JP2003033730A - Circulation cleaning method and cleaning unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleaning method, fouling separating method and cleaning unit which has high cleaning power, which prevents fouling from reattaching, which prevents oxidation and deterioration during cleaning under high temperature, which is low toxic, whose inflammability is low and which is favorable for high boiling point solvent that doesn't do the ozone layer any harm. SOLUTION: In this cleaning method, one or more than two compounds whose steam pressure of its ingredient is less than 1.33&times;10<3> Pa are added to non-chlorine- based fluorine compound whose steam pressure at 20 deg.C is 1.33&times;10<3> Pa or more, and a cleaning agent and rinse agent which jointly use antioxidant or the like are used, then ultrasonic cleaning is carried out by having the cleaning agent circulated in-between a cleaning tank 1 and a heating tank 2, and by controlling the temperature while agitating the cleaning tank without boiling the cleaning tank and further, rinsing/ steam cleaning is carried out by making use of the steam which generate when boiling the cleaning liquid, and the condensation liquid of the cleaning agent is used. In this case, a fouling separating method and a cleaning device which have the cleaning agent in the cleaning tank and the steam condensation liquid of the cleaning agent in a water separating tank 5 contacted in the foul separating tank to separate and remove the fouling ingredient in the cleaning agent are used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to processing oils, greases, waxes used for processing precision machine parts, optical machine parts and the like, and fluxes and liquid crystals used for soldering electric and electronic parts. The present invention relates to a cleaning method, a soil separation method, and a cleaning device suitable for cleaning all the soils.

[0002]

2. Description of the Related Art Various processing oils such as cutting oil, press oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, etc., or grease, wax when processing precision machine parts, optical machine parts, etc. Although stains and the like are used, these stains must be finally removed, and removal with a solvent is generally performed. Although soldering is the most commonly used method for joining electronic circuits, rosin is used for the purpose of removing and cleaning oxides on the metal surface to be soldered, preventing reoxidation, and improving solder wettability. It is common practice to pretreat the soldering surface with a flux containing as a main component. As a soldering method, the flux is attached to the substrate surface by dipping the substrate in a solution-like flux, 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 to heat things after supplying them to the place to be soldered,
In any case, since the flux residue causes corrosion of the metal and deterioration of the insulating property, it is necessary to sufficiently remove it after the soldering is completed.

[0003] These cleaning and removal have many characteristics such as nonflammability, low toxicity, and excellent solubility. Therefore, 1,1,2-trichloro-1,2,2-trifluoro is used. Ethane (hereinafter referred to as CFC113) and CFC113
It was washed with a mixed solvent of alcohol and alcohol. However, CFC113 was pointed out to have a problem of global environmental pollution such as ozone depletion, and its production was completely abolished at the end of 1995 in Japan. As an alternative to this CFC113, 3,3
-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 due to their slight ozone depletion potential, their use will be banned in Japan in 2020.

Furthermore, in recent years, there has been proposed a nonflammable fluorine-based solvent which has no ozone depleting ability such as hydrofluorocarbons (hereinafter referred to as HFC) and hydrofluoroethers (hereinafter referred to as HFE) that do not contain any chlorine atom. However, since it does not contain a chlorine atom, it has a low solubility and cannot be used alone as a cleaning agent.
Japanese Patent Laid-Open No. 94-199297 and Japanese Patent Application Laid-Open No. 10-197297 disclose a technique in which HFC or HFE is used as a rinse agent after washing with a detergent in which a high boiling point solvent is added to HFC or HFE.

However, in any of the techniques, the high boiling point solvent is used for the cleaning agent, and therefore the drying property of the cleaning object is deteriorated and the contamination components accumulated in the cleaning agent are increased, so that the surface of the cleaning object is contaminated. Re-adhesion becomes a problem. Therefore, in such a cleaning method, a high-boiling point component having excellent solubility is rinsed by providing a rinse tank containing HFC or HFE having low stain-dissolving ability and excellent drying property disclosed in JP-A-2000-8095. At the same time, a method of separating the dirt components accumulated in the cleaning agent by using the rinse liquid in the rinse tank has been proposed, but since the rinse liquid in the rinse tank is used, the dirt separation property is significantly reduced. However, since the dirt cannot be separated efficiently and the cleaning tank is used for boiling, it has a large effect on the mounting board on which the parts made of polymer material are mounted, and the bubbles generated during boiling are more effective. Since it is impossible to perform ultrasonic cleaning as much as possible, improvement is desired.

As described above, with the cleaning agents and cleaning methods proposed so far as alternatives to CFC113, even if cleaning is possible, their use will be prohibited in the future due to the problem of ozone layer depletion, or cleaning agents will be used in the future. Although the dirt components that accumulate inside can be separated continuously, the efficiency of dirt separation in the cleaning agent decreases significantly because the rinse liquid in the rinse tank is used, and effective ultrasonic cleaning cannot be performed at present. is there.

[0007]

DISCLOSURE OF THE INVENTION The present invention shows a high detergency comparable to that of HCFC225 with respect to all types of dirt, and prevents deterioration of detergency due to redeposition of dirt on the surface of an article to be washed. And, a cleaning agent containing a high boiling point solvent which is excellent in detergency with low toxicity, low flammability, and no danger of depleting the ozone layer while preventing oxidative deterioration during cleaning under high temperature or steam cleaning, or / And a rinse agent to reduce the effect on the item being washed,
Another object of the present invention is to provide a cleaning method, a dirt separation method, and a cleaning device that enable effective ultrasonic cleaning.

[0008]

In order to achieve the above object, the present inventor has (a1) a vapor pressure at 20 ° C. of 1.3.
Excellent dryness of non-chlorine type fluorine compound of 3 × 10 ³ Pa or more and (b) vapor pressure at 20 ° C. of 1.33 × 10 ³
As a result of intensive investigations to find a cleaning method, a dirt separation method, and a cleaning device using a cleaning agent and / or a rinse agent that make use of a high dissolving power of components less than Pa, (c) the cleaning agent and the cleaning agent Utilizing the cleaning agent vapor and condensate or (d) rinse agent generated by boiling,
Immersion rinsing and / or steam cleaning, and circulating the cleaning tank and heating tank reduce the effect on the material to be cleaned by cleaning the cleaning tank without boiling it, and further stir the cleaning tank. By controlling the temperature of the cleaning agent in the cleaning tank and enabling effective ultrasonic cleaning in the cleaning tank, we have found a cleaning method and / or a cleaning device suitable for precision cleaning that requires a higher cleaning level. It was

Further, the cleaning agent in the cleaning tank and the liquid obtained by condensing the vapor of the cleaning agent in the water separation tank are sent to the dirt separation tank.
By contacting the liquid, the dirt components dissolved in the cleaning agent in the dirt separation tank are separated and removed, and then the liquid from which the dirt has been separated is returned to the cleaning tank to effectively remove the dirt in the cleaning agent. It has been found that continuous separation can be achieved, and further, the separation of the finely dispersed dirt components in the return liquid to the washing tank with a separation filter can provide higher dirt separation properties. Furthermore, the liquid from which the dirt component has been separated by the dirt separation tank and / or the separation filter has a low dirt component concentration and is kept constant, and (c) compared with the condensate obtained by heating the cleaning agent, The present invention has been completed by discovering that by containing a large amount of the component (b) having excellent solubility, it has excellent pre-rinsing properties.

That is, the first aspect of the invention is (a1)
Vapor pressure at 1.33 × 10³Chlorine-free fluorine with Pa or more
Fluorine compounds and (b) Vapor pressure at 20 ℃ is 1.33 ×
10 ³Does not have a flash point containing components less than Pa
(C) In a method of cleaning using a cleaning agent, a heating tank
Of the cleaning agent obtained by heating the cleaning agent in
Rinsing and / or rinsing using vapor or condensate of vapor
Or perform steam cleaning and remove the cleaning agent in the cleaning tank and heating tank.
It is a cleaning method characterized by circulating. Second invention
Is an agitator in a cleaning tank.
Is the cleaning method. The third aspect of the invention is (a1) at 20 ° C.
Vapor pressure of 1.33 × 10³Non-chlorine foot with Pa or more
Elementary compound 80.0 mass% to 99.9 mass% and (b) 20
Vapor pressure at ℃ 1.33 × 10³Components less than Pa
Having a flash point containing 0.1% by mass to 20.0% by mass
Invention characterized by utilizing a rinsing agent (d)
The cleaning method according to the first or second aspect.

A fourth aspect of the present invention is the washing according to any one of the first to third aspects of the invention, wherein the component (a1) contains a compound selected from methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture thereof. Is the way. A fifth aspect of the present invention is the washing according to any one of the first to fourth aspects, wherein the component (b) contains at least one compound selected from the group consisting of organic compounds having an ether bond and / or an ester bond. Is the way. A sixth aspect of the invention is characterized in that the component (b) contains one or more compounds selected from the group consisting of glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters. The cleaning method according to any one of 1.

In a seventh aspect of the invention, the component (b) is a combination of (b1) one or more compounds selected from glycol ether monoalkyl ethers and (b2) one or more compounds selected from glycol ether dialkyl ethers. The cleaning method according to any one of the first to sixth aspects of the invention, which comprises: An eighth aspect of the invention is the cleaning method according to any one of the first to seventh aspects, wherein (c) the cleaning agent and / or (d) the rinse agent has (a2) a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more. The cleaning method is characterized by containing one or more compounds selected from the group consisting of alcohols, ketones, esters and hydrocarbons.

A ninth aspect of the invention is characterized in that in the cleaning method according to any one of the first to seventh aspects of the invention, the (c) detergent and / or (d) rinse agent contains (e) an antioxidant. The cleaning method according to any one of the first to eighth aspects of the invention. A tenth aspect of the invention is the cleaning method according to any one of the first to ninth aspects of the invention, which has a dirt separation tank. The eleventh aspect of the invention is the cleaning method according to any one of the first to tenth aspects of the invention, which has a separation filter. The twelfth aspect of the invention is the cleaning method according to any one of the first to eleventh aspects of the invention having a pre-rinsing mechanism.

In a thirteenth aspect of the invention, (c) the liquid obtained by condensing the vapor of the cleaning agent and / or (d) the rinsing agent is brought into contact with the cleaning agent containing the dirt in the cleaning tank in the dirt separation tank, and the cleaning is performed. After separating the dirt components dissolved in the agent,
13. The cleaning method according to any one of the first to twelfth aspects of the present invention, which has a dirt separation method characterized in that the liquid from which the dirt has been separated is returned to the cleaning tank. In a fourteenth aspect of the invention, after (c) a liquid obtained by condensing the vapor of the cleaning agent and / or (d) a liquid in which the rinsing agent is brought into contact with the cleaning agent in which dirt is mixed in the cleaning tank, a separation filter is applied, The cleaning method according to any one of the first to thirteenth aspects of the present invention, which has a dirt separation method characterized by returning to a cleaning tank. The fifteenth invention is the thirteenth invention and / or
Alternatively, the cleaning method according to any one of the first to the twelfth aspects of the invention is characterized in that the liquid treated by the stain separation method described in 14 is used as a pre-rinsing agent before rinsing to perform pre-rinsing.

The sixteenth aspect of the invention is to: (A) (c) a cleaning tank for cleaning an article to be cleaned with a cleaning agent; and (B) to generate vapor of at least one component or compound constituting the cleaning agent. A heating tank having a heating mechanism of (C), a steam zone for steam cleaning with steam generated from the heating tank (B), and (D) removing water from a condensate obtained by condensing the generated steam. Water separation tank for (E) water separation tank (D)
A rinse tank for rinsing with the condensate staying in
(F) A cleaning device having a mechanism for circulating the cleaning agent between the cleaning tank (A) and the heating tank (B).

A seventeenth aspect of the present invention is the cleaning method according to the sixteenth aspect of the invention, which comprises (G) a cleaning tank (A) and (c) a mechanism for stirring the cleaning agent. 18th of the invention
Are (A) (c) a cleaning tank for cleaning an object to be cleaned, (B) a heating tank having a heating mechanism for generating vapor of at least one component or compound constituting the cleaning agent. , (C) a steam zone for washing with steam generated from the heating tank (B), (D) a water separation tank for removing water from a condensate obtained by condensing the generated steam, ( H) A mechanism for shower rinsing the condensate staying in the water separation tank (D) in the steam zone (C), (F) Circulating the cleaning agent between the cleaning tank (A) and the heating tank (B) And (G) a mechanism for stirring the cleaning agent in the cleaning tank (A).

The nineteenth aspect of the invention is the cleaning apparatus according to any one of the sixteenth to eighteenth aspects of the invention, which comprises (I) a dirt separation tank. The twentieth aspect of the invention is the cleaning apparatus according to any one of the sixteenth to nineteenth aspects of the invention having a (J) separation filter. The twenty-first aspect of the invention is the cleaning apparatus according to the sixteenth to twentieth aspects of the invention having a (K) pre-rinsing mechanism.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the present specification, the term “cleaning” refers to removing dirt adhering to the object to be washed to a level that does not affect the next step.
In addition, rinsing is to replace the cleaning agent containing the dirt component attached to the object to be washed with a solvent containing no dirt component after cleaning. In addition, the shower rinse contains a dirt component adhering to the object to be washed by discharging a solvent containing no liquid or mist-like dirt component from a single or a plurality of outlets after washing and applying it to the object to be washed. Replacing the cleaning agent with a solvent that does not contain dirt components. The pre-rinse is to replace the cleaning agent containing the dirt component adhering to the object to be washed with a solvent after the washing and before the rinsing. Further, the steam cleaning is to remove a stain component slightly remaining on the surface of the object to be cleaned 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.

(A1) 20 which is a component of the cleaning agent and the rinse agent used in the cleaning method and / or the cleaning apparatus of the present invention.
Chlorine-fluorine compound or 1.33 × 10 ³ Pa vapor pressure and (a2) a vapor pressure at 20 ° C. is 1.33 × 10 ³ Pa or more alcohols in ° C., ketones,
Compounds having excellent dryness such as esters and hydrocarbons will be exemplified for each type.

