JP2002012894A - Low ignitable cleanser, method for cleansing and device for cleansing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cleanser which exhibits high cleansing abilities against all types of stains, prevents oxidative deterioration under high temperature on stream cleansing treatments and so on, is low toxic, exhibits high material stability for articles to be cleansed, has low ignitability, and is never liable to cause the disruption of the ozonosphere, and to provide a cleansing method and a cleansing device which are suitable for the cleanser. SOLUTION: This low ignitable cleanser is obtained by adding one or more compounds selected from glycol ethers to methyl perfluorobutyl ether and/or methyl perfluoroisobutyl ether, and then further adding a glycol ether acetate, a hydroxycarboxylic ester or the like to the mixture.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

[0003] These washing and removal methods have many features such as nonflammability, low toxicity and excellent solubility. For example, 1,1,2-trichloro-1,2,2-trifluoro is preferred. Ethane (hereinafter CFC113) or CFC113
It was washed with a solvent mixed with alcohol. However, CFC113 was pointed out as a problem of global environmental pollution such as depletion of the ozone layer, and its production was completely abolished in Japan at the end of 1995. As an alternative to this CFC 113,
A mixture of dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as HCFC225) or 1,1-dichloro- 1-fluoroethane (hereinafter H
Hydrochlorofluorocarbons (hereinafter referred to as HCFC) such as CFC141b) and hydrofluorocarbons (hereinafter referred to as HFC) such as 2H and 3H-perfluoropentane have been proposed. However, the use of HCFCs is scheduled to be banned in 2020 in Japan due to their ability to deplete the ozone layer. In recent years, it has been pointed out that HFCs have a high global warming potential that has emerged as a new problem. It is necessary to take measures such as reducing the amount of release, which makes it difficult to use in cleaning agent applications. Furthermore, in recent years, hydrofluoroethers containing no chlorine atom (hereinafter referred to as HFE)
Non-flammable fluorine-based solvents that have no ozone layer destruction ability, etc. have been proposed.However, because they do not contain chlorine atoms, they have low solubility and cannot be used alone as a cleaning agent. Agent technology is disclosed. But,
When a combustible solvent is combined, at least one selected from methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, and a mixture thereof, which has a low carbon number of an alkyl group or the like contained in the molecular structure of HFE and a high flash point appearance suppressing effect. It must be one or more compounds. Among the HFEs, at least one compound having a large number of carbon atoms in the alkyl group, for example, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether and a mixture thereof, has a low flash point appearance suppressing effect. When a combustible solvent is combined, there is a problem that a flash point appears.

Further, as a technique of a cleaning agent combining a combustible solvent with at least one compound selected from methyl perfluorobutyl ether, methyl perfluoroisobutyl ether and a mixture thereof, JP-A-10-36894, JP-A-10-36894, These are described in JP-A-10-212498 and JP-A-10-251892. However, the compounding ratio in these specifications is poor in cleaning properties, and cleaning of the flux attached to the electric and electronic parts required to have high cleanliness, for example, when used for pressing or drawing a steel sheet, It may not be used for cleaning oils that are relatively difficult to degrease.

As described above, the cleaning agents proposed so far as substitutes for the CFC 113 have been banned from being used in the future due to the problem of depletion of the ozone layer even if they can be cleaned, and there is a risk of ignition. Due to this, there are many problems in using as a cleaning agent, such as increasing the equipment cost to make the equipment such as the washing machine explosion-proof structure, and the lack of cleaning power as a cleaning agent. Is the current situation.

[0006]

SUMMARY OF THE INVENTION The present invention provides a high detergency against all types of dirt in cleaning,
In addition, the present invention provides a cleaning agent having low toxicity, no flash point and no risk of destruction of the ozone layer, and a cleaning method and a cleaning apparatus suitable for the cleaning agent, while preventing oxidative deterioration at high temperatures such as during steam cleaning. The task is to

[0007]

Means for Achieving the Object In order to achieve the above object, the present inventor has made use of the properties of methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether that do not have a flash point, and has been proposed to provide a cleaning agent having no flash point. As a result of diligent studies to find an agent, it contains (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether, and (b) one or more compounds selected from glycol ethers, and The compounding weight ratio (a) / (b) is 10/90
When it was ~ 49/51, it was found that both excellent detergency and low flammability could be achieved. Further, by adding one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters,
In addition to finding that a higher cleaning effect can be obtained, they have found that they can be used continuously at a high temperature by adding an antioxidant and the like, and have further found a cleaning method and a cleaning apparatus suitable for the cleaning agent, and completed the present invention. .

That is, a first aspect of the present invention comprises (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether, and (b) one or more compounds selected from glycol ethers, and Component (a) and component (b) compounding weight ratio (a) /
(B) is a low-flammable cleaning agent having a ratio of 10/90 to 49/51. A second aspect of the invention is that the (b) glycol ethers contain one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) and (2). The cleaning agent according to item 1.

[0009]

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(Wherein R ¹ and R ³ represent an alkyl group, alkenyl group or cycloalkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen or a methyl group.)

[0011]

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(Wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms;
An alkenyl group or a cycloalkyl group, R ⁵ represents hydrogen or a methyl group. The third aspect of the invention is the cleaning agent according to the first or second aspect of the invention, which comprises (c) one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. The fourth aspect of the invention is that (d) 1.01
The cleaning agent according to any one of the first to third aspects of the invention, which contains an additional component having a boiling point at 3 × 10 ⁵ Pa of 20 ° C. to 100 ° C.

A fifth aspect of the present invention is that (e) contains at least one or more selected from the group consisting of phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants and ultraviolet absorbers. The cleaning agent according to any one of the first to fourth aspects of the present invention. A sixth aspect of the present invention provides a method for cleaning an object to be washed with the cleaning agent according to any one of the first to fifth aspects of the present invention, wherein (f)
A cleaning method characterized by rinsing and / or steam cleaning with a composition containing methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether.

A seventh aspect of the present invention is the cleaning method according to the sixth aspect, which comprises at least one component or compound selected from the group consisting of the composition (f), the additional component (d), and the compound (e). It is. An eighth aspect of the present invention is (A) a washing tank for washing an object to be washed with the detergent according to any one of the first to fifth aspects of the invention, (B) a rinsing tank for rinsing with the composition (f), Composition (f) having no flash point
A steam generation tank for generating steam of at least one component or compound contained in the steam generator, a steam zone for performing steam cleaning with the steam generated from the steam generation tank, (C) condensing the generated steam, A washing device having a water separation tank for removing water from the condensed liquid and a mechanism for returning the condensed liquid from which water has been removed to the rinsing tank (B).

