having various hydrocarbons, alcohols, ketones and ether bonds and / or ester bonds. It is a compound having a good detergency against various stains such as a compound and having a vapor pressure at 20 ° C. of 13.3 Pa or more and less than 1.33 × 10 ³ Pa. When the vapor pressure of the component (d) is within this range, a finish cleaning agent having excellent cleaning properties and rinsing properties in the final cleaning step can be obtained. Preferably, it is 6.66 × 10 ² Pa or less at 20 ° C., more preferably 1.33 × 10 ² Pa or less.

Hereinafter, the component (d) will be described with specific examples.
Specific examples of hydrocarbons include decane, undecane, dodecane, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4,4,6,8,8-heptamethylnonane, and the like. Specific examples of alcohols include n-butanol, isobutanol, sec-butanol, isoamyl alcohol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, benzyl alcohol, furfuryl alcohol, ethylene glycol Propylene glycol and the like, and specific examples of ketones include methyl-n-amyl ketone, diisobutyl ketone, diacetone alcohol, phorone, isophorone, cyclohexanone, acetophenone, and the like. An organic compound having an ether bond is a compound containing at least one ether bond (C—O—C) in the molecular structure, and an organic compound having an ester bond is an ester bond in the molecular structure. It is a compound containing at least one (—COO—). Specific examples of the compound having an ether bond include 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, di Propylene glycol monomethyl ether, dipropylene glycol mono-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, Examples include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, and dipropylene glycol dimethyl ether. Compounds having an ester bond include: n-butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, γ-butyllactone, dimethyl succinate Dimethyl glutarate, dimethyl adipate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate and the like. As the component (d) used in the present invention, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol which do not produce alkoxyacetic acid in the metabolic system in the human body Dimethyl ether, 3-methoxybutanol and 3-methyl-3-methoxybutanol, butyl lactate, 3-methyl-3-methoxybutyl acetate and the like are preferred because of their lower toxicity.

(A) Non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or higher used as a component of the finish cleaning agent (c) is one or two of the compounds described in the pre-cleaning agent Combinations of the above are used. If necessary, an antioxidant and an ultraviolet absorber can be added.

The mass ratio of each component is not particularly limited as long as the high detergency, low toxicity, and non-flammability characteristic of the finish cleaning agent are not impaired, but (a) the vapor pressure at 20 ° C. Component (a) / component when a non-chlorine fluorine compound of 1.33 × 10 ³ Pa or more and (d) a component having a vapor pressure at 20 ° C. of 13.3 Pa or more and less than 1.33 × 10 ³ Pa are used together The range of the mass ratio of (d) is more preferably 90/10 to 20/80. When the mass ratio of the component (d) is greater than 10, a more preferable effect of improving the dissolving ability with respect to various types of dirt can be obtained, and when it is less than 80, a low residual property of the cleaning agent component on the surface of the object to be washed can be obtained. In consideration of the balance between the cleaning property of the cleaning agent and the persistence of the cleaning agent component on the surface of the object to be cleaned, the more preferable range of the mass ratio of the components (a) and (b) is 80/20 to 40/60. Preferably it is 70/30-50/50.

The cleaning method and cleaning device in the final cleaning process may be any method and device capable of cleaning the object to be cleaned, and improve the general cleaning method and cleaning device that have been used in the past with chlorine-based cleaning agents. Can also be used. Although not limited to a cleaning method and a cleaning apparatus, (a) non-chlorine having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C., which is particularly preferable when performing the final cleaning following the pre-cleaning of the present invention. A cleaning method and a cleaning apparatus using a finishing cleaning agent (c) containing a fluorine-based fluorine compound and (d) a component having a vapor pressure of 13.3 Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C. will be described below. .

  As a preferred cleaning method and cleaning device for precision cleaning requiring a high cleaning level, it is generated by cleaning dirt remaining on the object to be cleaned in the finishing cleaning tank and heating the finishing cleaning agent (c). Surface of the object to be washed by rinsing the object to be washed by dipping the condensed liquid of the component (a) having a high vapor pressure and the component (d) slightly contained in the steam to be immersed in the rinsing rinse tank. There may be mentioned a method and an apparatus for improving the steam cleaning effect by rinsing a slight dirt component that may adhere to the water and lowering the temperature of the object to be cleaned. As a rinse agent that can be used in the immersion rinse tank, in addition to using a condensate obtained by heating the finish cleaning agent, a component (a) or a component (a) appropriately mixed with component (d) is used. You can also. Furthermore, the rinsing agent used in the final cleaning process has the same composition as the pre-cleaning composition (b), which facilitates liquid management of the entire cleaning process including the pre-cleaning process and the final cleaning process. This is more preferable.