The non-chlorine type fluorine compound (a1) is a fluorine compound in which some hydrogen atoms of hydrocarbons and ethers are replaced by only fluorine atoms and no chlorine atom is contained.
For example, a cyclic HFC specified by the following general formula (5),
A chain HFC specified in (6) or a HFE specified in (7), which is selected from a compound not containing a chlorine atom, which is composed of a carbon atom, a hydrogen atom, an oxygen atom, a fluorine atom, and these A combination of two or more kinds of compounds can be mentioned. C _n H _2n-m F _m (5) (in the formula, represents an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1) C _x H _{2x + 2-y} F _y (6) (wherein, 4 ≦ x represents an integer of ≦ 6,6 ≦ y ≦ 12) C s F 2s + 1 OR (7) ( wherein, 4 ≦ s ≦ 6, R is an alkyl group having 1 to 3 carbon atoms)

Specific examples of the cyclic HFC are 3H, 4H,
4H-perfluorocyclobutane, 4H, 5H, 5H-
Perfluorocyclopentane, 5H, 6H, 6H-nonafluorocyclohexane etc. can be mentioned.

Specific examples of the chain HFC are 1H, 2H,
3H, 4H-perfluorobutane, 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 2
H, 3H-perfluorobutane, 4H, 4H-perfluorobutane, 1H, 1H, 3H-perfluorobutane,
1H, 1H, 4H-perfluorobutane, 1H, 2H,
3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 1H, 2H-perfluoropentane, 1
H, 4H-perfluoropentane, 2H, 3H-perfluoropentane, 2H, 4H-perfluoropentane,
2H, 5H-perfluoropentane, 1H, 2H, 3H
-Perfluoropentane, 1H, 3H, 5H-perfluoropentane, 1H, 5H, 5H-perfluoropentane, 2H, 2H, 4H-perfluoropentane, 1H,
2H, 4H, 5H-perfluoropentane, 1H, 4
H, 5H, 5H, 5H-perfluoropentane, 1H,
2H-perfluorohexane, 2H, 3H-perfluorohexane, 2H, 4H-perfluorohexane, 2
H, 5H-perfluorohexane, 3H, 4H-perfluorohexane and the like can be mentioned.

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

For the cleaning agent and rinsing agent used in the cleaning method and / or cleaning apparatus of the present invention, one or more compounds selected from these (a1) non-chlorine fluorine compounds are used in combination. However, preferably, a cyclic HFC or HFE having a high solubility in highly polar solvents such as alcohols, ketones, esters, glycol ethers, etc. and a low global warming potential can be mentioned. More preferably, 4H, 5H, 5H-perfluorocyclopentane, methyl perfluorobutyl ether and methyl perfluoroisobutyl ether and a mixture thereof, ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether and a mixture thereof can be mentioned. More preferred are methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and mixtures thereof.

(A2) 20 which is a component of the cleaning agent and the rinse agent used in the cleaning method and / or the cleaning apparatus of the present invention.
Examples of one or more compounds selected from the group consisting of alcohols, ketones, esters and hydrocarbons having a vapor pressure of 1.33 × 10 ³ Pa or more at 0 ° C. for each compound type are shown below. Examples of alcohols include methanol, ethanol, n-propanol, and isopropanol.

Examples of ketones include acetone and methyl ethyl ketone. Esters include ethyl formate, propyl formate, isobutyl formate, methyl acetate,
Examples thereof include ethyl acetate, methyl propionate, ethyl propionate and the like. As hydrocarbons, n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n
-Heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, isooctane and the like.

The specific gravity of the component (a2) or the component (b) is preferably within a range of ± 0.8 of the specific gravity of the component (a1) used in combination in order to improve the compatibility with the component (a1), More preferably, it is ± 0.7. Especially, the compatibility with other components of the non-chlorine type fluorine compound (a1) has a high temperature dependency, and in order to maintain the compatibility at low temperature, it is important to reduce the difference in specific gravity from the other components used in combination. . Ingredient (a
The boiling point of 2) is preferably within a range of ± 40 ° C., more preferably ± 30 ° C., of the boiling point of the component (a1) used in combination in order to reduce compositional fluctuation during use.

The component (a1) is the component (a) used in combination.
2) is an azeotropic composition with an azeotropic composition or a composition close to it
It is preferably a composition. Cleaning method of the present invention and
In the cleaning device, processing oils, greases,
Washing against all dirt such as wax and flux
(B) 20 ° C for the purpose of improving cleaning power and rinsing property
Vapor pressure at 1.33 × 10³Select from components less than Pa
Use one or a combination of two or more compounds
Need to use. For example, various hydrocarbons, alco
And ketones and ether linkages and / or essences
Good against various stains such as organic compounds with tellur bond
It has good detergency and has a vapor pressure of 1.3 at 20 ° C.
3 x 10³It is a compound of less than Pa. Steam of component (b)
When the pressure is in this range, the rinse according to the present invention
Cleaning method and / or cleaning device having excellent cleaning property and cleaning property
Is obtained. 6.66 × 1 at 20 ° C.
0 ²Pa or less, more preferably 1.33 × 10²
Pa or less. Below, the component (b) is added for each type of solvent.
To illustrate.

Among hydrocarbons, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,2
4,4,6,8,8-heptamethylnonane and the like can be mentioned. Alcohols include n-butanol, isobutanol, sec-butanol, isoamyl alcohol, n-butanol.
Heptanol, n-octanol, n-nonanol, n
-Decanol, n-undecanol, benzyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol and the like. Among ketones, methyl-n-amyl ketone, diisobutyl ketone, diacetone alcohol, phorone, isophorone, cyclohexanone,
Acetophenone and the like can be mentioned.

The organic compound having an ether bond, which is a component of the cleaning agent and the rinsing agent used in the cleaning method and / or the cleaning apparatus of the present invention, means at least an ether bond (C-O-C) in the molecular structure. An organic compound having at least one ester bond and an organic compound having an ester bond is a compound having at least one ester bond (—COO—) in its molecular structure. Examples of the compound having an ether bond include compounds specified by the following general formula (8).

[0031]

[Chemical 1]

(In the formula, R ¹⁵ and R ¹⁶ are aliphatic compound residues having at least one selected from an alkyl group, an alkenyl group, a cycloalkyl group, an acetyl group, a carbonyl group, a hydroxyl group, an ester bond and an ether bond. Represents an alicyclic compound residue, an aromatic compound residue and a heterocyclic compound residue, and R ^{17 to} R ²⁰ represent hydrogen or an alkyl group)

Examples of the compound having an ester bond include compounds specified by the following general formula (9).

[0034]

[Chemical 2]

(In the formula, R ²¹ and R ²² are aliphatic compound residues having at least one selected from an alkyl group, an alkenyl group, a cycloalkyl group, an acetyl group, a carbonyl group, a hydroxyl group, an ester bond and an ether bond. , Represents an alicyclic compound residue, an aromatic compound residue and a heterocyclic compound residue.)

Specific examples include -n-butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, γ-butyrolactone, dimethyl succinate, Dimethyl glutarate, dimethyl adipate,
Examples thereof include 3-methyl-3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate and the like. Among the above components (b), glycol ethers, glycol ether acetates and hydroxycarboxylic acid esters are preferable because they have a particularly high effect of suppressing the flammability of alcohols used in combination.

The glycol ethers include (b1)
Glycol ether monoalkyl ethers and (b2)
Mention may be made of glycol ether dialkyl ethers. (B1) Glycol ether monoalkyl ethers are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms,
A compound in which one hydrogen of the hydroxyl group is substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond,
(B2) Glycol ether dialkyl ethers are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, and each hydrogen of the two hydroxyl groups is a hydrocarbon residue. Alternatively, it is a compound substituted with a hydrocarbon residue containing an ether bond. For example, (b1) glycol ether monoalkyl ethers specified by the following general formula (10) and (b2) glycol ether dialkyl ethers specified by the following general formula (11) can be mentioned.

[0038]

[Chemical 3]

(In the formula, R ²³ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group, R ²⁴ , R ²⁵ ,
R ²⁶ is hydrogen or a methyl group, n is an integer of 0 to 1, m is 1
~ Indicates an integer of 4)

[0040]

[Chemical 4]

(Wherein R ²⁷ is an alkyl group, an alkenyl group or a cycloalkyl group having 1 to 6 carbon atoms, R ²⁸ is an alkyl group or an alkenyl group having 1 to 4 carbon atoms, R ²⁹ , R ³⁰ , R
³¹ is hydrogen or a methyl group, n is an integer of 0 to 1, and m is 1
Indicates an integer of 4)

Further, the hydrophilic glycol ether monoalkyl ethers and hydrophilic glycol ether dialkyl ethers which are components of the cleaning agent and the rinse agent used in the cleaning method and / or the cleaning apparatus of the present invention are 30
A glycol ether that can be dissolved without phase separation with water when mixed with glycol ethers / water in a mass ratio of 60/40 at 0 ° C. Are glycol ethers that phase-separate from water when glycol ethers / water are mixed at a mass ratio of 60/40 at 30 ° C.

Preferred hydrophilic glycol ether monoalkyl ethers and hydrophilic glycol ether dialkyl ethers are glycol ethers which can be dissolved in water at an arbitrary ratio at 30 ° C., and preferred hydrophobic glycol ether monoalkyl ethers. And the hydrophobic glycol ether dialkyl ethers have a solubility in water of 60% by mass at 30 ° C.
The following glycol ethers.

In the (b1) glycol ether monoalkyl ethers, for example, specific examples of the hydrophilic glycol ether monoalkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol mono-n-.
Propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, etc. Specific examples of the hydrophobic glycol ether monoalkyl ether include ethylene glycol mono-n-hexyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-. Examples include n-butyl ether. In addition,
Dipropylene glycol mono-n-propyl ether,
Dipropylene glycol mono-n-butyl ether is
Excellent cleaning properties for stains such as polymerized rosin and metal salts of rosin, which are produced by the soldering process and stains such as amine hydrochlorides and organic acids that cause ionic residues in flux cleaning. There is.

Furthermore, 3-methoxybutanol, 3-
The following general formula (1) such as methyl-3-methoxybutanol
The (b1) glycol ether monoalkyl ethers specified in (3) are compounds that have particularly good cleaning properties against various stains and that have excellent cleaning effects.

[0046]

[Chemical 5]

(In the formula, R ¹ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ² ,
R ³ and R ⁴ represent hydrogen or a methyl group, and n represents an integer of 0 or 1. )

In the (b2) glycol ether dialkyl ethers, specific examples of the hydrophilic glycol ether dialkyl ether include diethylene glycol dimethyl ether and diethylene glycol diethyl ether, and the hydrophobic glycol ether dialkyl ether is , Diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether and the like. In addition, diethylene glycol diethyl ether and dipropylene glycol dimethyl ether are particularly excellent in detergency against rosin contained in the flux component. Furthermore, the glycol ether dialkyl ethers (b2) specified by the following general formula (2) such as diethylene glycol di-n-butyl ether have good detergency against various stains and a compound having an excellent detergency effect. Is.

[0049]

[Chemical 6]

(In the formula, R ⁵ is an alkyl group having 4 to 6 carbon atoms, an alkenyl group, or a cycloalkyl group, R ⁷ ,
R ⁸ and R ⁹ are hydrogen or a methyl group, R ⁶ is an alkyl group having 3 to ⁶ carbon atoms, an alkenyl group or a cycloalkyl group, n
Represents an integer of 0 or 1. )

In the present invention, more preferable combinations of glycol ether monoalkyl ethers and glycol ether dialkyl ethers against various stains can be selected according to the purpose of cleaning.
For example, when one of the components (b1) and (b2) is hydrophilic and the other is hydrophobic, a thermosetting ink such as various flux cleaning or various solder resist inks applied on the substrate surface or UV curing is used. It is particularly suitable for cleaning functional inks and liquid crystal cleaning, and the combination of both components is hydrophilic. Epoxy and urethane type two liquids used for cleaning various fluxes and bonding and sealing various electric and electronic parts. It is particularly suitable for cleaning the mixer section and nozzle section of a mixed resin dispenser. In addition, the combination of both components being hydrophobic is a precision machine part with low polarity,
Especially suitable for cleaning various processing oils such as cutting oil, press oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, greases, waxes, liquid crystal etc. when processing optical mechanical parts etc. ing.

The glycol ethers used in the present invention include dipropylene glycol monomethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, and dipropylene glycol which do not form alkoxyacetic acid in the metabolic system of the human body. Propylene glycol dimethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol and the like are preferred because they have lower toxicity. The glycol ether acetates are compounds obtained by acetylating glycol ethers having a hydroxyl group, preferably the following general formula (3)
Specified by.

[0053]

[Chemical 7]

(In the formula, R10 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group, R11 and R1.
2, R13 is hydrogen or a methyl group, n is an integer of 0 to 1,
m is an integer of 1 to 4)

Specific examples include acetates of monoalkyl ethers such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, 3-methoxybutyl acetate, 3-methyl-3.
-Methoxybutyl acetate and the like can be mentioned.

The glycol ether acetates used in the present invention include dipropylene glycol monomethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate and dipropylene glycol mono-n-, which do not produce alkoxyacetic acid in the metabolic system of the human body. Butyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are preferred because they have lower toxicity. The hydroxycarboxylic acid esters are ester compounds having a hydroxyl group, and are preferably specified by the following general formula (4).

[0057]

[Chemical 8]

(In the formula, R14 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group or a cycloalkyl group.)

Specific examples include lactic acid ester, malic acid ester, tartaric acid ester, citric acid ester, glycol monoester, glycerin monoester, glycerin diester, ricinoleic acid ester and castor oil. Among the above components (b), lactate esters are particularly preferable, and specific examples thereof include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, pentyl lactate and the like.

Further, as particularly preferred component (b),
Compound containing at least one or more of butyl group or isobutyl group as a part of its molecular structure and having 4 to 6 carbon atoms
Examples thereof include compounds having a chain hydrocarbon structure and an oxygen atom in the molecule. For example, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate,
Butyl lactate, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-isobutyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-i-butyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol and Diethylene glycol di-n-butyl ether etc. can be mentioned. In flux cleaning, these compounds are not only excellent in rosin solubility, but also excellent in cleaning properties against ionic substances and white residue-causing substances. Of these components (b), it is preferable to add hydrocarbons for washing processing oil, grease, wax, liquid crystal, etc., and glycol ethers, esters, ketones are preferable for washing resins such as flux. Of these, glycol ethers are particularly preferable.