A ninth aspect of the present invention is the eighth cleaning tank of the invention having a heating mechanism for generating a vapor of at least one component or compound constituting the cleaning agent according to any one of the first to fifth aspects of the invention. A), a rinsing tank (B), and (D) a steam zone for steam washing with steam generated from the washing tank (A), a water separation tank (C), and a condensate from which water has been removed. This is a cleaning device having a mechanism for returning to A). A tenth aspect of the present invention is the cleaning apparatus according to the ninth aspect of the present invention, having a mechanism for shower-rinsing the condensate in the vapor zone (D) instead of the rinsing tank (B).

Hereinafter, the present invention will be described in detail. In the present specification, the term "washing" refers to removing dirt adhering to an object to be washed to a level that does not affect the next step. Rinsing refers to replacing a cleaning agent containing a dirt component adhering to an object to be washed with a solvent containing no dirt component.
Further, the steam cleaning is composed of a vapor component condensed on the surface of the object to be washed due to a temperature difference between the object to be washed and the steam to which the object is exposed. It is to remove with a liquid.

(A) Methyl perfluorobutyl ether and / or (a) used in the detergent and composition (f) of the present invention.
Alternatively, methyl perfluoroisobutyl ether is a non-flammable fluorine-containing compound that does not contain a chlorine atom and has a particularly high effect of suppressing the appearance of a flash point. Even in this case, it is possible to improve the detergency while maintaining the flash point appearance suppression effect, which is a characteristic of (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether. Further, (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether has no ozone layer destruction ability,
It has a low global warming potential and is optimal as a detergent component that does not adversely affect the environment.

In the cleaning agent of the present invention, it is necessary to use (b) one or a combination of two or more compounds selected from glycol ethers for the purpose of improving the detergency of any stain. The glycol ethers referred to herein are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms.
A compound in which one or both of the hydrogen atoms of the hydroxyl groups are substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond.

For example, specific examples of glycol ethers include ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl-n-
Propyl ether, ethylene glycol ethyl-n-propyl ether, ethylene glycol di-n-propyl ether, ethylene glycol di-i-propyl ether, ethylene glycol methyl-n-butyl ether,
Ethylene glycol ethyl-n-butyl ether, ethylene glycol-n-propyl-n-butyl ether,
Ethylene glycol di-n-butyl ether, ethylene glycol di-i-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether,
Diethylene glycol methyl-n-propyl ether,
Diethylene glycol ethyl-n-propyl ether,
Diethylene glycol di-n-propyl ether, diethylene glycol di-i-propyl ether, diethylene glycol methyl-n-butyl ether, diethylene glycol ethyl-n-butyl ether, diethylene glycol-n-propyl-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di- i-butyl ether, diethylene glycol di-tert-butyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl-n-propyl ether, triethylene glycol ethyl-n-propyl ether, triethylene glycol Ethylene glycol di-n-propyl ether, triethyl Glycol di-i-propyl ether, triethylene glycol methyl-n-butyl ether, triethylene glycol ethyl-n-butyl ether, triethylene glycol-n-propyl-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene Glycol di-i-butyl ether, triethylene glycol di-tert-butyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol diethyl ether, propylene glycol methyl-n-propyl ether, propylene glycol ethyl-n-propyl ether, propylene Glycol di-
n-propyl ether, propylene glycol di-i-
Propyl ether, propylene glycol methyl-n-
Butyl ether, propylene glycol ethyl-n-butyl ether, propylene glycol-n-propyl-
n-butyl ether, propylene glycol di-n-butyl ether, propylene glycol di-i-butyl ether, propylene glycol di-tert-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl -N-propyl ether, dipropylene glycol ethyl-n-propyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-i-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol ethyl- n-butyl ether, dipropylene glycol-n-propyl-n-butyl ether, dipropylene glycol di- - butyl ether, dipropylene glycol di -i- ether, dipropylene glycol di -tert- butyl ether, tripropylene glycol dimethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl -n-
Propyl ether, tripropylene glycol ethyl-
n-propyl ether, tripropylene glycol di-
n-propyl ether, tripropylene glycol di-
i-propyl ether, tripropylene glycol methyl-n-butyl ether, tripropylene glycol ethyl-n-butyl ether, tripropylene glycol-n-propyl-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol di-i -Butyl ether, tripropylene glycol di-tert-butyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene Glycol mono-i-butyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol mono- -Pentyl ether, ethylene glycol mono-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-i- Butyl ether, diethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-pentyl ether, diethylene glycol mono-n-hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene Glycol mono-i-propyl ether Triethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, triethylene glycol mono-tert-butyl ether, triethylene glycol mono-n-pentyl ether, triethylene glycol mono-n-hexyl ether, propylene glycol monomethyl Ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether, propylene glycol mono-tert-butyl ether, Propylene glycol mono-n-pentyl ether, propylene glycol mono-n-hexyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-i-butyl ether , Dipropylene glycol mono-tert-butyl ether, dipropylene glycol mono-n-pentyl ether, dipropylene glycol mono-n-hexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol mono-n- Propyl ether, tripropylene glycol mono-i-propyl ether, tripropylene glycol mono-n-butyl -Tel, tripropylene glycol mono-i-butyl ether, tripropylene glycol mono-tert-butyl ether, tripropylene glycol mono-n-pentyl ether, tripropylene glycol mono-n-hexyl ether, 3-methoxybutanol, 3-methyl-3 -Methoxybutanol and the like.

Further, when the glycol ether is a compound represented by the following general formula (1), it is possible to achieve both excellent low flammability and excellent solubility of rosin as a flux component. It becomes possible. Further, when the glycol ether is a compound represented by the following general formula (2), more excellent low flammability, an amine hydrochloride or an organic acid which causes an ionic residue, or a white residue It is possible to achieve both excellent removability with respect to polymerized rosin and metal salts of rosin, which are the cause.

[0021]

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(Wherein R ¹ and R ³ represent an alkyl, alkenyl, or cycloalkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen or a methyl group).

[0023]

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(Wherein R ⁴ is an alkyl group having 1 to ⁴ carbon atoms;
An alkenyl group or a cycloalkyl group, R ⁵ represents hydrogen or a methyl group. Specific examples of the glycol ethers represented by the general formula (1) include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, and dipropylene glycol dimethyl ether. Specific examples of the glycol ethers represented by the general formula (2) include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, and diethylene glycol mono-n- Butyl ether, diethylene glycol mono-i-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether And the like.

With respect to the weight ratio of each component, in order to satisfy the high detergency, low toxicity and low flammability characteristics of the detergent of the present invention, the compounding weight ratio of component (a) to component (b) ( a)
/ (B) needs to be 10/90 to 49/51. JP-A-10-212498, JP-A-10-210498
As described in JP-A-251692, the mixing weight ratio of (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether to (a) dipropylene glycol monoisopropyl ether (a) /
(A) a detergent of 70/30, (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether, and (c) a mixture of dipropylene glycol ethyl methyl ether and dipropylene glycol ethyl propyl ether Weight ratio (A) / (C)
However, with a 50/50 detergent, cutting oil, which is relatively easy to clean, can be degreased, but plastic working is used, for example, when pressing a thick steel plate or when performing a drawing process. As for oils and the like, since the burden on processing is greater than in the cutting step, oils having higher viscosity than cutting oils are generally used, and these plastic working oils cannot be sufficiently degreased.