An example of a specific cleaning method in the finish cleaning step using the finish cleaning agent (c) containing the component (a) and the component (d) will be described with reference to the accompanying drawings. FIG. 3 shows an example of a cleaning apparatus including the pre-cleaning apparatus according to the aspect (10) of the present invention and the finish cleaning apparatus according to the aspect (14) of the present invention.
Finishing cleaning tank (H) 28 having a heating mechanism for heating and / or heating at least one component constituting finishing cleaning agent (c) as a main structure of the finishing cleaning device and generating steam, the finishing cleaning Steam zone (I) 30 for cleaning with steam generated from the tank (H), water separation tank (J) 31 for removing moisture from the condensate obtained by condensing the generated steam, water separation It comprises a rinsing tank (K) 29 for immersion rinsing with the condensate from which moisture has been removed in the tank (J). In actual cleaning, the object to be cleaned that has undergone the pre-cleaning process is placed in a dedicated jig or basket, and the interior of the finishing cleaning apparatus is a finishing cleaning tank (H) 28, a rinsing tank (K) 29, and a steam zone (I) 30. Washing is completed while passing in the order of.

In the finish cleaning in the finish cleaning tank (H) 28, the finish cleaning agent (c) is heated with a heater, and dirt remaining on the pre-cleaned object is cleaned and removed in a boiling state. At this time, as a physical force, any method may be used as long as it is a physical force employed in a conventional washing machine such as rocking or a jet of finishing detergent in liquid.
In the rinsing tank (K) 29, the finishing cleaning agent (c) is heated by the heater in the finishing cleaning tank (H) 28, the evaporated finishing cleaning agent is condensed by the cooling pipe, and the cooling pipe is supplied by the water separation tank (J) 31. The liquid temperature of the condensate is reduced and moisture is removed, and the condensate from which moisture has been removed returned to the rinsing tank (K) 29 and adhered to the object to be washed by the ultrasonic waves generated by the ultrasonic vibrator 34. Clean and remove finish cleaner and soil components. At this time, as a physical force, any method may be used as long as it is a physical force employed in a conventional washing machine such as rocking or a jet of finishing detergent in liquid. Moreover, although the rinse agent composition used for a rinse tank may be adjusted arbitrarily, since the composition fluctuation | variation of a finishing cleaning agent can be suppressed by making it the same composition as the condensate obtained by heating a finishing cleaning agent, it is preferable.

  In the steam zone (I) 30, 31 water separation tank in which the steam of the component (a) having a high steam pressure and the steam of the component (d) slightly contained in the finish cleaning agent (c) are condensed in the cooling pipe. After being collected in (J), it is sent to the rinsing tank (K) 29 where it is dissolved and / or dispersed in the finished cleaning agent adhering by immersing the object to be washed in the condensate. Remove dirt components. After the condensate is collected in the water separation tank (J) 31, it enters the rinse tank (K) 29 from the pipe 39, overflows, returns to the finishing washing tank (H) 28 as indicated by the arrow 33, and is heated by the heater 32. After boiling, a part or all of the composition is converted into vapor and condensed in the cooling pipe 36 as shown by the arrow, and then returns to the water separation tank (J) 31 from the condensate pipe 37. The steam cleaning performed in the steam zone (I) 30 filled with the steam generated in the finishing cleaning tank (H) 28 does not contain any dirt components in the liquid formed by the condensation of steam on the surface of the object to be cleaned. Therefore, it is effective as a final cleaning at the end of the cleaning process. In the cleaning apparatus of the final cleaning process, the component (a) having a high vapor pressure and the component (d) slightly included in the final cleaning agent (c) are changed to a liquid or a gas in the cleaning apparatus. Precision that requires a higher cleaning level is obtained by cleaning in the rinsing tank (K) 29 and the steam zone (I) 30 dirt components that may circulate and adhere slightly to the object to be cleaned. Can be adapted for cleaning.