The cleaning agent and rinse agent used in the cleaning method and / or cleaning apparatus of the present invention may contain an antioxidant (c) for the purpose of preventing oxidation of the cleaning agent. A specific example is shown below. Its melting point is shown in parentheses. 1-oxy-3 as a phenolic antioxidant
-Methyl-4-isopropylbenzene (112 ° C),
2,4-Dimethyl-6-t-butylphenol (20 ° C
Liquid), 2,6-di-t-butylphenol (37
), Butylhydroxyanisole (57-63 ° C),
2,6-di-t-butyl-p-cresol (69-71
C.), 2,6-di-t-butyl-4-ethylphenol (44 to 45.degree. C.), 2,6-di-t-butyl-4-hydroxymethylphenol (141.degree. C.), triethylene glycol-bis [ 3- (3-t-butyl-5-methyl-
4-hydroxyphenyl) propionate (76-79)
C.), 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate] (104-108 ° C), octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Examples thereof include compounds such as propionate (50 to 52 ° C.).

Examples of amine antioxidants include diphenyl-p-phenylene-diamine (130 ° C.), 4-amino-p-diphenylamine (74 ° C.), p, p′-dioctyldiphenylamine (80-100 ° C.). A compound can be mentioned. Phosphorus-based antioxidants include phenylisodecyl phosphite (liquid at 20 ° C), diphenyldiisooctylphosphite (liquid at 20 ° C), diphenyldiisodecylphosphite (liquid at 20 ° C),
Compounds such as triphenyl phosphite (liquid at 20 ° C), trisnonylphenyl phosphite (liquid at 20 ° C), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (liquid at 20 ° C) Can be mentioned.

As the sulfur-based antioxidant, dilauryl-3,3'-thiodipropionate (34 to 42) is used.
° C), ditridecyl-3,3'-thiodipropionate (liquid at 20 ° C), dimyristyl-3,3'-thiodipropionate (49-55 ° C), distearyl-3,3'-thio. Dipropionate (63-
69 ° C.) and the like.

Among these exemplified compounds, the effect of adding the phenolic antioxidant is high, and particularly 2,6-di-
t-Butyl-p-cresol is preferred. In the case of steam cleaning in which the cleaning agent is continuously heated and used, at least one selected from the group consisting of a phenolic antioxidant and an amine antioxidant, a phosphorus antioxidant and a sulfur antioxidant are used. The combined use of one or more selected from the group makes it possible to suppress the oxidative decomposition of the detergent for a long period of time. Further, the melting point of the antioxidant is 120 ° C. in order to suppress spots generated on the surface of the article to be washed after washing.
The following is preferable, and it is preferable that the temperature is lower than the cleaning temperature in the steam cleaning.

The cleaning agent and the rinse agent used in the cleaning method and / or the cleaning apparatus of the present invention include (c) an ultraviolet absorber for the purpose of further improving the oxidation stability by the combined use with an antioxidant. May be added. Examples thereof include 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-.
4'-chlorobenzophenone, 2,2'-hydroxy-
4-n-octoxybenzophenone, 2-hydroxy-
Benzophenone such as 4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone , Phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, bisphenol A-di-
Phenyl salicylates such as salicylate and 2-
(5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α,
α'-Didimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t
-Butyl-5-methyl-2-hydroxyphenyl) -5
-Chlorobenzotriazole, 2- (3,5-di-t-
Amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
Examples thereof include benzotriazoles such as (2'-hydroxy-5'-t-octylphenyl) benzotriazole.

The cleaning agent used in the cleaning method and / or the cleaning apparatus of the present invention is a uniform mixture of the above-mentioned components (a1), (b), (c) and (d) according to a standard method. Can be obtained. The mass ratio of each component is not particularly limited as long as it does not impair the high detergency, low oxidative deterioration, low toxicity, and low flammability, which are the characteristics of the detergent, (a1) 20 ° C. Vapor pressure at 1.
Non-chlorine fluorine compound less than 33 × 10 ³ Pa (b)
It is more preferable that the mass ratio range of component (a1) / component (b) is 90/10 to 20/80 when a component having a vapor pressure at 20 ° C. of less than 1.33 × 10 ³ Pa is used in combination. . When the mass ratio of the component (b) is more than 10, a more preferable effect of improving the dissolving power for various stains is obtained, and when it is less than 80, a more preferable low residual property of the detergent component on the surface of the article to be washed is obtained. Considering the balance between the cleaning property of the cleaning agent and the residual property of the cleaning agent component on the surface of the object to be cleaned, the more preferable mass ratio range of the components (a1) and (b) is 80/10 to 40/60, and It is preferably 70/30 to 50/50.

When the component (a1) and the component (a2) are used in combination, the mass ratio range is 99/1 to 70/30.
Is more preferable. When the mass ratio of the component (a2) is larger than 1, a more preferable effect of improving the dissolving power for various stains is obtained, and when it is smaller than 30, a more preferable low flammability is obtained. When the component (b1) and the component (b2) are used in combination, the mass ratio range is 90/10.
It is more preferably from 10/90. Ingredient (b1)
When the mass ratio is more than 10, more preferable rosin solubility is obtained, and when it is less than 90, more preferable detergency for polymerized rosin or metal salt of rosin is obtained. Considering the balance between the solubility of the cleaning agent in rosin and the cleaning ability against stains that cause white residues such as polymerized rosin, the more preferable component (b1) / component (b)
The range of the mass ratio of 2) is 80/20 to 20/80, and more preferably 70/30 to 30/70. In the case of adding the component (c) antioxidant and the component (d) ultraviolet absorber, {(a) + (b)},
{(C) + (d)} is preferably 1 to 1000 ppm,
More preferably, it is 10 to 1000 ppm. Also,
The mass ratio range of (c) / (d) is 90/10 to 10 /.
90 is preferable, and 80/20 is more preferable.
~ 20/80.

The rinse agent used in the cleaning method and / or the cleaning apparatus of the present invention is, for example, the above-mentioned component (a1),
Examples of the method include a method in which the components (a2), (b), (c), and (d) are mixed according to a standard method and homogenized, and (c) a method of obtaining a condensate by distilling a detergent. be able to.

The blending amount of each component needs to be the following blending amount in order to exhibit characteristics as a rinse agent such as high rinsing property, high drying property, low oxidative deterioration property, low toxicity and low flammability. . The blending amount of the component (a1) chlorine-free fluorine compound is 80.0% by mass to 99.9% by mass, preferably 90.0% by mass to 99.9% by mass, and more preferably 95% by mass in the total composition. It is from 0.0 mass% to 99.5 mass%. When the compounding amount is 80.0 mass% or more, excellent drying property is obtained due to a sufficient evaporation rate, and when it is 99.9 mass% or less, excellent rinsing property for a detergent containing a large amount of stain components is obtained. The vapor pressure at 20 ° C. of component (b) is 1.33 × 10
The compounding amount of the component less than ³ Pa is 0.1% by mass to 20.0% by mass, preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 5% by mass. When the compounding amount is 0.1% by mass or more, an excellent rinsing effect is obtained,
Sufficient dryness can be obtained at 20.0 mass% or less.

(A2) One or more compounds selected from the group consisting of alcohols, ketones, esters and hydrocarbons are added to the rinse agent containing the component (a1) and the component (b). can do. The addition amount is 0.1% by mass to 2 with respect to {(a1) + (b)}
0.0 mass% can be added, preferably 0.1
It is from 10% by mass to 10% by mass, and more preferably from 0.5% by mass to 5% by mass. When the addition amount is 0.1% by mass or more, more preferable steam cleaning property is obtained, and when the addition amount is 20% by mass or less, a more preferable rinsing agent with low risk of ignition is obtained.

When the component (c) antioxidant and the component (d) ultraviolet absorber are added, {(c) + (d)} is preferably 1 to {(a1) + (b)}. ~ 1000
ppm, more preferably 10 to 500 ppm. Moreover, the range of the mass ratio of (c) / (d) is 90/10 to 1
It is preferably 0/90, more preferably 80 /
20 to 20/80. Further, it is preferable that the rinse agent component is the same as the rinsed detergent, because the rinse agent component can be held constant.

The melting point of the cleaning agent and the rinsing agent used in the cleaning method and / or the cleaning apparatus of the present invention is preferably 15 ° C. or less, but more preferably 10 ° C. or less, more preferably 5 ° C. in consideration of use in winter. It is the following. The cleaning agent and rinsing agent used in the cleaning method and / or the cleaning apparatus of the present invention may optionally contain various auxiliaries such as a surfactant, a stabilizer, a defoaming agent, and an ultraviolet absorber. You may add it.

Specific examples of additives that can be added to the cleaning agent and rinsing agent used in the cleaning method and / or the cleaning apparatus of the present invention will be illustrated below. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant may be added. Examples of the anionic surfactant include fatty acids having 6 to 20 carbon atoms, alkali metals such as dodecylbenzenesulfonic acid, alkanolamines and amine salts. Examples of the cationic surfactant include quaternary ammonium salts and the like. Examples of nonionic surfactants include alkylphenols, ethylene oxide adducts of linear or branched aliphatic alcohols having 8 to 18 carbon atoms, and block polymers of polyethylene oxide polypropylene oxide. Examples of the amphoteric surfactant include betaine type and amino acid type.

As stabilizers for suppressing metal corrosion, rusting and discoloration, nitroalkanes such as nitromethane and nitroethane, epoxides such as 1,2-butylene oxide, ethers such as 1,4-dioxane, Examples include amines such as triethanolamine and 1,2,3-benzotriazoles. Examples of the defoaming agent include self-emulsifying silicone, silicone, fatty acid, higher alcohol, polypropylene glycol polyethylene glycol, and fluorochemical surfactant.

The most effective cleaning can be performed by using the cleaning method, the dirt separation method and the cleaning apparatus of the present invention. The cleaning method according to any one of the first to ninth aspects of the present invention removes all types of stains adhering to the object to be washed (a1).
Washing with a non-chlorine type fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. (b) a cleaning agent containing a component having a vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. (c) However, excellent metal stability can be obtained by adding (e) an antioxidant, if necessary. Also, after cleaning the cleaning tank with a cleaning agent while applying physical force such as ultrasonic waves while controlling the temperature without boiling,
The cleaning agent vapor and the condensate generated by boiling the cleaning agent in the heating tank are used for rinsing and / or steam cleaning, and the cleaning agent in the cleaning tank and the heating tank is circulated. .. Furthermore, by stirring the inside of the cleaning tank with a stirring device such as a pump, the temperature of the cleaning agent can be kept below the boiling point, and cleaning with a higher ultrasonic cleaning effect can be achieved.

In particular, to make the cleaning agent a non-flammable cleaning agent
Contains a non-chlorine fluorine compound which is the component (a1)
There is a need. The purpose of the cleaning process is to improve the cleaning performance.
Such as hand towel, dip, spray, shower, ultrasonic
Effective cleaning by combining physical methods
Is possible. In addition, it improves the rinsing property in the rinsing process.
Dipping, spraying, showering, ultrasonic waves for the purpose of
By combining physical methods such as
Will be improved. Spray for cleaning or rinsing
-Discharge pressure when performing rinse or shower rinse
Then 1 × 10 ³~ 2 x 10⁶Preferably Pa
More preferably 1 × 10^Four~ 1 x 10⁶Pa.
The cleaning method of the present invention uses a cleaning agent,
It has excellent drying properties and has little effect on the material to be washed.
Can be said to be a suitable cleaning method.

The cleaning method and / or cleaning apparatus according to any one of the first to twenty-first aspects of the present invention may be any method and apparatus capable of cleaning an object to be cleaned, for example, a chlorine-based cleaning agent used so far. It can be used by improving a general cleaning method and a cleaning device, and the cleaning method and the cleaning device are not limited, but in using the cleaning method and / or the cleaning device of the present invention, A preferred cleaning device will be described below. A preferable cleaning device for cleaning without using a cleaning agent (b) containing a component (b) having a low vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. without boiling the cleaning tank. As a result, by circulating the cleaning agent in the cleaning tank and the heating tank and then controlling the temperature of the cleaning agent in the cleaning tank, the dirt attached to the object to be cleaned in the cleaning tank is subjected to physical force such as ultrasonic waves. In addition, a condensate of components (a1) and / or (a2) having a high vapor pressure mainly contained in the cleaning agent and a component (b) slightly contained, which is obtained by washing and boiling the heating tank, is obtained. A cleaning method and apparatus can be used that rinses a slight amount of dirt components that may adhere to the surface of the object to be cleaned and lowers the temperature of the object to be cleaned to enhance the steam cleaning effect. . In the cleaning method and the cleaning apparatus of the present invention, the cleaning system does not boil the cleaning tank to reduce the influence on the material used for the object to be cleaned, and enables effective ultrasonic cleaning. Can be

As a concrete example of the cleaning method, the cleaning apparatus described in the sixteenth aspect of the present invention can be preferably mentioned. The cleaning method and the cleaning apparatus of the present invention will be specifically described below with reference to the accompanying drawings. The cleaning device shown in FIG. 1 which is an example of the cleaning device according to the sixteenth aspect of the present invention has (c) a cleaning tank (A) 1 and a heating tank (B) 2 for containing a cleaning agent, Steam zone filled with steam (C)
4. The evaporated cleaning agent is condensed by the cooling pipe 7, and the condensed liquid and the water adhering to the cooling pipe are statically separated in the water separation tank (D) 5 and the water separation tank (D) 5. A rinse tank (E) 3 for immersion rinsing with the separated condensate, mechanisms (F) 11, 14 for circulating the cleaning agent between the cleaning tank (A) 1 and the heating tank (B) 2. Consists of. In the actual cleaning, the object to be cleaned is put in a dedicated jig, basket, etc., and cleaning is performed while passing through the cleaning device in the order of cleaning tank (A) 1, rinse tank (E) 3 and steam zone (C) 4. Let it complete.