[0026] Regarding the flux, RMA-type flux containing a small amount of activator added to remove oxides on the substrate surface or R-type flux containing no activator is used even with these cleaning agents. It is possible to wash, but when washing RA type flux containing activator such as amine or carboxylic acid halogen salt,
Among the flammable solvents, it is particularly important that the proportion by weight of polar glycol ether is large, and it is not possible to sufficiently wash with the above-mentioned detergent in which the proportion by weight of glycol ether is 50 or less.

Therefore, in order to obtain the effect of improving the dissolving power or dispersing power for all kinds of dirt, it is necessary that the weight ratio of the component (b) glycol ethers is 51 or more. When the weight ratio of the component (b) is 90 or less, low flammability is achieved. The more preferred weight ratio (a) / (b) in consideration of the balance between detergency and low flammability is 1
0/90 to 45/55, and more preferably 10/90.
90 to 40/60.

The detergent in the present invention is a low-flammable detergent containing the above components (a) and (b) at a predetermined ratio. As used herein, “low flammability” refers to JIS K
It means that the cleaning agent is recognized as having no flash point by a general flash point evaluation test such as 2265. The cleaning agent of the present invention is selected from the group consisting of (c) glycol ether acetates and hydroxycarboxylic esters for the purpose of improving the detergency of a wide variety of stains.
More than one compound can be used in combination.

The term "glycol ether acetates" used herein refers to a compound obtained by converting a glycol ether monoalkyl ether having a hydroxyl group into an acetate. The glycol ether monoalkyl ethers referred to here are:
In an aliphatic or alicyclic compound in which two hydroxyl groups are bonded to two different carbon atoms, any one hydrogen atom of the hydroxyl groups is a hydrocarbon residue or a hydrocarbon containing an ether bond. It is a compound substituted with a residue. For example, glycol ether acetates specified by the following general formula (3) can be mentioned.

[0030]

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(Wherein R ⁶ is an alkyl group having 1 to ⁶ carbon atoms;
Alkenyl group or cycloalkyl group, R ⁷ , R ⁸ , R
⁹ is a hydrogen or methyl group, a is an integer of 0 to 1, b is 1 to
Represents an integer of 4. Specific examples of glycol ether acetates include monoalkyl ether acetates corresponding to ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, and 3-methoxy-1.
-Butyl acetate, 3-methoxy-3-methyl-1-
Butyl acetate and the like can be mentioned.

The hydroxycarboxylic acid esters used in the detergent of the present invention are ester compounds having a hydroxyl group, such as lactic acid ester, malic acid ester, tartaric acid ester, citric acid ester, glycol monoester, glycerin monoester. Esters, glycerin diesters, ricinoleic esters, castor oil and the like can be mentioned. Among these, particularly preferred hydroxycarboxylic acid esters include lactic acid esters specified by the following general formula (4).

[0033]

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(In the formula, R ¹⁰ represents an alkyl group, alkenyl group or cycloalkyl group having 1 to 6 carbon atoms.) Specific examples of the lactic acid esters include methyl lactate, ethyl lactate, butyl lactate and pentyl lactate. Can be mentioned. When component (c) is further added, the compounding weight ratio (a) / {(b) + (c)} of component (a) / {component (b) + component (c)} is 10/90. ~ 49/5
More preferably, it is 1. Component {(b) + (c)}
When the weight ratio is 51 or more, a more favorable dissolving power improving effect on various stains is obtained.
More favorable flammability can be achieved. In consideration of the balance between detergency and low flammability, a more preferable compounding weight ratio (a) / {(b) + (c)} is 10/90 to 45/5.
5, more preferably from 10/90 to 40/60.
It is.

The vapor pressures of component (b) and component (c) are set so as to obtain a detergent composition having no flash point.
It is preferably less than 1.33 × 10 ³ Pa at 20 ° C.
It is more preferably 6.66 × 10 ² Pa or less, and further preferably 1.33 × 10 ² Pa or less. The cleaning agent and the composition (f) of the present invention have a boiling point at 1.013 × 10 ⁵ Pa of 20 ° C. to 100 ° C., and the components (a), (b) and component according to claim 1 to 4. Component (d), which is a compound different from (c), is added as an additional component such as a detergency improving agent, a stabilizer, a melting point depressant, etc., to suppress the amounts of components (b) and (c) added and to wash. It is also possible to improve the performance, improve the metal stability in the gas phase during steam cleaning, and prevent solidification of the cleaning agent during cooling.

As the component (d), for example, the following types can be exemplified. Examples of the hydrocarbons include n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, and isooctane And the like. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol and the like.

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, and ethyl propionate. Component (d) has a boiling point of 20 ° C.
100 ° C., and preferably within ± 40 ° C., more preferably ± 40 ° C. of the boiling point of methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether in order to reduce composition fluctuation during use. 30 ° C.

The component (d) is preferably an azeotropic composition with (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether used together or an azeotropic composition having a composition similar thereto. As the component (d), one or more kinds selected from organic compounds having a boiling point at 1.013 × 10 ⁵ Pa of 20 ° C. to 100 ° C. can be used. When the component (d) is added, the blending weight ratio ｛(a) + (b) +
(C) More preferably,｝ / (d) is 90/10 to 99.9 / 0.1. When the weight ratio of (d) is 10 or less, more preferable low flammability can be achieved, and when it is 0.1 or more, more preferable effects as a stabilizer and a melting point depressant can be obtained. More preferred compounding weight ratio ｛(a) +
(B) + (c)｝ / (d) is from 93/7 to 99/1.

The component (e) can be added for the purpose of preventing the cleaning agent and the composition (f) from oxidative deterioration. As the component (e), for example, each type shown below can be exemplified. As phenolic antioxidants,
1-oxy-3-methyl-4-isopropylbenzene,
2,4-dimethyl-6-t-butylphenol, 2,6
-Di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2,
6-di-t-butyl-4-ethylphenol, 2,6-
Di-t-butyl-4-hydroxymethylphenol, triethylene glycol-bis [3- (3-t-butyl-
5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

Examples of the amine antioxidant include compounds such as diphenyl-p-phenylene-diamine, 4-amino-p-diphenylamine, and p, p'-dioctyldiphenylamine. Phosphorous antioxidants include phenylisodecyl phosphite, diphenyldiisooctyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, trisnonyl phenyl phosphite, bis (2,4-di-tbutylphenyl) pentane Compounds such as erythitol diphosphite can be mentioned.