  FIG. 4 shows an example of a cleaning apparatus comprising the pre-cleaning apparatus according to aspect (10) of the present invention and the finish cleaning apparatus according to aspect (15) of the present invention. As the main structure of the finishing cleaning apparatus, a finishing cleaning tank (L) 40 for cleaning the article to be cleaned with the finishing cleaning agent (c), heating and / or at least one component constituting the finishing cleaning agent (c) and / or Heated tank (M) 42 for generating steam by heating, steam zone (N) 43 for cleaning with steam generated from the heated tank (M) 42, obtained by condensing the generated steam A water separation tank (O) 44 for removing moisture from the condensate, a rinse tank (P) 41 for immersion rinsing with the condensate from which water has been removed in the water separation tank (O) 44, and a finish cleaning agent (c ) In the finishing cleaning tank (L) 40 and the heating tank (M) 42. The finishing cleaning agent circulation pipe 57 and the circulation pump 58 constitute a mechanism (Q).

In the finishing washing tank (L) 40, the dirt adhering to the article to be washed is removed by washing with ultrasonic waves generated by the ultrasonic vibrator 45 while being controlled at a constant temperature. At this time, as a physical force, any method may be used as long as it is a physical force that has been employed in conventional washing machines such as rocking and a jet of finishing detergent.
In the rinsing tank (P) 41, the finishing cleaning agent (c) is heated by the heater 47 in the heating tank (M) 42, the evaporated finishing cleaning agent is condensed by the cooling pipe (53), and the water separation tank (O) 44 is obtained. In the cooling pipe 55, the liquid temperature of the condensate is lowered and the water is removed, and the condensate from which the water has been removed returned to the rinsing tank (P) 41 is washed by the ultrasonic waves generated by the ultrasonic vibrator 46. The finish cleaning agent and dirt components adhering to the object are washed away. At this time, as a physical force, any method may be used as long as it is a physical force employed in a conventional washing machine such as rocking or a jet of finishing detergent in liquid. Moreover, although the rinse agent composition used for the rinse tank (P) 41 may use what mixed the component (d) with the component (a) or the component (a) suitably, it is obtained by heating a finishing cleaning agent. It is preferable to use the same composition as that of the condensate because the composition variation of the finish cleaning agent can be suppressed. Furthermore, the rinsing agent used in the final cleaning process has the same composition as the pre-cleaning composition (b), which facilitates liquid management of the entire cleaning process including the pre-cleaning process and the final cleaning process. This is more preferable.

In the steam zone (N) 43, the steam of the component (a) having a high steam pressure and the steam of the component (d) slightly contained in the finish cleaning agent (c) are condensed in the cooling pipe 53 to be a water separation tank. (O) After being collected in 44, it is sent to the rinsing tank (P) 41, and in the rinsing tank (P) 41, the object to be cleaned is dissolved and / or dispersed in the finished cleaning agent adhering to the condensed liquid. Remove dirt components. After the condensate is collected in the water separation tank (O) 44, it enters the rinse tank (P) 41 from the pipe 56, overflows, enters the finishing washing tank (L) 40 as indicated by the arrow 51, and further enters the pipe inlet. 48, the pipe 49, and the pipe outlet 50 are entered into the heating tank (M) 42, heated and boiled by the heater 47, and part or all of the composition is converted to vapor and condensed in the cooling pipe 53 as indicated by the arrow 52. Return to the water separation tank (O) 44 from the pipe 54.
In the steam cleaning performed in the steam zone (N) 43 filled with the steam generated in the heating tank (M) 42, no dirt component is contained in the liquid formed by the condensation of steam on the surface of the object to be cleaned. It is effective as a final cleaning at the end of the cleaning process.