In the cleaning tank (A) 1, the dirt adhered to the object to be cleaned is cleaned and removed by ultrasonic waves 12 while controlling the temperature to be constant. At this time, as the physical force, any method may be used as long as it is a physical force such as rocking or a jet of a cleaning agent in a liquid that has been used in conventional cleaning machines. In the rinse tank (E) 3, the cleaning agent (c) is heated by the heater 6,
The evaporated cleaning agent is condensed by the cooling pipe 7, the liquid temperature of the condensate is lowered by the cooling pipe 9 in the water separation tank (D) 5, the water is removed, and the water returned to the rinse tank (E) 3 is removed. Ultrasonic waves 13 are used to wash and remove the cleaning agent and dirt components adhering to the object to be washed with the condensed liquid thus obtained. At this time, as the physical force, any method may be used as long as it is a physical force such as rocking or a jet of a cleaning agent in a liquid, which has been adopted in conventional cleaning machines. Further, by using the (d) rinse agent in the rinse tank in advance, it is possible to suppress the composition variation of the cleaning agent. Furthermore, the composition of the rinse agent (d) is more preferable because the composition variation of the detergent can be suppressed by making the same composition as the condensate obtained by boiling the detergent.

In the steam zone (C) 4, the steam of the component (a1) having a high vapor pressure mainly contained in the cleaning agent (c) and the component (b) slightly contained in the cleaning agent is condensed in the cooling pipe 7 and the water separation tank is formed. (D) After being collected in the rinse tank (E) 3, it is sent to the rinse tank (E) 3 to immerse the object to be washed in the condensate to dissolve and / or disperse dirt components in the cleaning agent attached thereto. Remove. The condensate is collected in the water separation tank (D) 5, then enters the rinse tank (E) 3 from the pipe 10, overflows, and flows from the cleaning tank (A) 1 to the heating tank (B) 2 as indicated by an arrow 16. After being heated and boiled by the heater 6, a part or all of the composition becomes vapor and is condensed in the cooling pipe 7 as shown by an arrow 74, and then returns from the pipe 8 to the water separation tank (D) 5.

In the steam cleaning carried out in the steam zone (C) 4 filled with the steam generated in the heating tank (B) 2, the liquid produced by the condensation of the steam on the surface of the object to be cleaned contains no contaminants. Therefore, it is effective as the final cleaning at the end of the cleaning process. Mechanisms (F) 11 and 14 for circulating the cleaning agent between the cleaning tank (A) 1 and the heating tank (B) 2 pass the cleaning agent from the heating tank (B) 2 through a pipe (F) 14. The circulating pump (F) 11 to the cleaning tank (A) 1, and the cleaning tank (A) 1
Overflow from the heating tank (B) as shown by arrow 15.
By returning to 2, washing tank (A) 1 and heating tank (B)
The cleaning agent composition of No. 2 is always kept the same, variation in composition of the cleaning agent in the cleaning tank (A) 1 is suppressed, and stable cleaning property can be obtained.

In the cleaning apparatus of the present invention, the effect on the material to be cleaned is reduced by ultrasonically cleaning the dirt adhering to the material to be cleaned while controlling the temperature to a constant temperature, and the steam mainly contained in the cleaning agent is used. The component (a1) having a high pressure and the component (b) contained in a small amount adhere to the circulating object to be washed while changing the state into a liquid or a gas in the cleaning device, and there is a possibility that a slight amount remains. By cleaning the rinsing tank (E) 3 and the steam zone (C) 4, it is possible to meet the required precision cleaning at a higher cleaning level.

In the cleaning apparatus shown in FIG. 1, the number of cleaning tanks and / or rinse tanks can be two or more depending on the purpose and application. In the cleaning method according to the second aspect of the present invention, the vapor pressure at 20 ° C. of the first aspect of the present invention is 1.
In cleaning using a cleaning agent (c) containing a component (b) having a low vapor pressure of less than 33 × 10 ³ Pa, a method of stirring the cleaning liquid in the cleaning tank by a stirring mechanism such as a pump provided in the cleaning tank. Is.

Also in the cleaning method according to the first aspect of the present invention, the cleaning agent in the cleaning tank is indirectly stirred by circulating the cleaning agent in the cleaning tank and the heating tank. Since it is low, it is necessary to circulate a large amount of cleaning liquid from the heating tank in order to obtain a sufficient stirring effect, and as a result, the temperature of the cleaning liquid in the cleaning tank rises. In some cases, physical properties are affected by heat, and when ultrasonic cleaning is also used in the cleaning tank, the ultrasonic cleaning efficiency may be deteriorated by heat.

In the cleaning tank 2, by providing a mechanism for agitating only the cleaning liquid in the cleaning tank, the temperature of the cleaning tank in the cleaning tank can be more accurately adjusted according to the type of the object to be cleaned and the ultrasonic cleaning conditions. It becomes possible to control, and as a result, it becomes possible to carry out more precise cleaning. The cleaning method according to the second aspect of the present invention is a cleaning method using a cleaning agent (c) containing a component (b) having a low vapor pressure of less than 1.33 × 10 ³ Pa at 20 ° C. By stirring the tank with a stirring mechanism such as a pump, it is possible to control the temperature of the cleaning tank in the cleaning method according to the first aspect of the present invention to a lower level, thereby reducing the influence on the material to be cleaned and performing precision cleaning. It is a preferred cleaning device when performing.

Specifically, a mechanism for agitating the inside of the cleaning tank is added to the cleaning method described in the first aspect of the present invention to sufficiently agitate the inside of the cleaning tank, whereby the cleaning tank and the heating tank It is possible to reduce the circulating amount of the cleaning agent, and it is possible to control the cleaning agent temperature in the cleaning tank to be lower. Furthermore, by adding a heat exchange mechanism to the stirring mechanism,
It is a cleaning system that can be freely set according to the purpose of cleaning and can be controlled with high accuracy.

As a concrete example of the cleaning method, the cleaning apparatus according to the seventeenth aspect of the present invention and the eighteenth aspect of the present invention are preferable.
The cleaning device described in 1. can be mentioned. The cleaning method and the cleaning apparatus of the present invention will be specifically described below with reference to the accompanying drawings. The cleaning apparatus shown in FIG. 2, which is an example of the cleaning apparatus described in the seventeenth aspect of the present invention, has a main structure as shown in FIG. 1 which is an example of the cleaning apparatus described in the first aspect of the present invention. This is a device with a mechanism for doing so.

Mechanism (G) 70 for stirring the cleaning tank,
71, the cleaning agent is sent from the heating tank (B) 2 through the pipe (G) 71 to the cleaning tank (A) 1 by the stirring pump (G) 70 to remove the cleaning agent in the cleaning tank (A) 1. By stirring and mixing to make the detergent composition uniform, it is possible to suppress compositional variation of the detergent in the cleaning tank (A) 1 and obtain stable cleaning properties. In the actual cleaning, the object to be cleaned is put in a dedicated jig, basket, etc., and cleaning is performed while passing through the cleaning device in the order of cleaning tank (A) 1, rinse tank (E) 3 and steam zone (C) 4. Let it complete.

In the cleaning apparatus of the present invention, the influence on the material to be cleaned is reduced by ultrasonically cleaning the dirt adhering to the material to be cleaned while controlling the temperature of the cleaning tank with higher accuracy, and the cleaning agent is mainly used. High vapor pressure component (a
1) and component (b), which is slightly contained, circulates in the cleaning device while changing to a liquid or gas state, and rinses dirt components adhering to the object to be washed that may remain slightly. By cleaning in (E) 3 and steam zone (C) 4, it is possible to meet the required precision cleaning of higher cleaning level.

Next, the cleaning apparatus shown in FIG. 3 has (c) a cleaning tank (A) 17 and a heating tank (B) 18 for containing a cleaning agent, and a vapor zone (C) filled with the cleaning agent vapor. ) 19, the evaporated cleaning agent is condensed by the cooling pipe 25, and the condensed liquid and the water adhering to the cooling pipe are statically separated in a water separation tank (D) 20 and a water separation tank (D) 20. Mechanism (H) 21, 29, 30, 36, 37 for shower-rinsing the separated condensate, and a circulating agent for cleaning agent between the cleaning tank (A) 17 and the heating tank (B) 18. Mechanisms (F) 23, 33 and mechanisms (G) 22, 32 for stirring the cleaning tank. In the actual cleaning, the object to be cleaned is put in a dedicated jig or basket, and the cleaning is completed while passing through the cleaning device (A) 17 and the steam zone (G) 19 in this order.

In the vapor zone (C) 19, the vapor of the component (a1) having a high vapor pressure mainly contained in the cleaning agent (c) and the vapor of the component (b) slightly contained in the cleaning agent are condensed in the cooling pipe 25 to obtain water. After collecting in the separation tank (D) 20 and lowering the liquid temperature of the condensate by the cooling pipe 27, these condensates are shower pump (H) 2
1 to the pipes (H) 29, 30 and showering the articles to be washed from the shower nozzles (H) 36, 37 to dissolve and / or disperse in the detergent adhering to the articles to be washed. Remove the soiled components. After the condensate is collected in the water separation tank (D) 20, the condensate enters the cleaning tank (A) 17 from the pipe 28 and the shower pump (H) 21 and overflows, and as shown by an arrow 34, the heating tank (B) 18 Then, it is heated and boiled by the heater 24, and a part or all of its composition becomes vapor and is condensed in the cooling pipe 25 as shown by an arrow 35, and then returns from the pipe 26 to the water separation tank (D) 20.

In the steam cleaning carried out in the steam zone (C) 19 filled with the steam generated in the heating tank (B) 18, the liquid produced by the condensation of the steam on the surface of the object to be cleaned contains no contaminants. Therefore, it is effective as the final cleaning at the end of the cleaning process. Mechanisms (F) 23 and 33 for circulating the cleaning agent between the cleaning tank (A) 17 and the heating tank (B) 18 are
The cleaning agent is sent from the heating tank (B) 18 through the pipe (F) 33 to the cleaning tank (A) 17 by the circulation pump (F) 23, and overflows from the cleaning tank (A) 17 as indicated by an arrow 34. By returning to the heating tank (B) 18 to the cleaning tank (A)
It is possible to keep the cleaning agent composition of the cleaning tank 17 and the heating tank (B) 18 always the same, suppress the compositional change of the cleaning agent in the cleaning tank (A) 17, and obtain a stable cleaning property.

Mechanism (G) 22 for stirring the cleaning tank,
32 is a pipe (G) 32 for cleaning agent from the cleaning tank (A) 17
Through the stirring pump (G) 22 to the cleaning tank (A) 17 and the cleaning agent in the cleaning tank (A) 17 is stirred and mixed to make the composition of the cleaning agent uniform. It is possible to suppress compositional variation of the cleaning agent and obtain stable cleaning performance. Furthermore, by adding a heat exchanger to the mechanism for stirring the cleaning tank, the temperature of the cleaning tank can be freely set according to the purpose of cleaning and can be controlled with high accuracy.

In the cleaning apparatus of the present invention, the component (a1) having a high vapor pressure mainly contained in the cleaning agent and the component (b) slightly contained in the cleaning agent are circulated in the cleaning device while changing their states to liquid or gas. By this, it is possible to rinse and steam-clean the dirt components adhering to the object to be washed that may remain slightly, without using a rinse agent, and to adjust the temperature of the cleaning tank according to the cleaning purpose. By freely setting and controlling with high precision, precision cleaning with less influence on the material to be washed can be performed.

In the cleaning apparatus shown in FIG. 2 or 3, the number of cleaning tanks and / or heating tanks can be two or more depending on the purpose and application. First of the present invention
The method for separating dirt according to 0 or 13 is (c) a cleaning agent in which dirt is mixed in a cleaning tank with a liquid obtained by condensing the steam of the cleaning agent accumulated in the water separator generated by boiling the cleaning agent. Contaminating the dirt in the cleaning agent by contacting and in a dirt separation tank to separate the dirt components dissolved in the cleaning agent and then returning the liquid from which the dirt is separated to the cleaning tank. Is characterized by. In particular, in order to make the cleaning agent (c) a non-flammable cleaning agent, it is necessary to contain the non-chlorine fluorine compound as the component (a1). Further, in order to improve the dirt separation efficiency, it is possible to more efficiently separate the dirt by increasing the amount of the cleaning agent supplied to the dirt separation tank and lowering the temperature inside the dirt separation tank. The temperature in the dirt separation tank is preferably maintained at 20 ° C or lower, more preferably 10 ° C or lower. Furthermore, when the specific gravity of the separated dirt component is different from the specific gravity of the liquid in the dirt separation tank, the specific gravity difference separation is possible, which is preferable. The stain separation method of the present invention uses (c) a detergent,
The life of the cleaning agent is dramatically improved, the frequency of operations such as liquid exchange of the cleaning agent can be reduced, and the running cost can be reduced.

(C) The cleaning apparatus for cleaning with a cleaning agent may be provided with the method for separating dirt according to the eleventh or fourteenth aspects of the present invention. For example, in the dirt separation method according to the tenth or thirteenth aspect of the present invention, a dirt separation filter is incorporated into a pipe in which the liquid treated in the dirt separation tank returns to the cleaning tank, so that the amount of liquid contained in the liquid returned to the cleaning tank is reduced. It is possible to separate dispersed dirt components. The “separation filter” used in the present invention may be any of woven cloth, knitted cloth and non-woven cloth. Further, the fiber constituting the "separation filter" is not limited at all, for example, fibers of polyester copolymer such as polyethylene terephthalate, polybutylene terephthalate, polyhexamethylene adipamide, polycapramide and the like. Polyamide fibers, polyamide-imide fibers, aromatic polyamide fibers, polyester ether fibers such as polyparaoxybenzoate, halogen-containing polymer fibers such as polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, and polyolefins such as polypropylene and polyethylene. Fibers, various acrylic fibers and polyvinyl alcohol fibers, natural fibers such as regenerated cellulose, acetate, cotton, hemp, silk and wool. These fibers are used alone or in combination. Further, it is also possible to use those obtained by subjecting these fibers to a water-repellent treatment with dimethylpolysiloxane or a fluororesin having a perfluoroalkyl group.

The single fiber diameter of the fibers forming the "separation filter" used in the present invention is not particularly limited as long as the dirt separation property is not impaired, but preferably 0.1 to 10 μm.
m is the main, more preferably single fiber diameter 2 μm
The following are the main subjects. The term “mainly composed” means that the total weight of the fibers having the above-mentioned single fiber diameter is 50% or more with respect to the total weight of the fibers constituting the separation filter. When the diameter of the single fiber is 10 μm or less, a more preferable removal property of finely dispersed dirt components and a treatment speed are obtained, and
It can be easily obtained with a thickness of μm or more.