Examples of the sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, Compounds such as distearyl-3,3'-thiodipropionate can be mentioned. 4 as UV absorber
-Hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2,2'-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone , 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-
Benzophenones such as dimethoxybenzophenone, 4-dodecyl-2-hydroxybenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate,
-Octylphenyl salicylate, bisphenol A-
Phenyl salicylates such as di-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-
Benzotriazoles such as (2'-hydroxy-5'-t-octylphenyl) benzotriazole may be mentioned.

Among these exemplified compounds, the effect of adding a phenolic antioxidant is high.
t-Butyl-p-cresol is preferred. In the case of steam cleaning or the like in which the cleaning agent is continuously heated and used, at least one or more selected from the group consisting of a phenolic antioxidant and an amine antioxidant, a phosphorus antioxidant and a phosphorus antioxidant By using at least one member selected from the group above, oxidative decomposition of the cleaning agent can be suppressed for a long time.

When component (e) is added, ｛(a) +
(B) + (c) + (d)}, 1 to 1000 pp
m, more preferably 10 to 1000 ppm. The cleaning agent of the present invention is obtained by mixing and homogenizing the above-described components (a) to (e) according to a standard method. Further, the composition (f)
Is obtained by mixing the above-mentioned components (a) alone or each of the components (a), (d) and (e) according to a standard method and homogenizing them.

In the composition (f), when the component (d) is added to the component (a), the weight ratio of (a) / (d) is in the range of 90/10 to 99.9 / 0.1. More preferably, there is. When the weight ratio of (d) is less than 10, more preferable low flammability can be achieved, and when it is more than 0.1, more favorable effects as a stabilizer and a melting point depressant can be obtained. A more preferable weight ratio range is 93 / 7-9.
9/1. In the case where the component (e) is added to the composition (f), 1 to 100 with respect to {(a) + (d)}.
0 ppm, more preferably 10 to 1000 ppm.

The melting point of the cleaning agent and the composition (f) of the present invention is preferably 15 ° C. or lower, more preferably 10 ° C. or lower in consideration of use in winter, and further preferably 5 ° C.
It is as follows. Further, the cleaning agent of the present invention exhibits excellent cleaning properties against any stains, but is particularly suitable for cleaning resins such as flux. The cleaning agent and the composition (f) of the present invention may optionally contain various auxiliaries, for example, a surfactant, a stabilizer, and an antifoaming agent.

The detergent and composition (f) of the present invention are described below.
Specific examples of various auxiliaries that can be added to the composition are described below. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant may be added. As the anionic surfactants, those having 6 carbon atoms
To 20 fatty acids, alkali metals such as dodecylbenzenesulfonic acid, alkanolamines and amine salts. Examples of the cationic surfactant include a quaternary ammonium salt. Examples of the nonionic surfactant include an alkylphenol, an ethylene oxide adduct of a linear or branched aliphatic alcohol having 8 to 18 carbon atoms, and a block polymer of polyethylene oxide polypropylene oxide. Examples of the amphoteric surfactant include a betaine type and an amino acid type.

Examples of the stabilizer include nitroalkanes such as nitromethane and nitroethane, epoxides such as butylene oxide, ethers such as 1,4-dioxane, amines such as triethanolamine, and benzotriazoles. Self-emulsifying silicones as antifoaming agents
Examples include silicon, fatty acids, higher alcohols, polypropylene glycol polyethylene glycol, and fluorine-based surfactants.

The cleaning agent and the composition (f) of the present invention can be prepared by using the following cleaning method and cleaning apparatus.
The most effective cleaning can be performed. The cleaning method of the present invention removes all types of dirt adhering to an object to be cleaned.
Compound (b) is contained in methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether, and if necessary, compounds (c) and (d) 1.013 ×
By adding an additional component having a boiling point of 20 ° C to 100 ° C at 105 Pa and (e) a phenolic antioxidant, an amine antioxidant, a phosphorus antioxidant, a sulfur antioxidant, and an ultraviolet absorber, After cleaning with a detergent that has excellent detergency and has no flash point,
Rinsing and / or steam cleaning of a dirt component or the like is performed with the composition (f) according to the sixth aspect of the invention or the composition (f) according to the seventh aspect of the invention.

The composition (f) may be any composition as long as it contains the component (a), but the composition can be properly selected as needed. For example, the composition of the detergent component on the surface of the article to be washed can be used. When importance is placed on suppression of residues and stains, a composition composed of only the highly volatile component (a) is preferable.
It is preferable to add an additive having a boiling point at 13 × 105 Pa of 20 ° C. to 100 ° C. Effective cleaning can be performed by combining physical methods such as hand wiping, dipping, spraying, and showering for the purpose of improving cleaning and rinsing properties in the cleaning step and the rinsing step.
The cleaning method of the present invention, which uses the cleaning agent of the present invention, has excellent cleaning properties and drying properties, has little influence on the material of the object to be cleaned, and can be said to be the most suitable cleaning method.

As a device for carrying out the cleaning method of the present invention, a general cleaning device such as a three-tank type cleaning device which has been used for a chlorine-based cleaning agent such as trichloroethane or CFC113 can be used. Although it is possible and does not limit the cleaning device, as a specific example of the cleaning device, the cleaning device according to the eighth embodiment of the present invention shown in FIG.
And the cleaning device according to the ninth aspect of the present invention shown in FIG. 3 and the tenth aspect of the present invention shown in FIG.

Hereinafter, the cleaning method and the cleaning apparatus of the present invention will be described in detail with reference to the accompanying drawings. The cleaning apparatus shown in FIG. 1 has a cleaning tank (A) 1 for storing a cleaning liquid, a rinsing tank (B) 2 for storing a composition (f), a steam generation tank 3, and a vapor of the composition (f) as main components. And a water separation tank (C) 5 for condensing the evaporated composition (f) by the cooling pipe 9 and allowing the condensed liquid and the water adhering to the cooling pipe to stand and separate. In actual cleaning, an 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) 1, the rinsing tank (B) 2, and the steam zone 4.

In the cleaning tank (A) 1, the cleaning agent of the present invention is heated and heated by a heater 7, and the dirt adhering to an object to be cleaned is cleaned by cavitation generated by an ultrasonic vibrator 8 while controlling the temperature to a constant temperature. Remove. At this time, as the physical force, other than the ultrasonic wave, any method used in conventional cleaning machines such as rocking or jetting of a cleaning agent into a liquid may be used. In this cleaning device, the object to be cleaned is stored in a cleaning tank (A).
When the cleaning agent moves from the cleaning tank 1 to the rinsing tank (B) 2, the cleaning agent adheres to the surface of the object to be washed, thereby preventing the dirt component from sticking to the surface of the object to be washed while drying. )
2 can be moved.