  The mechanisms (Q) 57 and 58 for circulating the finishing cleaning agent between the finishing cleaning tank (L) 40 and the heating tank (M) 42 are piped from the heating tank (M) 42 to the finishing cleaning agent (c). (Q) 57 is sent to the finishing washing tank (L) 40 by the circulation pump (Q) 58, overflows from the finishing washing tank (L) 40, and is heated from the overflow port 48, the pipe 49, and the pipe outlet 50. By returning to (M) 42, the composition of the finishing cleaning agent (c) in the finishing cleaning tank (L) 40 and the heating tank (M) 42 is always kept the same, and the finishing cleaning agent (L) 40 in the finishing cleaning tank (L) 40 ( The composition fluctuation of c) can be suppressed, and stable detergency can be obtained. In actual cleaning, the object to be cleaned that has undergone the pre-cleaning process is placed in a dedicated jig or basket, and the interior of the final cleaning apparatus is a final cleaning tank (L) 40, a rinsing tank (P) 41, and a steam zone (N) 43. Washing is completed while passing in the order of. In the cleaning method and the cleaning apparatus shown in FIG. 4, since the finish cleaning tank is not boiled, ultrasonic cleaning is possible, and the cleaning method and apparatus are suitable for precision cleaning that requires high cleanliness.

In addition, various cleaning methods can be used as a finishing cleaning method in the post-process. For example, in the case of cleaning with one liquid without using a rinse agent, a preferable cleaning device is by heating the finishing cleaning tank. In the finishing cleaning tank, dirt remaining on the object to be cleaned is heated and cleaned, and the condensate of the component (a) having a high vapor pressure and the component (d) slightly contained in the finishing cleaner is mainly used in the vapor zone. Indicate a cleaning method that improves the steam cleaning effect by rinsing a slight dirt component that may adhere to the surface of the object to be cleaned and lowering the temperature of the object to be cleaned by shower rinsing inside Can do. In this cleaning method, it is not necessary to use a rinse agent, so that one-liquid cleaning is possible and a cleaning system with easy liquid management can be obtained.
In any of the above examples, the liquid management of the entire process is facilitated by setting the liquid composition of the condensate obtained by heating the finish cleaning agent (c) and the pre-cleaning composition (b) to the same composition. This is preferable.

The present invention will be described based on examples. The effects of the cleaning method and the cleaning apparatus were measured and evaluated as follows.
(1) Degreasing and detergency test An aluminum test sample (20 × 50 × 2 mm) having a mirror-finished surface was dipped in a metal working oil, pulled up and allowed to stand at room temperature for 1 hour to obtain a test sample. Using a cleaning agent, cleaning is performed in the order of rough cleaning, pre-cleaning and finish cleaning based on the test conditions shown below, and degreasing cleaning properties are evaluated.

1) Rough cleaning conditions Ultrasonic cleaning (28 kHz, 100 W) with 300 ml of kerosene at 25 ° C. for 1 minute.
2) Pre-cleaning conditions Ultrasonic cleaning (28 kHz, 100 W) is performed with 300 ml of the composition (b) at 25 ° C. for 10 minutes.
3) Finishing cleaning conditions Cleaning: 1 minute, boiling, liquid volume 300ml
Rinse: 1 minute, liquid temperature 30 ° C., liquid volume 300 ml (HFC365mfc, trade name: Solcan 365mfc, manufactured by Nippon Solvay Co., Ltd.), ultrasonic wave / 28 kHz, 100 W
Steam cleaning: 1 minute, 300 ml of liquid (HFC365mfc, trade name: Solcan 365mfc, manufactured by Nippon Solvay Co., Ltd.)

<Evaluation method (degreasing detergency)>
After the above finish cleaning, the sample surface condition is visually evaluated.
Evaluation is based on the following criteria.
◎: No white stain ○: Slight white stain △: Partial white stain ×: White stain Metal processing oil used in the test:
A-54 (trade name: Daikator, manufactured by Daido Chemical Industry Co., Ltd.)

[Examples 1 to 8]
Each component was mixed with the composition of Table 1, and the target composition (b) and the finishing cleaning agent (c) were obtained. The above evaluation test was performed using the composition (b) and the finish cleaning agent (c), and the results are summarized in Table 1. An excellent degreasing performance was obtained by pre-cleaning with the composition (b) containing the component (a), and the degreasing performance was improved by adding rough cleaning with kerosene.

[Comparative Example 1]
Rough cleaning and pre-cleaning performed in the above evaluation test were not performed, and only the same finish cleaning as in Examples 1 to 8 was performed. The results are summarized in Table 1. White stains were observed on the entire surface of the aluminum test sample, and sufficient degreasing performance was not obtained.