The thickness of the separation filter is not particularly limited as long as the dirt separation property is not impaired, but it is preferably 0.1 to 70 mm. When the thickness is 0.1 mm or more, a more preferable separation effect can be obtained, and when 70 mm or less, a more preferable pressure loss during liquid permeation can be suppressed. The separation filter used in the present invention is a flat membrane, a cylinder, a spiral,
It can be used in any form such as a pleated form. From the viewpoint of processing efficiency, the separation filter is preferably used in the form of pleats. Further, the separation filter is used by stacking one sheet or a plurality of sheets, and the liquid passing method may be any method such as liquid permeation by gravity, liquid permeation by pressure feeding, and is not limited at all.

For the separation filter used in the present invention,
It is also possible to use a reinforcing agent such as a wire mesh, plastic, or a fiber structure for the purpose of reinforcement. It is also possible to place a prefilter for collecting dust or the like, for example, a membrane-like or cotton-like dust collecting material before passing the return liquid through the separation filter used in the present invention. As the separation filter used in the present invention, a separation filter having the characteristics (a) or (b) sold under the trademark "U-Tech" by Asahi Kasei Co., Ltd. is particularly preferable.

The separation filter (a) has a monofilament diameter of 0.1.
Mainly composed of fibers of 10 to 10 μm and having a porosity of 30 to 90%,
A filter having a thickness of 0.1 to 70 mm and having a fiber surface with a critical surface tension of 3.5 × 10 ⁻² N / m or more for coarse-grain separation. The separation filter (b) is a single fiber. It is a filter that mainly separates fibers of a diameter of 0.1 to 10 μm and has a water repellent separation filter with a porosity of 30 to 90% to separate dirt components in the return liquid. When the dirt component is separated by the separation filter (a) and / or (b) of the present invention, the temperature of the liquid is adjusted to prevent the dirt component finely dispersed in the dirt separation tank from being redissolved in the return liquid. It is preferable to keep 20 ° C. lower, more preferably 10 ° C. or lower.

In the cleaning method according to the twelfth or fifteenth aspect of the present invention, the prerinsing agent containing the component (b) is pre-rinsed before the rinsing to increase the soil concentration in the cleaning agent. It is possible to suppress the occurrence of poor rinse. The pre-rinsing agent is not particularly limited as long as it is a solvent that does not impair the high pre-rinsing property, which is a characteristic of the pre-rinsing agent, but it is possible to add the components of the cleaning agent and / or the rinsing agent of the present invention. In particular, it is preferable to contain the component (b) because the pre-rinsing property is enhanced. In order to make the pre-rinsing agent non-flammable, it is necessary to contain the non-chlorine type fluorine compound which is the component (a1). Furthermore, it is preferable that the pre-rinsing agent component is the same as the cleaning agent and the rinsing agent component, because it is possible to suppress the composition variation of the cleaning agent and the rinsing agent. The concentration of the component (b) in the pre-rinsing agent is not particularly limited as long as it does not impair the high pre-rinsing property, which is a characteristic of the pre-rinsing agent, but when it is lower than the concentration of the component (b) in the cleaning agent. It is preferable that the rinsing property of the rinsing agent in the rinsing tank is improved and a high drying property is obtained, or
When the concentration is higher than the concentration of the component (b) in the rinse agent, the substituting property of the detergent component including the stain component is improved and a high pre-rinsing property is obtained, which is preferable. Further, the concentration of the component (b) in the pre-rinsing agent is lower than the concentration of the component (b) in the cleaning agent to be used, and higher than the concentration of the component (b) in the liquid condensed with the cleaning agent vapor or the rinsing agent. Is more preferable. Furthermore, the concentration of the component (b) in the pre-rinsing agent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. Furthermore, the use of the liquid treated by the soil separation method according to the twenty-seventh to twenty-ninth aspects of the present invention as a pre-rinsing agent makes the soil concentration in the pre-rinsing agent low and constant in continuous washing. Since it is possible to retain the pre-rinsing agent and the running cost can be reduced without requiring liquid exchange of the pre-rinsing agent, the concentration of the component (b) in the pre-rinsing agent and the concentration of the component (b) in the cleaning agent and the rinsing agent are preferable. The preferred concentration of the component (b) intermediate to that of the component (b) and the ability to maintain a constant concentration are preferable because higher rinsing properties in the rinse tank can be obtained. In the pre-rinsing step, effective pre-rinsing can be performed by combining physical methods such as immersion shower and ultrasonic waves for the purpose of improving the pre-rinsing property. The discharge pressure when performing pre-rinse with a shower is
It is preferably 1 × 10 ^{3 to} 2 × 10 ⁶ Pa, and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ Pa. The cleaning method of the present invention is the most suitable cleaning method because it is excellent in cleaning property and drying property when using a cleaning agent and has little influence on the material of the object to be cleaned.

The stain separation method and pre-rinse method of the present invention can be used in any combination, and as the cleaning method and cleaning apparatus using these in combination, any method and apparatus capable of cleaning the object to be cleaned may be used. , For example, it can be used by improving a general cleaning method and a cleaning device that have been used for chlorine-based cleaning agents so far. After separating the dirt by the separation method,
As a method of performing pre-rinsing with a pre-rinsing agent containing the component (b) before rinsing, it is preferable to combine physical methods such as dipping, showering, and ultrasonic waves because the pre-rinsing property is improved. As an example of a specific cleaning method preferable for using the cleaning agent and pre-rinsing agent of the present invention, the cleaning apparatus according to the eighteenth and twenty-first aspects of the present invention, which is preferable for performing pre-rinsing by a shower,
The cleaning device according to the sixteenth and twenty-first aspects of the present invention and the cleaning device according to the seventeenth and twenty-first aspects of the present invention which are preferable for performing the pre-rinsing by immersion can be mentioned. The cleaning method and the cleaning apparatus of the present invention will be specifically described below with reference to the accompanying drawings. The cleaning apparatus shown in FIG. 4, which is an example of the cleaning apparatus according to the eighteenth and twenty-first aspects of the present invention, has a main structure (c) a cleaning tank (A) 17 and a heating tank (B) 18 for containing a cleaning liquid, and a cleaning apparatus. A vapor zone (C) 19 filled with the vapor of the agent, a water separation tank (D) 20 for condensing the evaporated cleaning agent by a cooling pipe 25 and statically separating the condensed liquid and the water adhering to the cooling pipe. A dirt separation tank (I) 38 for contacting the condensate staying in the water separation tank (D) 20 with the cleaning agent containing dirt in the cleaning tank to separate and remove the dirt components dissolved in the cleaning agent. A mechanism (J) 40 to 44 for separating the dirt components in the liquid treated in the dirt separation tank by a separation filter, and a condensate and a separation filter statically separated in the water separation tank (D) 20 Mechanism for shower rinsing liquid (H K) 21,2
9, 30, 36, 37, 45 to 49, mechanisms (F) 23 and 33 for circulating the cleaning agent between the cleaning tank (A) 17 and the heating tank (B) 18, and the cleaning tank (A) 17 The mechanisms (L) 50 and 51 for continuously feeding the cleaning agent of No. 2 to the dirt separation tank, and the mechanisms (G) 22 and 32 for stirring the cleaning tank. In the actual cleaning, the object to be cleaned is put in a dedicated jig or basket, and the cleaning is completed while passing through the cleaning device in the order of the cleaning tank (A) 17 and the steam zone (C) 19.

In the cleaning tank (A) 17, the stains adhered to the object to be cleaned are cleaned and removed by ultrasonic waves 31 while controlling the temperature to be constant. At this time, as the physical force, any method may be used as long as it is a physical force such as rocking or a jet of a cleaning agent in a liquid that has been used in conventional cleaning machines. Further, by the mechanism (G) 22, 32 for stirring the cleaning tank, (c) the cleaning agent circulating in the cleaning tank (A) 17 and the heating tank (B) 18 and the condensate collected in the water separator. The washing tank (A) 17 is returned to the washing tank (A) 17 by the stirring pump (G) 22 through the pipe (G) 32, and the washing tank (A) 1
The detergent in 7 is circulated to mix with stirring.

In the steam zone (C) 19, the pre-rinse liquid that has passed through the separation filter (J) 42 is once retained in the storage tank (K), and the pipe (K) 47 and the three-way valve (K) 4
9. Shower pump (H, K) 21 piping (H, K)
The liquid is sent to 29 and 30, and the shower nozzle (H, K) 36,
By showering the article to be washed from 37, the stain components dissolved and / or dispersed in the detergent adhering to the article to be washed are removed with a pre-rinsing agent, and thereafter, the detergent of the present invention is mainly used. The vapor of the component (a) having a high vapor pressure and the component (b) slightly contained therein are condensed in the cooling pipe 25 and collected in the water separation tank (D) 20, and the liquid temperature is lowered by the cooling pipe 27. The flow path is switched by the valve 49, and the condensate containing no such contaminants is sent to the pipes (H, K) 29, 30 by the shower pump (H, K) 21, and the shower nozzle (H, K
K) By showering on the article to be washed from 36, 37, it is dissolved and / or dissolved in the pre-rinsing agent adhering to the article to be washed.
Alternatively, the dispersed dirt component is removed.

In the dirt separation tank (I) 38, the condensate of the water separation tank (D) 20 entering from the pipe 28 and the cleaning agent liquid feed pump (L) 50, and the washing tank (L) 51 which feeds the washing liquid ( A)
By contacting the cleaning agent 17 and lowering the liquid temperature with the cooling pipe 39, the dirt component dissolved in the cleaning agent is separated and removed, and then the cleaning agent and the condensate from which the dirt is separated are washed in the cleaning tank. By returning to (A) 17, the dirt component brought into the cleaning agent is continuously removed. Dirt separation tank (I) 3
Before returning to the cleaning tank (A) 17, the liquid treated in 8 is once collected in the dirt separation tank processing liquid tank (J) 40 and the cooling pipe 4
The liquid temperature was lowered by 1 and the contaminant component finely dispersed in the liquid was separated by passing through the separation filter (J) 42 by the pump (J) 43, and was once retained in the liquid storage tank (K) 46. After that, it can be used as a pre-rinsing agent while the piping 4
Pass through 8 and return to the washing tank (A) 17 as it is. The condensate is
After being collected in the water separation tank (D) 20, it passes through the pipe 28, the dirt separation tank (I) 38, and the pipe 48 to wash the cleaning tank (A) 17.
Return to the above, and from the shower pump (H, K) 21 to the pipes (H, K) 29, 30 shower nozzle (H, K) 3
6 and 37, and returns to the cleaning tank (A) 17, overflows from the cleaning tank (A) 17, enters the heating tank (B) 18 as indicated by an arrow 34, and is heated by the heater 24. After the whole becomes steam and is condensed in the cooling pipe 25 as shown by an arrow 35, the water separation tank (D) is supplied from the pipe 26.
Return to 20.

In the steam cleaning performed in the steam zone (C) 19 filled with the steam generated in the heating tank (B) 18, the liquid produced by the condensation of the steam on the surface of the object to be cleaned contains no contaminant. Since it is not present, it is effective as the final cleaning at the end of the cleaning process. Mechanisms (F) 23 and 33 for circulating the cleaning agent between the cleaning tank (A) 17 and the heating tank (B) 18 are
The cleaning agent is sent from the heating tank (B) 18 through the pipe (F) 33 to the cleaning tank (A) 17 by the circulation pump (F) 23, and overflows from the cleaning tank (A) 17 as indicated by an arrow 34. By returning to the heating tank (B) 18 to the cleaning tank (A)
It is possible to keep the cleaning agent composition of the cleaning tank 17 and the heating tank (B) 18 always the same, suppress the compositional change of the cleaning agent in the cleaning tank (A) 17, and obtain a stable cleaning property. In the cleaning apparatus of the present invention, by shower rinsing with the pre-rinsing agent containing the component (b) before rinsing, the residual amount of the dirt component dissolved in the cleaning agent on the surface of the object to be washed is reduced, and
The life of the cleaning agent can be dramatically improved by continuously separating and removing the dirt components brought into the cleaning agent.

Next, the cleaning apparatus shown in FIG. 5, which is an example of the cleaning apparatus according to the sixteenth and twenty-first aspects of the present invention, has as a main structure at least one component constituting the cleaning agent for heating and / or steam. Cleaning tank (A) 1 having a heating mechanism for generating, steam zone (C) 4 for steam cleaning with steam generated from the heating tank (B) 2, condensation obtained by condensing the generated steam Water separation tank (D) 5 for removing water from the liquid, rinse tank (E) for immersion rinsing with the condensed liquid from which water has been removed in the water separation tank (D)
3. Contamination of the cleaning agent in the cleaning tank (A) 1 with the cleaning tank (I) 53 for separating the cleaning agent containing the cleaning agent and the condensate to separate the cleaning agent dissolved in the cleaning agent Mechanism (L) 55, 56, water separation tank (D) that sends to the dirt separation tank
Mechanism (M) 57, 58 for continuously sending the condensate from which water has been removed to the dirt separation tank (M) 57, 58 Mechanism (J) 60 for separating dirt components in the liquid treated in the dirt separation tank by a separation filter 65 is a cleaning device having a pre-rinse tank (K) 66 for performing immersion pre-rinsing with a liquid that has passed through a separation filter. In the actual cleaning, the object to be cleaned is put in a dedicated jig, basket, etc., and the inside of the cleaning device is cleaned tank (A) 1, pre-rinse tank (K) 66, rinse tank (E).
The cleaning is completed while passing through 3 and the steam zone (C) 4 in this order.

In the cleaning tank (A) 1, the contaminants adhered to the object to be cleaned are cleaned and removed by the ultrasonic waves 12 while controlling the temperature to be constant. At this time, as the physical force, any method may be used as long as it is a physical force such as rocking or a jet of a cleaning agent in a liquid that has been used in conventional cleaning machines. In the pre-rinse tank (K) 66, the dirt separation filter (J) 64
The liquid treated in the dirt separation tank (I) 53 that has passed through is used as a pre-rinsing agent, and the component (a), the cleaning agent adhering to the object to be washed and the dirt component are washed and removed by the ultrasonic wave 67. At this time, as the physical force, any method may be used as long as it is a physical force that has been adopted in conventional cleaning machines such as rocking and jetting of a cleaning agent in a liquid.