In the rinsing tank (B) 2, dirt components dissolved in the cleaning agent adhering to the object to be washed are removed with the composition (f) of the present invention. The composition (f) is provided in a rinsing tank (B) 2
From the steam generation tank 3 through the overflow pipes 11, 16 and 12, and is heated and boiled by the heater 6 of the steam generation tank 3, and a part or the whole of the composition becomes steam and becomes an arrow 1
After being condensed in the cooling pipe 9 as shown in FIG. 3, the water is collected from the pipe 14 into the water separation tank (C) 5 and separated from water, and then returns to the rinsing tank (B) 2 through the pipe 15.

By circulating the composition (f) while changing the state of the composition into a liquid or a gas in the cleaning apparatus, the cleaning component and the dirt component brought into the rinsing tank (B) 2 can be continuously converted into a steam generating tank. 3 and maintain the cleanliness of the rinsing tank (B) 2 and perform steam cleaning in the steam zone 4.
Steam zone 4 filled with steam generated in steam generation tank 3
Is effective as a final cleaning at the end of the cleaning step, since the liquid produced by condensation of the vapor on the surface of the article to be cleaned does not contain any dirt components. Further, in order to enhance the cleaning effect, the cooling pipe 10 of the rinsing tank (B) 2
By keeping the temperature of the composition (f) low and suppressing the temperature of the object to be immersed to be low, it is effective to widen the temperature difference from the steam temperature and increase the amount of condensation.

The cleaning apparatus of the present invention has an independent immersion tank structure for using two kinds of liquids of the cleaning agent and the composition (f), but the space above each tank is commonly used as a vapor zone. By using it, (a) the evaporation loss of (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether from the cleaning agent is suppressed, and as a result, the composition fluctuation of the cleaning agent is reduced, and it is possible to use the cleaning agent for a long time. Become. Next, the cleaning apparatus shown in FIG. 2 has a cleaning tank (A) 17 for storing a cleaning liquid as a main structure, and a composition (f).
A rinsing tank (B) 18 for filling the inside, a vapor zone (D) 19 filled with the vapor of the cleaning agent, and a cooling pipe 23 for evaporating the cleaning agent.
And a water separation tank (C) 20 for statically separating the condensed liquid from the water attached to the cooling pipe. In actual cleaning, the object to be cleaned is put in a dedicated jig or basket, and the inside of the cleaning device is cleaned by a cleaning tank (A) 17 and a rinsing tank (B) 1.
8. The washing is completed while passing through the steam zone (D) 19 in this order. If a high degree of cleanliness such as precision cleaning is required, the number of rinsing tanks may be increased to two or more as necessary.

In the cleaning tank (A) 17, the cleaning agent of the present invention is heated by the heater 21 to wash and remove dirt adhering to the object to be washed in a boiling state. At this time, as the physical force, any method may be used as long as it is a physical force that has been employed in a conventional cleaning machine such as a swing or a jet of a cleaning agent in a liquid.
In the present cleaning apparatus, when the object to be washed is moved from the washing tank (A) 17 to the rinsing tank (B) 18, the detergent component adheres to the surface of the object to be washed, so that the dirt component due to drying on the surface of the object to be washed. It is possible to move to the rinsing tank (B) 18 while preventing the sticking of the water.

The cleaning agent is the heater 2 in the cleaning tank (A) 17.
After heating and boiling at 1, a part or all of the composition turns into steam to fill the steam zone (D) 19 as shown by an arrow 25, is condensed by the cooling pipe 23, and is then separated from the pipe 26 through a water separation tank ( C) After being collected at 20 and separated from the water, it is returned to the rinsing tank (B) 18 through the pipe 27 and then overflows from the rinsing tank (B) 18 and finally flows as indicated by an arrow 28. Is returned to the cleaning tank (A) 17.

As described above, the cleaning apparatus shown in FIG. 2 is different from the cleaning apparatus shown in FIG. 1 in that the cleaning agent and the composition (f) are mixed in the cleaning tank (A) 17. It is preferable that (a) a fluorine-containing compound containing no chlorine atom and (d) an additional component having a boiling point of 20 ° C. to 100 ° C. at 1.013 × 105 Pa contained in the product (f) be the same component. This detergent and (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether contained in the composition (f) and (d) 1.
By circulating additional components having a boiling point of 20 ° C. to 100 ° C. at 013 × 105 Pa in the cleaning device, and allowing a part of the composition in the rinsing bath (B) 18 to overflow into the cleaning bath (A) 17, Steam zone (D) 19
Not only is possible to perform steam cleaning, but also (b) in the cleaning agent brought into the rinsing tank (B) 18 by the object to be washed.
Glycol ethers, (c) glycol ether acetates and hydroxycarboxylic acid esters, and (e) phenolic antioxidants, amine antioxidants,
The phosphorus-based antioxidant, the sulfur-based antioxidant, and the ultraviolet absorber can be continuously returned to the cleaning tank (A) 17, and the cleaning agent in the cleaning tank (A) 17 and the rinsing tank (B)
The composition of composition (f) of No. 18 can be kept constant.

In the steam cleaning performed in the steam zone (D) 19 filled with the steam generated in the cleaning tank (A) 17, dirt components are completely contained in the liquid formed by the condensation of the steam on the surface of the object to be washed. Therefore, it is effective as the final cleaning at the end of the cleaning process. Further, in order to enhance the cleaning effect, the temperature of the composition (f) is kept low by the cooling pipe 24 of the rinsing tank (B) 18 and the temperature of the object to be washed is lowered, thereby reducing the temperature difference from the steam temperature. It is effective to increase the amount of condensation by spreading.

Next, the cleaning apparatus shown in FIG. 3 has a cleaning tank (A) 29 for storing a cleaning liquid, a vapor zone (D) 30 filled with the vapor of the cleaning agent, and a cooling pipe 34 for evaporating the cleaning agent. A water separation tank (C) 31 for standingly separating the condensed and condensed liquid from water adhering to the cooling pipe, and a shower rinse for the condensed liquid that has been left and separated in the water separation tank (C) 31. And a pump 33. In actual cleaning, the object to be cleaned is put in a dedicated jig, basket, or the like, and the cleaning is completed while moving in the cleaning device in the order of the cleaning tank (A) 29 and the steam zone (D) 30.

In the cleaning tank (A) 29, the cleaning agent of the present invention is heated by the heater 32 to wash and remove dirt adhering to the object to be washed in a boiling state. At this time, as the physical force, any method may be used as long as it is a physical force that has been employed in a conventional cleaning machine such as a swing or a jet of a cleaning agent in a liquid. In the vapor zone (D) 30, (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether mainly contained in the cleaning agent of the present invention and (d) a boiling point at 1.013 × 105 Pa of from 20 ° C.
After the vapor of the component having a high vapor pressure such as the added component at 100 ° C. is condensed by the cooling pipe 34 and collected in the water separation tank (C) 31, these condensed liquids are sent to the pipes 38 and 39 by the pump 33 and showered. By washing the object to be washed from the nozzles 40 and 41, dirt components dissolved in the cleaning agent adhering to the object to be washed are rinsed. The condensate is supplied to the water separation tank (C) 31
After being collected into the washing tank (A) 29 from a pipe 37 and a pump 33, it is heated and boiled by a heater 32, converted into steam and condensed by a cooling pipe 34 as indicated by an arrow 35, and then separated into water from a pipe 36. It returns to tank (C) 31.