(2) Actual machine cleaning test The composition (b) is put into the pre-cleaning tank (A) 1, the distillation tank (B) 2 and the water separation tank (C) 4 of the cleaning apparatus shown in FIG. 28. Finished detergent is put in 28, rinse agent is put in rinse tank (K) 29 and water separation tank (J) 31, and the finished detergent in finish washing tank (H) 28 is heated and boiled by heater 32, and the object to be washed is The pre-cleaning tank (A) 1, the finishing cleaning tank (H) 28, the rinsing tank (K) 29, and the steam zone (I) 30 are moved in this order. It was measured.

1) Pre-cleaning conditions Pre-cleaning bath (A) 1: 10 minutes, liquid temperature 25 ° C., liquid volume 3000 ml, ultrasonic / 28 kHz, 100 W
2) Finish washing conditions Finish washing tank (H) 28: 1 minute, boiling, liquid volume 3000ml
Rinse tank (K) 29: 1 minute, liquid temperature 30 ° C., liquid volume 3000 ml, ultrasonic / 28 kHz, 100 W
Steam zone (I) 30: 1 minute Rinse agent: The same composition liquid as the condensate composition of steam obtained by heating each finish cleaning agent (c)

<Evaluation method (pre-cleanability)>
After impregnating metal processing oil with 75,000 stainless steel ball balls for ball bearings (φ2 mm) in a washing basket and pulling it up, at room temperature until the metal processing oil adhesion amount falls within the range of 18-22 g / 75,000. A sample was left for a certain period of time. This was transferred to another washing basket, and 75,000 stainless steel ball bearing balls (φ2 mm) with metalworking oil were immersed in the composition (b) by ultrasonic pre-cleaning, followed by boiling immersion with a finishing cleaner. Wash in the order of finish cleaning, ultrasonic immersion rinse with rinse agent, and steam cleaning. In the cleaning operation, samples with metalworking oil adhered are washed repeatedly, and the precleanability is evaluated by measuring the amount of residual oil remaining on the surface of the parts due to a decrease in cleanability due to an increase in the concentration of metalworking oil in the finish cleaning agent. . The washing operation is terminated when the residual oil amount reaches 5 μg / cm ² . The amount of residual oil was measured with an oil content measuring device (OIL-20, manufactured by Central Science Co., Ltd.). Evaluation is based on the following criteria.
◎: Number of cleanings 300 times or more ○: Number of cleanings 200 times or more to less than 300 times Δ: Number of cleaning times 100 times or more to less than 200 times ×: Metal processing oil used for the test: 1 time or more to less than 100 times
AM30 (trade name: Unicut Terrami, manufactured by Nippon Oil Corporation)
DM15 (trade name: Unicut Terrami, manufactured by Nippon Oil Corporation)

[Examples 9 to 13]
Each component was mixed with the composition of Table 2, and the target pre-cleaning agent and finishing cleaning agent were obtained. The above evaluation tests were conducted using the pre-cleaning agent and the finish cleaning agent, and the results are summarized in Table 2. Due to the pre-cleaning effect of the composition (b) containing the component (a), the number of times of cleaning is greatly increased compared to Comparative Examples 2 and 3, and the effect of reducing the amount of dirt brought into the finish cleaning agent is excellent. It was confirmed.

[Comparative Examples 2 and 3]
The above-described cleaning evaluation test was performed on the finish cleaning agents described in Table 2. The results are summarized in Table 2. Since no pre-cleaning was carried out, the remaining oil content exceeded 5 μg / cm ² with less than 100 cleanings.

The present invention relates to various processing oils and greases and waxes used when processing precision machine parts and optical machine parts, fluxes used when soldering electrical and electronic parts, and screens used when manufacturing substrates. Provided are a cleaning method and a cleaning device for cleaning ink and paste adhered to a resin and resins adhered to a mixing part of a resin discharge device.

It is an example of the washing | cleaning apparatus as described in aspect (10) of this invention. It is an example of the washing | cleaning apparatus as described in aspect (11) of this invention. It is an example of the washing | cleaning apparatus as described in aspect (14) of this invention. It is an example of the washing | cleaning apparatus as described in aspect (15) of this invention.