In the rinsing tank (E) 3, the component (a), the rinsing agent of the present invention and the condensate thereof cleans and removes the pre-rinsing agent and dirt components adhering to the object to be washed with ultrasonic waves 13. At this time, as the physical force, any method may be used as long as it is a physical force that has been adopted in conventional cleaning machines such as rocking and jetting of a cleaning agent in a liquid. The steam cleaning performed in the steam zone (C) 4 filled with the steam generated in the heating tank (B) 2 does not contain any dirt component in the liquid produced by the condensation of the 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 (F) 11 and 14 for circulating the cleaning agent between the cleaning tank (A) 1 and the heating tank (B) 2 are provided with the cleaning agent from the heating tank (B) 2 to the pipe (F). The cleaning tank (A) 1 is supplied to the cleaning tank (A) 1 through the circulating pump 14 and is returned from the cleaning tank (A) 1 to the heating tank (B) 2 as indicated by an arrow 15 to return to the cleaning tank (A) 1. The cleaning agent composition of the (A) 1 and the heating tank (B) 2 are always kept the same, variation in composition of the cleaning agent in the cleaning tank (A) 1 is suppressed, and stable cleaning property can be obtained.

In the dirt separation tank (I) 53, the condensate in the water separation tank (D) 5 and the pipe 5 which are supplied by the condensate feed pump 58.
The cooling pipe 54 is brought into contact with the cleaning agent in the cleaning tank (A) 1 which is fed by the cleaning agent delivery pump (L) 56 through the cooling pipe 54.
By lowering the liquid temperature by separating and removing the dirt components dissolved in the cleaning agent, the cleaning agent and the condensate from which the dirt has been separated are returned to the cleaning tank (A) 1 Contamination components that are brought in are continuously removed. The liquid treated in the dirt separation tank (I) 53 is once collected in the dirt separation tank treatment liquid tank (J) 60, the liquid temperature is lowered by the cooling pipe 61, and the separation filter (J) is set by the pipe 62 and the pump (J) 63. ) 64 to separate dirt components finely dispersed in the liquid, enter the pre-rinsing tank (K) 66, and use as a component of the pre-rinsing agent, and then overflow as shown by arrow 68 to wash tank (K). A) Return to 1.

The condensate is collected in the water separation tank (D) 5 and the cooling pipe 9
After lowering the liquid temperature with, the liquid temperature is lowered with the cooling pipe 69 containing the rinse tank (E) 3 through the pipe 10 to be used as the rinse liquid, and while returning to the cleaning tank (A) 1 as shown by an arrow 16, the condensate From the pump 58 for the dirt through the dirt separation tank (I) 53, the pipe 59, the tank for the dirt separation tank treatment liquid (J) 60, and further divided,
One of the liquids is a dirt separation tank treatment liquid pump (J) 63, separation filter (J) 64, pipe 65, pre-rinse tank (K)
After entering 66 and using it as a component of the pre-rinsing agent, it overflows as shown by arrow 68 and returns to the cleaning tank (A) 1. The condensate returned to the cleaning tank (A) 1 is heated and boiled by the heater 6, and a part or all of its composition becomes vapor and is condensed in the cooling pipe 7 as shown by an arrow 74, and then separated from the pipe 8 by water. Return to tank (D) 5.

Next, the cleaning apparatus shown in FIG. 6 has a main structure, as an example of the cleaning apparatus described in the sixteenth and twenty-first aspects of the present invention, in FIG. 5 (G) as a mechanism for stirring the inside of the cleaning tank. This is a device with a pump. The mechanism (G) 70, 71 for stirring the cleaning tank returns the cleaning agent from the cleaning tank (A) 1 to the cleaning tank (A) 1 through the pipe (G) 71 and the stirring pump (G) 70 to the cleaning tank (A) 1. The washing tank (A) 1 is agitated and mixed to homogenize the detergent composition, whereby the washing tank (A)
It is possible to suppress the compositional variation of the cleaning agent in No. 1 and obtain a stable cleaning property. In the actual cleaning, put the item to be cleaned in a dedicated jig, basket, etc.
The cleaning is completed while passing through the pre-rinse tank (K) 66, the rinse tank (E) 3, and the vapor zone (C) 4 in this order.

In the cleaning apparatus shown in FIGS. 5 and 6 of the present invention, the pre-rinsing agent containing the component (b) is immersed and rinsed before rinsing to wash the object to be washed of the dirt component dissolved in the cleaning agent. By reducing the amount of residue on the surface and continuously separating and removing the dirt components brought into the detergent, the life of the detergent can be dramatically improved.

The present invention will be specifically described below with reference to examples. The various cleaning properties and stain removability of the cleaning agent were evaluated as follows. [Example 1 and Comparative Example 1] (1) Actual machine cleaning test 1 Cleaning tank (A) 1 and heating tank (B) of the cleaning apparatus shown in FIG.
2, the rinse agent is put in the rinse tank (E) 3 and the water separation tank (D) 5, and the cleaner in the heating tank (B) 2 is heated and boiled by the heater 6, and the steam is condensed in the cooling pipe 7. After confirming that the condensate overflows from the water separation tank (D) 5 into the rinsing tank (E) 3, it is possible to clean polymerized rosin, rosin metal salts, and other stains and processing oil that cause white residue. Was measured by the following operation and washing conditions. operation

Flux detergency evaluation glass epoxy printed circuit board (35 mm x 48 mm)
Was immersed in flux on one side, air-dried, and then soldered at 250 ° C. to a test piece, which was ultrasonically cleaned using the cleaning device described above. dry. Detergency is based on ionic residue (unit: μg
NaCl / sqin Omega meter (600R-S
C, manufactured by Alpha Metals Co., Ltd., and the measured value is designated as "β". Evaluation is based on the following criteria. ⊚: β ≦ 7 ○: 7 <β ≦ 14 x: β> 14 Trade name of the flux used in the test: ES-1040S
(Senju Metal Industry Co., Ltd.)

Degreasing and detergency evaluation 30-mesh stainless wire mesh (10 mm x 20 mm)
Is impregnated with the following metalworking oil and heated at 100 ° C. for 30 minutes to ultrasonically clean a test piece prepared by the above cleaning apparatus,
(C) After rinsing with the condensate of the cleaning agent, steam cleaning and drying. Detergency is evaluated visually. Evaluation is based on the following criteria. ◎: No residual processing oil ○: Slight residual processing oil △: Some residual processing oil ×: Some residual processing oil Metalworking oil used in the test: Unicut AM30 (trade name, Mitsubishi Nisseki (Made by Co., Ltd.)

Liquid Crystal Detergency Test Liquid crystal was applied to a gap portion (gap: 6 μm) outside the liquid crystal chamber, which was surrounded by the sealant of the liquid crystal cell, and left for 10 minutes to fill the gap portion with the liquid crystal. The sample is ultrasonically cleaned by the above cleaning apparatus, rinsed with the condensate of the cleaning agent (c), steam cleaned and dried. The detergency is evaluated by observing the gap part of the liquid crystal cell with a polarizing microscope. ◎: No liquid crystal stain remains in the gap part ○: Very little liquid crystal stain remains in the gap part △: Small amount of liquid crystal stain remains in the gap part ×: Large amount of liquid crystal stain remains in the gap part Liquid crystal used for the test: ZLI-4792 (manufactured by Merck Japan)

Cleaning conditions Cleaning tank (A) 1: ultrasonic cleaning for 2 minutes (40 kHz,
200w, liquid temperature 65 ° C) Rinse tank (E) 3: ultrasonic cleaning for 2 minutes (40kHz,
200w) Steam zone (C) 4: Cleaning agent used for static test for 2 minutes: Mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Limited)
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%)

[0120]

Example 1 The results are summarized below. Flux cleaning property: ◎ Degreasing cleaning property: ◎ Liquid crystal cleaning property: ○ Ultrasonic cleaning without boiling the cleaning tank by circulating the cleaning agent in the cleaning tank and the heating tank, and the cleaning agent in the heating tank It was confirmed that excellent cleaning properties with respect to flux, oil and liquid crystal were confirmed by rinsing and steam cleaning using the cleaning agent steam or the condensate of the steam obtained by heating. In addition, the vapor and condensate generated by boiling the cleaning agent contained almost no component (b), and sufficient rinsing properties were obtained by immersion rinsing with the condensate.

[0121]

[Comparative Example 1] The heater 6 of the heating tank (B) 2 was cut and not used in the cleaning apparatus shown in FIG. 7 in which the heater 72 was installed in the cleaning tank of the cleaning apparatus shown in FIG. 1 used in Example 1. ,
Instead, the washing tank (A) 1 is boiled by the heater 72 (75
C.) and the other evaluation test conditions were the same as in Example 1 for evaluation. The results are summarized below. Flux detergency: ○ Degreasing detergency: ○ Liquid crystal detergency: × When the washing tank is boiled and used, detergency against flux and oil is obtained, but liquid crystal cleaning, which requires the most ultrasonic cleaning, is insufficient. Met.

[Example 2 and Comparative Example 2] (2) Actual Machine Cleaning Test 2 Cleaning tank (A) 1 and heating tank (B) 2 of the cleaning apparatus shown in FIG.
To the rinse tank (E) 3 and the water separation tank (D) 5 and the heating agent in the heating tank (B) 2 is heated and boiled by the heater 6, and the steam is condensed in the cooling pipe 7 to condense water. After confirming that the condensate overflows from the separation tank (D) 5 into the rinse tank (E) 3, the polymer rosin, the rosin metal salt, and other stains that cause white residue and the detergency for processing oil are The measurement was performed according to the following operations and washing conditions.

Operation / flux detergency evaluation Glass epoxy printed circuit board (35 mm x 48 mm)
Was immersed in flux on one side, air-dried, and then soldered at 250 ° C. to a test piece, which was ultrasonically cleaned using the cleaning device described above. dry. Detergency is based on ionic residue (unit: μg
NaCl / sqin Omega meter (600R-S
C, manufactured by Alpha Metals Co., Ltd., and the measured value is designated as "β". Evaluation is based on the following criteria. ⊚: β ≦ 7 ○: 7 <β ≦ 14 x: β> 14 Trade name of the flux used in the test: ES-1040S
(Senju Metal Industry Co., Ltd.)

Degreasing and detergency evaluation 30-mesh stainless wire mesh (10 mm x 20 mm)
Is impregnated with the following metalworking oil and heated at 100 ° C. for 30 minutes to ultrasonically clean a test piece prepared by the above cleaning apparatus,
(C) After rinsing with the condensate of the cleaning agent, steam cleaning and drying. Detergency is evaluated visually. Evaluation is based on the following criteria. ◎: No residual processing oil ○: Slight residual processing oil △: Some residual processing oil ×: Some residual processing oil Metalworking oil used in the test: Unicut AM30 (trade name, Mitsubishi Nisseki (Made by Co., Ltd.)

Liquid Crystal Detergency Test Liquid crystal was applied to a gap portion (gap: 6 μm) outside the liquid crystal chamber, which was surrounded by the sealant of the liquid crystal cell, and left for 10 minutes to fill the gap portion with the liquid crystal. The sample is ultrasonically cleaned by the above cleaning apparatus, rinsed with the condensate of the cleaning agent (c), steam cleaned and dried. The detergency is evaluated by observing the gap part of the liquid crystal cell with a polarizing microscope. ◎: No liquid crystal stain remains in the gap part ○: Very little liquid crystal stain remains in the gap part △: Small amount of liquid crystal stain remains in the gap part ×: Large amount of liquid crystal stain remains in the gap part Liquid crystal used for the test: ZLI-4792 (manufactured by Merck Japan)

Cleaning conditions Cleaning tank (A) 1: ultrasonic cleaning for 2 minutes (40 kHz,
200w, liquid temperature 50 ° C) Rinse tank (E) 3: ultrasonic cleaning for 2 minutes (40 kHz,
200w) Steam zone (C) 4: Cleaning agent used for static test for 2 minutes: Mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Limited)
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%)

[0127]

Example 2 The results are summarized below. Flux detergency: ◎ Degreasing detergency: ◎ Liquid crystal detergency: ◎ By circulating the cleaning agent in the cleaning tank and the heating tank, and stirring the cleaning tank to control it at a constant temperature, the cleaning tank does not boil. Superior to flux, oil and liquid crystal by rinsing and steam cleaning using the cleaning agent vapor obtained by ultrasonic cleaning and heating the cleaning agent in the heating tank or the condensate of the vapor. The cleanability was confirmed. In addition, the vapor and condensate generated by boiling the cleaning agent contained almost no component (b), and sufficient rinsing properties were obtained by immersion rinsing with the condensate.

[0128]

[Comparative Example 2] The heater 6 of the heating tank (B) 2 was cut and not used in the cleaning apparatus shown in FIG. 7 in which the heater 72 was installed in the cleaning tank of the cleaning apparatus shown in FIG. 1 used in Example 1. ,
Instead, the washing tank (A) 1 is boiled by the heater 72 (75
C.) and the other evaluation test conditions were the same as in Example 1 for evaluation. The results are summarized below. Flux detergency: ○ Degreasing detergency: ○ Liquid crystal detergency: × When the washing tank is boiled and used, detergency against flux and oil is obtained, but liquid crystal cleaning, which requires the most ultrasonic cleaning, is insufficient. Met.

(3) Actual machine cleaning test 3 Cleaning tank (A) 17 and heating tank (B) of the cleaning apparatus shown in FIG.
18 and the water separation tank (D) 20 are filled with the cleaning agent, the cleaning agent in the heating tank (B) 18 is heated and boiled by the heater 24, and is idled for 1 hour to be included in the cleaning agent in the water separation tank (D) 20. After reducing the concentration of the component having a low vapor pressure, the detergency against stains and processing oil that cause white residue such as polymerized rosin and rosin metal salt was measured by the following operations and washing conditions.