In the steam washing performed in the steam zone (D) 30 filled with the steam generated in the washing tank (A) 29, the dirt component is not contained in the liquid condensed on the surface of the object to be washed. It is effective as the final finish cleaning. In the cleaning apparatus of the present invention, (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether contained in the cleaning agent and (d) a vapor pressure of 1.013 × 10 5 Pa at a vapor pressure of 20 ° C. to 100 ° C. The high component circulates mainly in the cleaning device while changing its state into a liquid or a gas, so that the dirt component that may be slightly remaining on the object to be washed is removed from the composition (f), and Rinsing and steam cleaning are possible without using the rinsing tank (B).

Each of the cleaning apparatuses shown in FIGS. 1 to 3 can be used properly according to its purpose and application. For precision cleaning or the like requiring high cleanliness, the cleaning tank (A) and the rinsing tank (B) are used. A washing apparatus having one or more tanks is more preferable.

[0064]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples. In addition, various physical properties of the cleaning agent were measured and evaluated as follows. [Examples 1 to 11 and Comparative Examples 1 to 9] (1) Flash point According to JIS K 2265, the flash point was measured by a closed tag type up to a measurement temperature of 80 ° C and an open type Cleveland at a measurement temperature of 81 ° C or more. . The evaluation is based on the following criteria. ○: No flash point ×: Flash point

(2) Global warming potential (100-year integration) The global warming potential is a relative value when the warming potential of carbon dioxide is set to “1” on the basis of carbon dioxide. Evaluate at least 10% by weight of solvent. The evaluation is based on the following criteria. ：: less than 350 ×: 350 or more

(3) Flux solubility test The flux is heated to evaporate a solvent component such as isopropanol to dryness, and then about 0.2 g of pellets are prepared. This was rocked and washed with 5 ml of a detergent at 60 ° C. for 2 minutes (2
00 times / min), and a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Ltd.)
After rinsing with, air blow to dry. The solubility is determined by measuring the weight of the pellet before and after the test and using the following formula. Flux solubility (%) = [(weight before test−weight after test) / weight before test] × 100 Evaluation is based on the following criteria. ：: 40% or more ×: less than 40% Trade name of the flux used in the test: JS-64ND
(Made by Hiroki Corporation)

(4) Degreasing Test A 30-mesh stainless steel mesh (60 × 30 mm) is impregnated with the following metal working oil and heated at 100 ° C. for 30 minutes.
This was shake-washed for 3 minutes with 500 ml of a detergent at 40 ° C. (8
(0 times / min), rinse with a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether (trade name: HFE7100, manufactured by Sumitomo 3M Ltd.), wash with steam with HFE7100, and dry.
The degreasing rate is calculated from the amount of oil adhering before and after washing by the following formula. Metal working oil used for the test: Yushiron Former FH75
00 (trade name, manufactured by Yushiro Chemical Industry Co., Ltd.) Degreasing rate (%) = {(oil content before washing−oil content after washing) / oil content before washing} × 100 The evaluation is based on the following criteria. ◎: 90% or more ○: 80% or more and less than 90% ×: less than 80%

[0068]

Examples 1 to 11 The components shown in Table 1 were mixed to obtain the desired detergent. An evaluation test was performed for each cleaning agent, and the results are summarized in Table 1. The flash point is eliminated by uniformly mixing (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether and (b) a combination of one or more compounds selected from glycol ethers. Thus, excellent detergency against fluxes such as rosin, polymerized rosin, metal salts of rosin, hydrochlorides of amines and organic acids, and metal working oils was confirmed.

Further, it was confirmed that a higher cleaning effect could be obtained by adding together at least one compound selected from (c) glycol ether acetates and hydroxycarboxylic acid esters. (D)
The boiling point at 1.013 × 10 ⁵ Pa is 20 ° C. to 100 ° C.
By adding the component at ° C., the amount of component (b) or component (c) added was suppressed, and excellent cleaning properties were obtained.

[0070]

[Comparative Example 1] The same evaluation test as that of the examples was conducted for the solvents shown in Table 2. The results are summarized in Table 2. The mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether was insufficient in both flux solubility and degreasing properties.

[0071]

Comparative Examples 2 to 4 Each component was mixed with the composition shown in Table 2 to obtain a detergent. The same evaluation test as in the example was performed on this cleaning agent. The results are summarized in Table 2. When using a mixture of ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether instead of (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether as the nonflammable fluorine-based solvent, the cleaning agent has a flash point Was confirmed.

[0072]

Comparative Example 5 Each component was mixed with the composition shown in Table 2 to obtain a detergent. The same evaluation test as in the example was performed on this cleaning agent. The results are summarized in Table 2. When (A) 2H, 3H-perfluoropentane, which is a chain HFC, is used instead of (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether as the nonflammable fluorine-based solvent, the global warming potential is 350. Crossed.

[0073]

Comparative Examples 6 to 9 The components shown in Table 2 were mixed to obtain a detergent. The same evaluation test as in the example was performed on this cleaning agent. The results are summarized in Table 2. (A) The mixture weight ratio (a) / (b) of the mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether and the glycol ether used as the component (b) is 10/9.
Outside the range of 0 to 49/51, the flux solubility and / or degreasing properties were all insufficient.

[Examples 12 to 13 and Comparative Example 10] (5) Cleaning Test 1 for Actual Machine A cleaning agent having a predetermined composition is put in a cleaning tank (A) 1 of a cleaning apparatus shown in FIG. , A predetermined composition (f) is put in the steam generating tank 3 and the water separating tank (C) 5, and the following operation and cleaning are performed for the cleaning property against stains that cause white residue such as polymerized rosin and rosin metal salt. It was measured under the conditions.