Explanation of symbols

1 Pre-cleaning tank (A)
2 Distillation tank (B)
3 Steam zone 4 Water separation tank (C)
5 Ultrasonic vibrator 6 Flow of composition (b) 7 Pipe for composition (b) 8 Heater 9 Flow of steam 10 Cooling pipe 11 Condensate pipe 12 Cooling pipe 13 Condensate pipe 14 after water separation Cooling pipe 15 Condensate piping 16 Pre-cleaning tank (D)
17 Heating tank (E)
18 Steam zone (F)
19 Water separation tank (G)
20 Ultrasonic Vibrator 21 Composition (b) Flow 22 Heater 23 Steam Flow 24 Cooling Pipe 25 Condensate Pipe 26 Cooling Pipe 27 Condensate Pipe 28 After Water Separation Finish Washing Tank (H)
29 Rinse tank (K)
30 Steam zone (I)
31 Water separation tank (J)
32 Heater 33 Condensate flow 34 Ultrasonic vibrator 35 Steam flow 36 Cooling pipe 37 Condensate pipe 38 Cooling pipe 39 Condensate pipe 40 after water separation Finish washing tank (L)
41 Rinse tank (P)
42 Heating tank (M)
43 Steam zone (N)
44 Water separation tank (O)
45 Ultrasonic vibrator 46 Ultrasonic vibrator 47 Heater 48 Finishing detergent overflow port 49 Finishing detergent pipe 50 Finishing detergent pipe outlet 51 Condensate flow 52 Steam flow 53 Cooling pipe 54 Condensate pipe 55 Cooling pipe 56 Condensate pipe after water separation 57 Finish detergent circulation pipe (Q)
58 Circulation pump (Q)

Claims (14)