Operation / flux detergency evaluation Glass epoxy printed circuit board (35 mm x 48 mm)
After one side is dipped in flux and air dried, the test piece prepared by soldering at 250 ° C. is ultrasonically cleaned using the above cleaning device, (c) Shower rinse with a condensate of the cleaning agent, and then steam cleaning. To dry. Detergency is measured by measuring the ionic residue (unit: μg NaCl / sqin) with an omega meter (60
0R-SC, manufactured by Alpha Metals Co., Ltd., and the measured value is defined as “β”. Evaluation is based on the following criteria. ⊚: β ≦ 7 ○: 7 <β ≦ 14 x: β> 14 Trade name of the flux used in the test: ES-1040S
(Senju Metal Industry Co., Ltd.)

Degreasing and detergency evaluation 30-mesh stainless wire mesh (10 mm x 20 mm)
Is impregnated with the following metalworking oil and heated at 100 ° C. for 30 minutes to ultrasonically clean a test piece prepared by the above cleaning apparatus,
(C) After shower rinsing with the condensate of the cleaning agent, steam cleaning and drying. Detergency is evaluated visually. Evaluation is based on the following criteria. ◎: No residual processing oil ○: Slight residual processing oil △: Some residual processing oil ×: Some residual processing oil Metalworking oil used in the test: Unicut AM30 (trade name, Mitsubishi Nisseki (Made by Co., Ltd.)

Liquid Crystal Detergency Test Liquid crystal was applied to a gap portion (gap: 6 μm) outside the liquid crystal chamber, which was surrounded by the sealant of the liquid crystal cell, and left for 10 minutes to fill the gap portion with the liquid crystal. The sample is ultrasonically cleaned by the above cleaning device, (c) shower rinsed with a condensate of the cleaning agent, and then steam cleaning and drying.
The detergency is evaluated by observing the gap part of the liquid crystal cell with a polarizing microscope. ◎: No liquid crystal stain remains in the gap part ○: Very little liquid crystal stain remains in the gap part △: Small amount of liquid crystal stain remains in the gap part ×: Large amount of liquid crystal stain remains in the gap part Liquid crystal used for the test: ZLI-4792 (manufactured by Merck Japan)

Cleaning conditions Cleaning tank (E) 14: ultrasonic cleaning for 2 minutes (40 kHz
z, 200 w, liquid temperature 50 ° C.) Steam zone (G) 16: 2 minutes shower rinse (5 L /
After that, a cleaning agent used for the static test for 1 minute: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Limited)
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%)

[0134]

Example 3 The results are summarized below. Flux detergency: ◎ Degreasing detergency: ◎ Liquid crystal detergency: ◎ By circulating the cleaning agent in the cleaning tank and the heating tank, and stirring the cleaning tank to control it at a constant temperature, the cleaning tank will not be boiled. Excellent cleaning for flux, oil, and liquid crystal by rinsing and steam cleaning using the cleaning agent vapor obtained by sonic cleaning and heating the cleaning agent in the heating tank or the condensate of the cleaning agent. Detergency was confirmed.

[0135]

[Comparative Example 3] The heater 24 of the heating tank (B) 18 was cut and not used in the cleaning apparatus shown in FIG. 8 in which the heater 73 was installed in the cleaning tank of the cleaning apparatus shown in FIG. 3 used in Example 3. Instead, the cleaning tank (A) 17 was boiled (75 ° C.) with the heater 73, and the other evaluation test conditions were the same as in Example 3 for evaluation. The results are summarized below. Flux detergency: ○ Degreasing detergency: ○ Liquid crystal detergency: × When the washing tank is boiled and used, detergency against flux and oil is obtained, but liquid crystal cleaning, which requires the most ultrasonic cleaning, is insufficient. Met.

[Example 4 and Comparative Example 4] (4) Separation of dirt and cleaning test by actual machine A cleaning agent was put into the cleaning tank (A) 17 and the water separation tank (D) 20 of the cleaning apparatus shown in Fig. 4 and heated. The cleaning agent in the tank (A) 18 is heated and boiled by the heater 24, and idle operation is performed for 1 hour to remove components of low vapor pressure contained in the cleaning agents in the water separation tank (D) 20 and the dirt separation tank (I) 38. After decreasing the concentration, the cleaning agent delivery pump (L) 50 is used for the cleaning tank (A) 17
The processing oil dissolved in the cleaning agent is separated by continuously sending the cleaning agent of No. 3 to the soil separation tank (I) 38. Since the specific gravity of the separated processing oil is lighter than the specific gravity of the liquid in the dirt separation tank and floats, it is continuously discharged from the dirt separation tank. While continuously separating the processing oil, which is a soil component, as described above, the cleaning performance for the processing oil and the change in the oil concentration in the cleaning agent were measured by the following operations and cleaning conditions.

Operation Washing Samples (250 bearings) are impregnated with the following metalworking oil and then placed in a basket for barrel washing. 2% by mass of processing oil is added to the cleaning agent in the cleaning tank (A) 17 of the cleaning apparatus, and then cleaning is performed, and (c) shower rinse is performed with the condensate of the cleaning agent, and then steam cleaning is performed and drying is performed. The liquid that has passed through the separation filter (J) 42 is returned to the cleaning tank (A) 17 through the pipe 48 without pre-shower rinsing. Washing without pre-shower rinsing is performed continuously for 15 hours at a tact time of 15 minutes (160 times), and the washability of the bearing and the oil concentration in the detergent after the first and 40-hour operation are measured. The detergency is measured by measuring the processing oil remaining on the surface of the cleaned part with an oil content measuring device (OIL-20, Central Science Co., Ltd.). Evaluation is based on the following criteria. ⊚: Residual oil content of less than 70 μg / piece O: Residual oil content of 70 μg or more / piece to less than 100 μg / piece x: Residual oil content of 100 μg or more / piece Regarding the oil concentration in the cleaning agent, use 20 ml of the cleaning agent in a vacuum dryer (110 Dry at 0 ° C. and 0 Pa) and measure the concentration of non-volatile residue. Evaluation is based on the following criteria. ◎: Increased oil concentration is less than 1% by mass ○: Increased oil concentration is 1% by mass or more and less than 2% by mass ×: Increased oil concentration is 2% by mass or more

Cleaning conditions Cleaning tank (A) 17: 2 minutes boiling cleaning steam zone (C) 19: 2 minutes shower rinse (5 L /
2 minutes later, the amount of the condensate of the cleaning agent left for 2 minutes: 500 ml / min, the feed rate of the cleaning agent to the dirt separation tank: 110 ml / min, the temperature of the dirt separation tank: 3 to 6 ° C., the operation status of the dirt separation tank: ""Cleaning" used in the "operation" and "stop" tests in the comparative example: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Limited)
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Metalworking oil used in the test: FM220 (trade name, Yusilon Former, Yushiro Chemical Co., Ltd.)

[0139]

Example 4 The results are summarized below. Detergency 1st time: ○, 40 hours later (160 times): ○ Oil concentration change 40 hours (160 times): ◎ Processing oil carried into the cleaning agent is continuously separated and removed in the dirt separation tank and separated. By separating the processing oil that is finely dispersed in the return liquid with a filter, it is possible to suppress the oil concentration in the cleaning agent to a lower level, and the processing oil cleaning property after 40 hours is the first time in the cleaning test. The same high cleaning level was maintained.

[0140]

Comparative Example 4 The results are summarized below. Detergency 1st time: ○, 40 hours later (160 times): × Oil concentration change 40 hours later (160 times): × Oil concentration in the cleaning agent increased by the processing oil brought into the cleaning agent for 40 hours The subsequent processing oil detergency deteriorated.

[Embodiments 5 to 6] (5) Separation of dirt and cleaning test by actual machine Cleaning tank (A) 17 and heating tank (B) of the cleaning apparatus shown in FIG.
18 into which a cleaning agent is added, and a water separation tank (D) 20, a dirt separation tank (I) 38, a liquid storage tank (J) 40, and a separation filter unit (J) 42 are added with a rinse agent, and a heating tank (B) 18
The cleaning agent is heated and boiled by the heater 24, and the cleaning agent circulating pump (F) 23 circulates the cleaning agent in the cleaning tank (A) 17 and the heating tank (B) 18 for 1 hour while maintaining a constant composition. Processing oil dissolved in the cleaning agent by continuously feeding the cleaning agent in the cleaning tank (A) 17 to the dirt separation tank (I) 38 by the cleaning agent liquid supply pump (L) 50 after performing idle operation. Separation and washing. The detergency against the processing oil and the oil concentration change in the detergent were measured by the following operations and washing conditions.

Operation Washing Samples (250 bearings) are impregnated with the following metalworking oil and then put in a basket for barrel washing. After adding 2% by mass (Example 4) or 4% by mass (Example 5) of processing oil to the cleaning agent in the cleaning tank (A) 17 and the heating tank (B) 18 of the above cleaning apparatus, the cleaning agent is washed and separated. After pre-shower rinsing with the liquid that has passed through the filter (J) 42, further shower rinsing with the condensate of the cleaning agent (c), and finally steam cleaning and drying. Cleaning is performed for 15 minutes with a takt time, and the cleaning property of the bearing is measured. Detergency is measured by the oil content measuring device (OIL
-20, manufactured by Central Science Co., Ltd. Evaluation is based on the following criteria. ⊚: Residual oil content less than 70 μg / piece ◯: Residual oil content 70 μg or more / piece to less than 100 μg / piece x: Residual oil content 100 μg or more / piece

Cleaning conditions Cleaning tank (A) 17: ultrasonic cleaning for 2 minutes (40 kHz
z, 200w, liquid temperature 50 ° C) Steam zone (C) 19: 2 minutes pre-shower rinse (5
2 minutes after shower rinse (5 L / minute), 2
Minute static cleaning agent condensate flow rate: 500 ml / min Cleaning agent feed rate to the dirt separation tank: 110 ml / min Dirt separation tank solution temperature: 3 to 6 ° C Liquid temperature of the storage tank (J) 40: 3 to 6 ° C Separation filter: EUS04AV (Brand name: U-Tech, manufactured by Asahi Kasei Co., Ltd.) Detergent used in the test: Mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (Brand name: HFE7100, manufactured by Sumitomo 3M Limited)
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%) Metalworking oil used in the test: FM220 (trade name, Yusilon Former, Yushiro Chemical Co., Ltd.)

[0144]

Example 5 The results are summarized below. Detergency: ◎ Prewasher rinse was performed after washing with a detergent containing 2% by mass of processing oil, whereby excellent detergency was confirmed.

[0145]

Example 6 The results are summarized below. Detergency: ○ Sufficient detergency was obtained by performing pre-shower rinse after washing with a detergent containing 4% by mass of processing oil.

[Examples 7 to 8] (6) Separation of dirt and cleaning test by actual machine Cleaning tank (A) 1 and heating tank (B) of the cleaning apparatus shown in FIG.
A cleaning agent is put in 2, and a pre-rinse tank (K) 66, a rinse tank (E) 3, a water separation tank (D) 5, a dirt separation tank (I) 53,
A rinse agent is put in the liquid storage tank (J) 60 and the separation filter unit (J) 64, and the cleaning agent in the heating tank (B) 2 is heated and boiled by the heater 6 and idled for 1 hour, and then washed. Cleaning tank (A) 1 with agent delivery pump (L) 56
The cleaning agent is continuously sent to the dirt separation tank (J) 53, and the dirt separation tank treatment liquid feed pump (J) 63 is operated to separate and clean the processing oil dissolved in the cleaning agent. The detergency against the processing oil and the oil concentration change in the detergent were measured by the following operations and washing conditions.

Operation Washing Samples (250 bearings) are impregnated with the following metalworking oil and then placed in a basket for barrel washing. 2% by mass (Example 6) or 4% by mass (Example 7) of processing oil was added to the cleaning agent in the cleaning tank (A) 1 of the above-described cleaning device, followed by cleaning and separation filter (J) in the pre-rinsing tank. After pre-immersion rinse with the liquid passing through 64, (c)
Immersion rinse with a condensate of the cleaning agent, and finally steam cleaning and drying. Cleaning is performed for 15 minutes with a tact, and the cleaning property of the bearing is measured. The detergency is measured by measuring the processing oil remaining on the surface of the cleaned part with an oil content measuring device (OIL-20, Central Science Co., Ltd.). Evaluation is based on the following criteria. ⊚: Residual oil content less than 70 μg / piece ◯: Residual oil content 70 μg or more / piece to less than 100 μg / piece x: Residual oil content 100 μg or more / piece

Cleaning conditions Cleaning tank (A) 1: ultrasonic cleaning for 2 minutes (40 kHz,
200w, liquid temperature 65 ° C) Pre-rinse tank (K) 66: 1 minute ultrasonic cleaning (40kH
z, 200w) Rinse tank (E) 3: ultrasonic cleaning for 1 minute (40 kHz)
z, 200w) Steam zone (C) 4: 2 minutes static cleaning agent condensate flow rate: 500 ml / min Cleaning agent feed rate to the dirt separation tank: 110 ml / min Contamination separation tank liquid temperature: 3 to 6 ° C Storage tank (J) Liquid temperature of 60: 3 to 6 ° C Separation filter: EUS04AV (trade name: U-Tech, manufactured by Asahi Kasei Co., Ltd.) Cleaning agent used in the test: Mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (product) Name: HFE7100, manufactured by Sumitomo 3M Limited
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%) Metalworking oil used in the test: FM220 (trade name, Yusilon Former, Yushiro Chemical Co., Ltd.)

[0149]

Example 7 The results are summarized below. Detergency: ◎ Excellent detergency was confirmed by performing pre-dip rinse after cleaning with a detergent containing 2% by mass of processing oil.

[0150]

Example 8 The results are summarized below. Detergency: ◎ Excellent detergency was obtained by performing pre-dip rinse after washing with a detergent containing 4% by mass of processing oil.

[Examples 9 to 10] (7) Separation of dirt and cleaning test by actual machine Cleaning tank (A) 1 and heating tank (B) of the cleaning apparatus shown in FIG.
A cleaning agent is put in 2, and a pre-rinse tank (K) 66, a rinse tank (E) 3, a water separation tank (D) 5, a dirt separation tank (I) 53,
A rinse agent is put in the liquid storage tank (J) 60 and the separation filter unit (J) 64, and the cleaning agent in the heating tank (B) 2 is heated and boiled by the heater 6 and idled for 1 hour, and then washed. Cleaning tank (A) 1 with agent delivery pump (L) 56
The cleaning agent is continuously sent to the dirt separation tank (J) 53, and the dirt separation tank treatment liquid feed pump (J) 63 is operated to separate and clean the processing oil dissolved in the cleaning agent. The detergency against the processing oil and the oil concentration change in the detergent were measured by the following operations and washing conditions.