Operation ・ Evaluation of flux washability Printed board made of glass epoxy (35 mm × 48 mm)
Is immersed in a flux on one side and air-dried, and the test piece prepared by soldering at 250 ° C. is washed using the above-mentioned washing apparatus, rinsed with the composition (f), steam-washed and dried. Detergency is ionic residue (unit: μg NaCl / sq
in) is measured with an omegameter (600R-SC, manufactured by Alpha Metals), and the measured value is defined as “β”. The evaluation is based on the following criteria. ◎: β ≦ 7 ○: 7 <β ≦ 14 ×: β> 14 Trade name of the flux used in the test: JS-64ND
(Made by Hiroki Corporation)

Evaluation of degreasing and cleaning properties A 30-mesh stainless steel mesh (10 mm × 2 mm) was impregnated with the following metal working oil, and heated at 100 ° C. for 30 minutes. After rinsing with the object (f), steam washing and drying are performed. Detergency is evaluated visually. The evaluation is based on the following criteria. ：: no processing oil remains △: processing oil remains in some parts ×: processing oil remains Metal working oil used in the test: 0.1% by weight of dye (Sudan) in perchlorethylene, Unicut GH35 ( A liquid containing 25% by weight (trade name, manufactured by Nippon Oil Co., Ltd.) was prepared and used as a metal working oil for testing. Cleaning condition Cleaning tank (A) 1: 40 ° C., ultrasonic cleaning for 2 minutes (output: 110 w, frequency: 28 kHz) Rinse tank (B) 2: 15 ° C., immersion rocking for 2 minutes (20 times / minute) Steam zone 4 : Leave for 2 minutes

[0077]

Examples 12 and 13 The components shown in Table 3 were mixed to obtain the desired detergent and composition (f). The above evaluation test was performed using the detergent and the composition (f), and the results are shown in Table 3. Ignition with (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether, (b) a detergent uniformly mixed with a compound selected from glycol ethers, and (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether By washing with composition (f) having no spots, excellent washing against flux and oil was confirmed. In the composition (f), (d) 1.013 × 1
By adding a component having a boiling point of 20 ° C. to 100 ° C. at 05 Pa, the amount of ionic residue was reduced.

[0078]

Comparative Example 10 The same evaluation test as in Examples 12 and 13 was conducted for the cleaning agents and rinsing agents described in Table 3. The results are summarized in Table 3. The mixture of the component (a) methyl perfluorobutyl ether and methyl perfluoroisobutyl ether alone was insufficient in both flux and oil detergency.

[Examples 14 to 15 and Comparative Example 11] (6) Cleaning test 2 for actual machine A cleaning agent having a predetermined composition is put in the cleaning tank (A) 17 of the cleaning apparatus shown in FIG. And a predetermined composition (f) in a water separation tank (C) 20;
In addition, the detergency against stains that cause white residues such as rosin metal salts and the like was measured by the following operation and cleaning conditions. operation

Evaluation of flux washing performance Printed board made of glass epoxy (35 mm x 48 mm)
Is immersed in a flux on one side and air-dried, and the test piece prepared by soldering at 250 ° C. is washed using the above-mentioned washing apparatus, rinsed with the composition (f), steam-washed and dried. Detergency is ionic residue (unit: μg NaCl / sq
in) is measured with an omegameter (600R-SC, manufactured by Alpha Metals), and the measured value is defined as “β”. The evaluation is based on the following criteria. ◎: β ≦ 7 ○: 7 <β ≦ 14 ×: β> 14 Trade name of the flux used in the test: JS-64ND
(Made by Hiroki Corporation)

Evaluation of degreasing cleaning property A 30-mesh stainless steel wire mesh (10 mm × 2 mm) was impregnated with the following metal working oil and heated at 100 ° C. for 30 minutes. After rinsing with the object (f), steam washing and drying are performed. Detergency is evaluated visually. The evaluation is based on the following criteria. ：: no processing oil remains △: processing oil remains in some parts ×: processing oil remains Metal working oil used in the test: 0.1% by weight of dye (Sudan) in perchlorethylene, Unicut GH35 ( A liquid containing 25% by weight (trade name, manufactured by Nippon Oil Co., Ltd.) was prepared and used as a metal working oil for testing.

Cleaning Conditions Cleaning tank (A) 17: Boiling cleaning Rinse tank (B) 18: 15 ° C., immersion rocking for 2 minutes (20
Times / min) Steam zone (D) 19: Let stand for 2 minutes

[0083]

Examples 14 and 15 The components shown in Table 3 were mixed to obtain the desired detergent and composition (f). The above evaluation test was performed using the detergent and the composition (f), and the results are shown in Table 3. (A) a detergent obtained by uniformly mixing a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether and (b) a compound selected from glycol ethers, and (a) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether. By cleaning the composition (f) having no flash point and the vapor and condensate generated by boiling the cleaning agent, excellent cleaning properties against flux and oil were confirmed. Further, in the composition (f),
(D) The boiling point at 1.013 × 105 Pa is from 20 ° C.
By adding the component at 100 ° C., the amount of ionic residue was reduced.

[0084]

Comparative Example 11 Example 1 for the cleaning agents listed in Table 3
The same evaluation tests as in 4 and 15 were performed. The results are summarized in Table 3. The mixture of the component (a) methyl perfluorobutyl ether and methyl perfluoroisobutyl ether alone was insufficient in both flux and oil detergency.

Example 16 and Comparative Example 12 (7) Cleaning test 3 for actual machine A cleaning agent having a predetermined composition was put into the cleaning tank (A) 29 and the water separation tank (C) 31 of the cleaning apparatus shown in FIG. Cleaning tank (A)
Of the components (a), (b), (c) and (e) contained in the cleaning agent of the water separation tank (C) 31 by heating and boiling the cleaning agent by the heater 32 and performing an idle operation for one hour. After reducing the concentration of components having a low vapor pressure in the medium, the detergency against stains that cause white residue such as polymerized rosin and rosin metal salt was measured by the following operation and cleaning conditions.

Operation ・ Evaluation of flux washability Printed board made of glass epoxy (35 mm × 48 mm)
Was immersed in a flux on one side and air-dried, and the test piece prepared by soldering at 250 ° C. was washed with a detergent using the above-described washing device, and rinsed with a condensate generated by boiling the detergent. Wash, steam and dry. Detergency is measured by measuring an ionic residue (unit: μg NaCl / sqin) with an omegameter (600R-SC, manufactured by Alpha Metals), and the measured value is defined as “β”. The evaluation is based on the following criteria. ◎: β ≦ 7 ○: 7 <β ≦ 14 ×: β> 14 Trade name of the flux used in the test: JS-64ND
(Made by Hiroki Corporation)

Evaluation of degreasing cleaning property A 30-mesh stainless steel wire mesh (10 mm × 2 mm) was impregnated with the following metal working oil, and heated at 100 ° C. for 30 minutes to clean a test piece with a cleaning agent using the above-described cleaning apparatus. After rinsing with a condensed liquid generated by boiling the cleaning agent, the cleaning agent is washed with steam and dried. Detergency is evaluated visually. The evaluation is based on the following criteria. ：: no processing oil remains △: processing oil remains in some parts ×: processing oil remains Metal working oil used in the test: 0.1% by weight of dye (Sudan) in perchlorethylene, Unicut GH35 ( A liquid containing 25% by weight (trade name, manufactured by Nippon Oil Co., Ltd.) was prepared and used as a metal working oil for testing.