In the step of washing the article, the component (a) non-chlorinated above 1.33 × 10 ³ Pa is the vapor pressure at 20 ° C. fluorine compound a composition containing 95 volume% to 100 volume% or less (b), the After pre-cleaning to remove the dirt components attached to the surface of the wash ,
Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher and 1.33 at 20 ° C. Washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 10 ³ Pa ,
Finishing cleaning containing a stain component adhering to the surface of the object to be cleaned with a rinsing agent which is a condensate obtained by heating the finishing cleaning agent (c) or a rinsing agent having the same composition as the composition (b) A cleaning method comprising rinsing to remove the agent (c) .   The cleaning method according to claim 1, wherein the component (a) contains hydrofluorocarbon (HFC) and / or hydrofluoroether (HFE).   Component (a) is 2H, 2H, 4H, 4H, 4H-pentafluorobutane (HFC365mfc), 2H, 3H-perfluoropentane (HFC43-10mee), methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and mixtures thereof (HFE7100), ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether and mixtures thereof (HFE7200), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (HFE347pc-) The cleaning method according to claim 1 or 2, comprising one or a combination of two or more selected from the group consisting of f) and 4H, 5H, 5H-heptafluorocyclopentane.   The cleaning method according to any one of claims 1 to 3, wherein the component (d) is any of an organic compound having a hydrocarbon, an alcohol, a ketone, an ether bond and / or an ester bond.   Component (d) is dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, 3-methoxybutanol and 3-methyl-3-methoxybutanol; It is butyl lactate and 3-methyl-3- methoxybutyl acetate, The washing | cleaning method of any one of Claims 1-4 characterized by the above-mentioned.   The cleaning method according to any one of claims 1 to 5, wherein the pre-cleaning is performed in a state where the composition (b) is heated and / or in a state where steam is generated by heating.   The pre-cleaning step with the composition (b) is a rough cleaning with one or a combination of two or more selected from hydrocarbons (e). The cleaning method described.   The cleaning method according to claim 7, wherein the hydrocarbon (e) is a C8 to C16 saturated hydrocarbon and / or kerosene.   9. The cleaning method according to claim 1, wherein in the pre-cleaning, the soil component is separated by distilling the composition (b) including the soil component. (A) Component (a) The article to be washed is immersed in a composition (b) containing 90% by volume or more and 100% by volume or less of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more. (B) a distillation tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition; (C) a condensate obtained by condensing the generated vapor A pre-cleaning device having a water separation tank for removing water from (A) a pre-cleaning tank and (B) a distillation tank connected by a pipe;
(H) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher at 20 ° C. Heating to generate steam by heating and / or heating at least one component constituting the finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 1.33 × 10 ³ Pa A finish washing tank having a mechanism;
(I) a steam zone for steam cleaning with steam generated from the finish cleaning tank (H);
(J) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam;
(K) It has a rinse tank for carrying out immersion rinse with the condensate from which the water | moisture content was removed in a water separation tank, It is for implementing the washing | cleaning method of any one of Claims 1-9 Cleaning device. (D) Component (a) Wash | cleans to-be-washed object by the composition (b) which contains 90 to 100 volume% of non-chlorine type fluorine compounds whose vapor pressure in 20 degreeC is 1.33 * 10 < ³ > Pa or more. (E) a heating tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, (F) steam generated by the steam generated from the heating tank (E) A steam zone for cleaning, (G) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam, (D) a pre-cleaning tank and (E) a heating tank A pre-cleaning device connected by piping;
(H) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) a vapor pressure of 13.3 Pa or higher at 20 ° C. Heating to generate steam by heating and / or heating at least one component constituting the finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component less than 1.33 × 10 ³ Pa A finish washing tank having a mechanism;
(I) a steam zone for steam cleaning with steam generated from the finish cleaning tank (H);
(J) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam;
(K) It has a rinse tank for carrying out immersion rinse with the condensate from which the water | moisture content was removed in a water separation tank, It is for implementing the washing | cleaning method of any one of Claims 1-9 Cleaning device. (A) Component (a) The article to be washed is immersed in a composition (b) containing 90% by volume or more and 100% by volume or less of a non-chlorine fluorine compound having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more. (B) a distillation tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition; (C) a condensate obtained by condensing the generated vapor A pre-cleaning device having a water separation tank for removing water from (A) a pre-cleaning tank and (B) a distillation tank connected by a pipe;
(L) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) the vapor pressure at 20 ° C. of 13.3 Pa or higher. A finish washing tank for washing an object to be washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component of less than 1.33 × 10 ³ Pa;
(M) an immersion rinse bath for immersion rinse with a rinse agent having the same composition as component (a) or composition (b) ;
(N) a heating tank having a heating mechanism for generating vapor of a rinse agent having the same composition as component (a) or composition (b) ;
(O) a steam zone for steam cleaning with steam generated from the heating tank (N);
(P) It has a water separation tank for removing a water | moisture content from the condensate obtained by condensing the generated vapor | steam, The washing | cleaning method of any one of Claims 1-9 characterized by the above-mentioned cleaning apparatus for. (D) Component (a) Wash | cleans to-be-washed object by the composition (b) which contains 90 to 100 volume% of non-chlorine type fluorine compounds whose vapor pressure in 20 degreeC is 1.33 * 10 < ³ > Pa or more. (E) a heating tank having a heating mechanism for generating vapor of at least one component or compound constituting the composition, (F) steam generated by the steam generated from the heating tank (E) A steam zone for cleaning, (G) a water separation tank for removing moisture from the condensate obtained by condensing the generated steam, (D) a pre-cleaning tank and (E) a heating tank A pre-cleaning device connected by piping;
(L) Component (a) 10% by volume or more and less than 90% by volume of a non-chlorine fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or higher at 20 ° C. and component (d) the vapor pressure at 20 ° C. of 13.3 Pa or higher. A finish washing tank for washing an object to be washed with a finish cleaning agent (c) containing 10% by volume or more and less than 90% by volume of a component of less than 1.33 × 10 ³ Pa;
(M) an immersion rinse bath for immersion rinse with a rinse agent having the same composition as component (a) or composition (b) ;
(N) a heating tank having a heating mechanism for generating vapor of a rinse agent having the same composition as component (a) or composition (b) ;
(O) a steam zone for steam cleaning with steam generated from the heating tank (N);
(P) It has a water separation tank for removing a water | moisture content from the condensate obtained by condensing the generated vapor | steam, The washing | cleaning method of any one of Claims 1-9 characterized by the above-mentioned cleaning apparatus for.   The cleaning device according to any one of claims 10 to 13, wherein the pre-cleaning device has a mechanism for discharging the soil component separated from the composition (b) out of the system.

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