Operation Washing Samples (250 bearings) are impregnated with the following metalworking oil and then placed in a basket for barrel washing. After adding 2% by mass (Example 8) or 4% by mass (Example 9) of processing oil to the cleaning agent in the cleaning tank (A) 1 of the above cleaning apparatus, the cleaning agent is cleaned and then separated in the pre-rinse tank (J). After pre-immersion rinse with the liquid passing through 64, (c)
Immersion rinse with a condensate of the cleaning agent, and finally steam cleaning and drying. Cleaning is performed for 15 minutes with a takt time, and the cleaning property of the bearing is measured. The detergency is measured by measuring the processing oil remaining on the surface of the cleaned part with an oil content measuring device (OIL-20, Central Science Co., Ltd.). Evaluation is based on the following criteria. ⊚: Residual oil content less than 70 μg / piece ◯: Residual oil content 70 μg or more / piece to less than 100 μg / piece x: Residual oil content 100 μg or more / piece

Cleaning conditions Cleaning tank (A) 1: ultrasonic cleaning for 2 minutes (40 kHz
z, 200w, liquid temperature 50 ° C.) Pre-rinse tank (K) 66: 1 minute ultrasonic cleaning (40 kHz)
z, 200w) Rinse tank (E) 3: ultrasonic cleaning for 1 minute (40 kHz)
z, 200w) Steam zone (C) 4: 2 minutes static cleaning agent condensate flow rate: 500 ml / min Cleaning agent feed rate to the dirt separation tank: 110 ml / min Contamination separation tank liquid temperature: 3 to 6 ° C Storage tank (J) Liquid temperature of 60: 3 to 6 ° C Separation filter: EUS04AV (trade name: U-Tech, manufactured by Asahi Kasei Co., Ltd.) Cleaning agent used in the test: Mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (product) Name: HFE7100, manufactured by Sumitomo 3M Limited
/ 3-Methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 50/30/20 (mass%) Rinse agent used in the test: a mixture of methyl perfluorobutyl ether and methyl purple oroisobutyl ether (trade name: HFE7100, Sumitomo 3M Ltd.
Manufactured) / 3-methyl-3-methoxybutanol / dipropylene glycol dimethyl ether = 99 / 0.6 / 0.
4 (mass%) Metalworking oil used in the test: FM220 (trade name, Yusilon Former, Yushiro Chemical Co., Ltd.)

[0154]

Example 9 The results are summarized below. Detergency: ◎ Excellent detergency was confirmed by performing pre-dip rinse after cleaning with a detergent containing 2% by mass of processing oil.

[0155]

Example 10 The results are summarized below. Detergency: ◎ Excellent detergency was obtained by performing pre-dip rinse after washing with a detergent containing 4% by mass of processing oil.

[0156]

EFFECTS OF THE INVENTION By using components having different vapor pressures in combination, it has excellent solubility for all kinds of dirt such as oil and flux, and reduces the risk of ignition (c) detergent and (d) In the cleaning method, soil separation method and cleaning device of the present invention using a rinse agent, cleaning is performed without boiling the cleaning tank by circulating the cleaning agent in the cleaning tank and the heating tank, and by further stirring the cleaning tank. By carrying out effective ultrasonic cleaning and utilizing the vapor and condensate of the cleaning agent (c) generated by boiling the cleaning agent in the heating tank, cleaning to drying can be performed.

That is, although the drying property is excellent and there is no risk of ignition, the cleaning property is remarkably inferior. (A1) Various stains are caused by a chlorine-free fluorine compound having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. (B) 2 which has excellent detergency against
By adding a component having a vapor pressure of less than 1.33 × 10 ³ Pa at 0 ° C., the cleaning agent containing the component (b) is circulated in the cleaning tank and the heating tank to boil the cleaning agent. Cleaning without stirring and stirring the cleaning tank enables efficient ultrasonic cleaning and rinsing with a condensate of the cleaning agent containing a small amount of component (b), resulting in excellent cleaning performance against various stains. It is possible to provide a cleaning method and a cleaning device that effectively utilize the characteristics of the component (b) having

Further, in the detergent containing the non-chlorine type fluorine compound as the component (a1), due to the characteristic of the non-chlorine type fluorine compound that it does not have a flash point, the detergent is a detergent having no flash point. Since it is possible to do so and the risk of ignition is reduced, it is not necessary to have an explosion-proof structure to prevent ignition, explosion, etc. on the equipment such as washing machines, and existing washing equipment can be used as it is. Therefore, it is possible to establish a low-cost cleaning system.

Further, the cleaning agent in the cleaning tank and the liquid obtained by condensing the vapor of the cleaning agent in the water separation tank are sent to the dirt separation tank.
By contacting the liquid, the dirt components dissolved in the cleaning agent in the dirt separation tank are separated and removed, and then the liquid from which the dirt has been separated is returned to the cleaning tank to effectively remove the dirt in the cleaning agent. Can be continuously separated, and by adding a separation filter, it becomes possible to obtain a higher dirt separation property. Further, the liquid in which the dirt component is separated by the dirt separation tank and / or the separation filter has a low dirt component concentration and is kept constant, and (c) is compared with the condensate obtained by heating the cleaning agent, By containing a large amount of the component (b) having excellent solubility, it becomes possible to obtain excellent detergency due to the excellent pre-rinsing property.

By using the cleaning method, dirt separation method and cleaning apparatus of the present invention in combination as required, the cleaning agent has a long life and the risk of oxidative decomposition and ignition is reduced, so that all types of dirt can be obtained. Can be easily dissolved and washed from the surface of the object to be washed.

[Brief description of drawings]

FIG. 1 is an example of the cleaning apparatus according to the first aspect of the present invention.

FIG. 2 is an example of the cleaning device according to the second aspect of the present invention.

FIG. 3 is an example of the cleaning apparatus according to the second aspect of the present invention.

FIG. 4 is an example of the cleaning apparatus according to the sixteenth and twenty-first aspects of the present invention.

FIG. 5 is an example of the cleaning apparatus according to the seventeenth and twenty-first aspects of the present invention.

FIG. 6 is an example of the cleaning apparatus according to the eighteenth and twenty-first aspects of the present invention.

FIG. 7 is an example of a cleaning apparatus for carrying out Comparative Examples 1 and 2.

FIG. 8 is an example of a cleaning apparatus for carrying out Comparative Example 3.

[Explanation of symbols]

1 cleaning tank (A) 2 heating tanks (B) 3 rinse tank (E) 4 Steam zone (C) 5 Water separator (D) 6 heater 7 Cooling pipe 8 Condensate piping 9 Cooling pipe 10 Condensate piping after water separation 11 Cleaning agent circulation pump (F) 12 ultrasonic waves 13 ultrasonic waves 14 Cleaning agent circulation pipe (F) 15 Flow of cleaning agent 16 Condensate flow 17 Cleaning tank (A) 18 Heating tank (B) 19 Steam zone (C) 20 Water separator (D) 21 Shower pump (H, K) 22 Pump for stirring (G) 23 Circulation pump (F) 24 heater 25 cooling pipe 26 Piping for condensate 27 Cooling pipe 28 Condensate piping after water separation 29 Condensate piping for shower (H, K) 30 Condensate piping for shower (H, K) 31 Ultrasound 32 piping (G) 33 Piping (F) 34 Cleaning agent flow 35 Steam flow 36 shower nozzles (H, K) 37 Shower nozzle (H, K) 38 Dirt Separation Tank (I) 39 Cooling pipe 40 Liquid storage tank (J) 41 Cooling pipe (J) 42 Separation filter (J) 43 Pump (J) 44 Piping (J) 45 piping 46 Liquid storage tank (K) 47 Piping (K) 48 piping 49 Three-way valve (F, K) 50 Detergent pump (L) 51 Cleaning agent liquid supply pipe (L) 52 Return pipe after separation of dirt 53 Dirt Separation Tank (I) 54 Cooling pipe 55 Cleaning agent liquid delivery pipe (L) 56 Detergent Liquid Delivery Pump (L) 57 Condensate delivery pipe (M) 58 Condensate Liquid Delivery Pump (M) 59 Return pipe after separation of dirt 60 Liquid storage tank (J) 61 cooling pipe 62 Liquid transfer piping (J) 63 Liquid Delivery Pump (J) 64 Separation filter (J) 65 Liquid supply piping 66 Pre-rinse tank (K) 67 ultrasound 68 Flow of pre-rinse liquid 69 cooling pipe 70 Stirring pump (F) 71 Piping (F) 1 heater 2 heater 3 Steam flow

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) C11D 7/60 C11D 7/60 17/00 17/00 17/08 17/08 C23G 3/00 C23G 3/00 Z 5 / 032 5/032 F term (reference) 3B201 AA46 AB02 BB02 BB11 BB21 BB82 BB83 BB87 BB92 CC01 CD22 4H003 DA14 DA15 DA16 DB01 DC02 DC03 DC04 ED26 ED29 ED32 FA21 FA45 4K053 QA05 QA07 RA04 RA32 RA13 RA06 SA08 RA41 SA40 SA08 RA41 SA40 SA08 RA41 SA08 XA15 YA02 YA03

Claims (21)

[Claims] 1. (a1) The vapor pressure at 20 ° C. is 1.3.
Non-chlorine type fluorine compound of 3 × 10 ³ Pa or more and (b) 2
In a method of cleaning using a cleaning agent (c) having a flash pressure of less than 1.33 × 10 ³ Pa and having no flash point, the cleaning agent is heated in a heating tank. A cleaning method comprising rinsing and / or steam cleaning using the steam of the cleaning agent thus obtained or a condensate of the steam, and circulating the cleaning agent in the cleaning tank and the heating tank. 2. The cleaning method according to claim 1, wherein the cleaning tank is agitated. 3. (a1) The vapor pressure at 20 ° C. is 1.3.
Non-chlorine type fluorine compound of 3 × 10 ³ Pa or more 80.0% by mass to 99.9% by mass and (b) a component whose vapor pressure at 20 ° C. is less than 1.33 × 10 ³ Pa, 0.1% by mass to 20% ．
The cleaning method according to claim 1 or 2, wherein a rinsing agent having no flash point (d) containing 0% by mass is used. 4. The cleaning as claimed in claim 1, wherein the component (a1) contains a compound selected from methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture thereof. Method. 5. The component (b) contains one or more compounds selected from the group consisting of organic compounds having an ether bond and / or an ester bond, according to any one of claims 1 to 4. The cleaning method described in. 6. The component (b) is a glycol ether,
The cleaning method according to any one of claims 1 to 5, which comprises one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. 7. The component (b) contains a combination of (b1) one or more compounds selected from glycol ether monoalkyl ethers and (b2) one or more compounds selected from glycol ether dialkyl ethers. 7. The cleaning method according to any one of claims 1 to 6. 8. The cleaning method according to claim 1, wherein (c) the cleaning agent and / or (d) the rinse agent has (a)
2) It contains one or more compounds selected from the group consisting of alcohols, ketones, esters and hydrocarbons having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more. Cleaning method. 9. The cleaning method according to claim 1, wherein the cleaning agent (c) and / or the rinse agent (e) is added to the cleaning agent (e).
The cleaning method according to claim 1, further comprising an antioxidant. 10. The cleaning method according to claim 1, wherein a dirt separation tank is used. 11. The method according to claim 1, wherein a separation filter is used.
The cleaning method according to any one of 0. 12. The method according to claim 1, which has a pre-rinse mechanism.
The cleaning method according to 1. 13. (c) A liquid obtained by condensing vapor of a cleaning agent and / or (d) a rinsing agent and the cleaning agent in which dirt is mixed in the cleaning tank are brought into contact with each other in the dirt separation tank and dissolved in the cleaning agent. The cleaning method according to any one of claims 1 to 12, further comprising a dirt separation method characterized by returning the dirt-separated liquid to a cleaning tank after separating the dirt components. 14. A method in which a liquid obtained by contacting (c) a vapor of a cleaning agent vapor and / or (d) a rinsing agent with the cleaning agent contaminated with dirt in a cleaning tank is treated with a separation filter and then washed. The cleaning method according to any one of claims 1 to 13, which has a dirt separation method characterized by returning to the tank. 15. The liquid treated by the soil separation method according to claim 13 and / or 14 is used as a pre-rinsing agent before rinsing, and pre-rinsing is performed. The cleaning method described in. 16. (A) (c) a cleaning tank for cleaning an article to be cleaned with a cleaning agent, (B) a heating mechanism for generating vapor of at least one component or compound constituting the cleaning agent A heating tank having, (C) a steam zone for steam cleaning with steam generated from the heating tank (B), (D) water separation for removing water from a condensate obtained by condensing the generated steam Tank, (E) rinse tank for rinsing with the condensate retained in the water separation tank (D), (F) mechanism for circulating the cleaning agent between the cleaning tank (A) and the heating tank (B) A cleaning device. 17. The cleaning device according to claim 16, wherein the cleaning device has a mechanism for agitating a cleaning agent in (G) the cleaning tank (A). 18. (A) (c) a cleaning tank for cleaning an object to be cleaned with a cleaning agent, (B) a heating mechanism for generating vapor of at least one component or compound constituting the cleaning agent. A heating tank having, (C) a steam zone for steam cleaning with steam generated from the heating tank (B), (D) water separation for removing water from a condensate obtained by condensing the generated steam Tank, (H) a mechanism for shower rinsing the condensate retained in the water separation tank (D) in the steam zone (C), (F) the cleaning agent between the cleaning tank (A) and the heating tank (B) A cleaning device having a mechanism for circulating between (G) a cleaning tank (A) and a mechanism for stirring a cleaning agent in the cleaning tank (A). 19. The method according to claim 16, further comprising (I) a dirt separation tank.
The cleaning device according to any one of items 1 to 18. 20. The cleaning device according to claim 16, further comprising (J) a separation filter. 21. The cleaning device according to claim 16, further comprising (K) a pre-rinse mechanism.