Cleaning conditions Cleaning tank (A) 17: Boiling cleaning for 2 minutes Steam zone (D) 19: 2 minutes shower rinsing (5 L /
Minutes) and then let stand for 2 minutes

[0089]

Example 16 Each component was mixed according to the composition shown in Table 3 to obtain a desired detergent. The above evaluation test was performed using a cleaning agent, and the results are summarized in Table 3. (A) a mixture of methyl perfluorobutyl ether and methyl perfluoroisobutyl ether, and (b) a detergent uniformly mixed with a compound selected from glycol ethers, and washing with steam and condensate generated by boiling the detergent. As a result, excellent cleaning of flux and oil was confirmed. The component (b) was hardly contained in the vapor and the condensate generated by boiling the cleaning agent, and sufficient rinsing properties were obtained by shower rinsing with the condensate.

[0090]

Comparative Example 12 Using the cleaning agents shown in Table 3, Example 16
The same evaluation test was performed. The results are summarized in Table 3. The mixture of the component (a) methyl perfluorobutyl ether and methyl perfluoroisobutyl ether alone was insufficient in both flux and oil detergency.

[0091]

[Table 1]

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

The cleaning agent of the present invention has excellent detergency and is safe without a flash point. That is, although it does not have a flash point, it has poor solubility in stains such as flux (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether,
(B) When a compound selected from glycol ethers or a combination of two or more compounds is blended and the blending weight ratio (a) / (b) is 10/90 to 49/51, the flash point It has excellent detergency while maintaining the properties of methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether that do not have any.

Further, glycol ether acetates,
By adding one or more compounds selected from the group consisting of hydroxycarboxylic esters, a detergent having more excellent detergency can be provided. Since the cleaning agent does not have a flash point, the danger of ignition is reduced, and there is no need to use an explosion-proof structure to prevent ignition, explosion, etc. in the equipment such as the washing machine, and the existing cleaning equipment can be used as it is. Since it can be used, a low-cost cleaning system can be established.

Further, an antioxidant or 1.013 × 10 ⁵ P
By the additive component having a boiling point of 20 ° C to 100 ° C in a,
Improvement of metal stability and effect of suppressing oxidation deterioration during steam cleaning,
It is possible to prevent solidification of the cleaning agent. ADVANTAGE OF THE INVENTION According to the composition of this invention, all types of dirt can be easily melt | dissolved and wash | cleaned from the to-be-cleaned object surface, without worrying about the danger of ignition.

[Brief description of the drawings]

FIG. 1 is an example of a cleaning apparatus using a cleaning agent and a cleaning method of the present invention.

FIG. 2 is an example of a cleaning apparatus using the cleaning agent and the cleaning method of the present invention.

FIG. 3 is an example of a cleaning apparatus using the cleaning agent and the cleaning method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cleaning tank (A) 2 Rinse tank (B) 3 Steam generation tank 4 Steam zone 5 Water separation tank (C) 6 Heater 7 Heater 8 Ultrasonic transducer 9 Cooling pipe 10 Cooling pipe 11 Overflow pipe 12 Overflow pipe 13 Steam Flow 14 Condensate pipe 15 Condensate pipe after water separation 16 Overflow liquid pipe 17 Wash tank (A) 18 Rinse tank (B) 19 Steam zone (D) 20 Water separation tank (C) 21 Heater 22 Ultrasonic Vibrator 23 Cooling pipe 24 Cooling pipe 25 Steam flow 26 Condensate piping 27 Condensate piping after water separation 28 Composition (f) flow 29 Cleaning tank (A) 30 Steam zone (D) 31 Water separation tank (C) 32 heater 33 pump 34 cooling pipe 35 steam flow 36 condensate pipe 37 condensate pipe after water separation 38 condensate pipe for shower 39 condensate for shower Tube 40 shower nozzle 41 shower nozzle

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 7/28 C11D 7/28 7/32 7/32 7/34 7/34 7/36 7/36 C23G 5/032 C23G 5/032 5/04 5/04 F term (reference) 3B201 AA46 AB01 AB38 AB45 BB04 BB05 BB13 BB21 BB82 BB83 BB92 BB94 BB95 CB15 CC01 CC12 CC21 CD22 4H003 BA12 DA14 DA15 DA16 DB02 DB03 EB03 EB13 EB21 EB21 EB21 ED29 ED30 ED32 FA01 FA15 FA45 4K053 QA05 QA07 RA04 RA41 RA48 RA52 RA57 RA61 SA06 SA09 SA18 TA13 TA17 XA11 XA15 YA05 ZA10

Claims (10)

[Claims] 1. A composition comprising (a) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether and (b) one or more compounds selected from glycol ethers, and the component (a) and the component The blending weight ratio (a) / (b) of (b) is 10/90 to 4
9/51 low flammable detergent. 2. The (b) glycol ethers contain one or more compounds selected from the group consisting of compounds represented by the following general formulas (1) and (2).
The cleaning agent as described. Embedded image (In the formula, R ¹ and R ³ represent an alkyl group, alkenyl group, or cycloalkyl group having 1 to 4 carbon atoms, and R ² represents hydrogen or a methyl group.) (In the formula, R ⁴ represents an alkyl group, alkenyl group, or cycloalkyl group having 1 to ⁴ carbon atoms, and R ⁵ represents hydrogen or a methyl group.) 3. The cleaning agent according to claim 1, further comprising (c) one or more compounds selected from the group consisting of glycol ether acetates and hydroxycarboxylic acid esters. 4. The composition according to claim 1, further comprising (d) an additive having a boiling point at 1.013 × 10 ⁵ Pa of 20 ° C. to 100 ° C.
The cleaning agent according to any one of Items 1 to 3. 5. The method according to claim 1, which further comprises (e) at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, phosphorus antioxidants, sulfur antioxidants and ultraviolet absorbers. The cleaning agent according to any one of Items 1 to 4. 6. After washing an object to be washed with the detergent according to any one of claims 1 to 5, rinsing with a composition containing (f) methyl perfluorobutyl ether and / or methyl perfluoroisobutyl ether. And / or steam cleaning. 7. The cleaning method according to claim 6, wherein the composition (f) contains at least one component or compound selected from the group consisting of the additive component (d) and the compound (e). 8. A washing tank for washing an object to be washed with the cleaning agent according to claim 1, (B) a rinsing tank for rinsing with the composition (f), and ignition. A steam generation tank for generating steam of at least one component or compound contained in the composition (f) having no spot;
A steam zone for steam washing with steam generated from the steam generation tank, (C) a water separation tank for removing water from the obtained condensate after condensing the generated steam, and a water removed. A cleaning device having a mechanism for returning condensed liquid to the rinsing tank (B). 9. The cleaning tank (A) and the rinsing tank according to claim 8, further comprising a heating mechanism for generating a vapor of at least one component or compound constituting the cleaning agent according to claim 1. (B), (D) a steam zone for steam washing with steam generated from the washing tank (A), a water separation tank (C), and a mechanism for returning the condensate from which water has been removed to the washing tank (A). Cleaning device having a. 10. The cleaning apparatus according to claim 9, further comprising a mechanism for shower-rinsing the condensate in the vapor zone (D) instead of the rinsing tank (B).