JP7045854B2 - Cleaning method, how to use the cleaning device and the cleaning device - Google Patents

Description

The present invention relates to a cleaning method, a method of using the cleaning device, and a cleaning device.

In the manufacture of ICs, electronic parts, precision machine parts, optical parts, etc., the parts are washed with a cleaning solvent composition in the manufacturing process, assembly process, final finishing process, etc., and the flux, processing oil, wax adhering to the parts are cleaned. , A mold release agent, dust, etc. are removed.

The cleaning solvent used for such cleaning is nonflammable, has low toxicity, has excellent drying properties and stability, does not attack substrates such as metals, plastics, and elastomers, and has excellent chemical and thermal stability. From 1,1,2-trichloro-1,2,2-trifluoroethan and other chlorofluorocarbons (hereinafter referred to as "CFC"), 2,2-dichloro-1,1,1-trifluoroethane, 1, 1-dichloro-1-fluoroethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane (hereinafter referred to as "HCFC-225ca"), 1,3-dichloro-1,1,2 , 2,3-Pentafluoropropane (hereinafter referred to as "HCFC-225cc") and the like containing hydrochlorofluorocarbons (hereinafter referred to as "HCFC") and the like have been used.

However, since CFCs and HCFCs are chemically extremely stable, they have a long life in the troposphere after vaporization, and diffuse to reach the stratosphere. Therefore, there is a problem that CFCs or HCFCs that have reached the stratosphere are decomposed by ultraviolet rays and generate chlorine radicals to destroy the ozone layer.

On the other hand, perfluorocarbon (hereinafter referred to as "PFC") is known as a solvent that does not have a chlorine atom and does not adversely affect the ozone layer. Further, as alternative solvents for CFCs and HCFCs, hydrofluorocarbons (hereinafter referred to as “HFC”), hydrofluoroethers (hereinafter referred to as “HFE”) and the like have also been developed. However, HFCs and PFCs have a problem of having a large global warming potential.

As a new solvent that has the characteristics of CFC, HCFC, HFC, HFE and PFC that are nonflammable and low in toxicity, but does not adversely affect the ozone layer, has a small global warming potential, and does not adversely affect the global environment. (Z) -1-Chloro-3,3,3-trifluoro-1-propen (CF ₃ CH = CCLH, HCFO-1233zd (Z), hereinafter also referred to as "1233zd (Z)") has been proposed. ..

Patent Document 1 discloses a cleaning agent containing 1233 zd (Z). 1233zd (Z) has excellent properties that it has a short life in the atmosphere because it is easily decomposed, has a small ozone depletion potential and a global warming potential, and has a small impact on the global environment.

Japanese Unexamined Patent Publication No. 2014-181405

The inventors have clarified that when 1233 zd (Z) is used as a solvent that does not adversely affect the global environment, stains may not be sufficiently cleaned. Further, although the inventors have clarified that 1233zd (Z) is inferior in stability because it is easily decomposed, there is a possibility that stains may not be sufficiently cleaned even when a stabilizer is used. The present invention provides a method for cleaning articles, a method for using a cleaning device, and a cleaning device that can sufficiently clean stains when a solvent composition containing 1233 zd (Z) as a solvent, particularly a solvent composition containing a stabilizer is used. With the goal.

As a result of diligent studies to solve the above problems, the present inventors dip the article in a solvent composition containing 1233 zd (Z) and expose it to steam generated from the solvent composition containing 1233 zd (Z). Further, they have found that by using a cleaning tank and a cleaning device having a steam generation tank, stains can be sufficiently cleaned in cleaning a solvent composition article containing 1233 zd (Z) as a solvent, and the present invention has been completed. ..
The present invention provides a cleaning method, a method of using the cleaning device, and a cleaning device having the following configurations.

In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is described in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary. Further, (E) attached to the abbreviation of the compound having a geometric isomer indicates an E form (trans form), and (Z) indicates a Z form (cis form). When the E-form and Z-form are not specified in the name and abbreviation of the compound, the name and abbreviation mean an E-form, a Z-form, and a general term including a mixture of E-form and Z-form.

[1] A dipping step of immersing the article in a solvent composition containing (Z) -1-chloro-3,3,3-trifluoro-1-propene contained in a washing tank.
Steam that generates steam of (Z) -1-chloro-3,3,3-trifluoro-1-propene from the solvent composition contained in the steam generation tank and exposes the article to the generated steam. Has a contact process and
The temperature of the steam generation tank is 5 ° C. or higher higher than the temperature of the washing tank,
The solvent composition comprises the (Z) -1-chloro-3,3,3-trifluoro-1-propene and phenols, ethers, epoxides or pyrroles as stabilizers.
The phenols are selected from the group consisting of phenol, 1,2-benzenediol, 2,6-ditercious butyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol. At least one species,
The ethers are at least one selected from the group consisting of ethylphenyl ether, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether.
The epoxides are at least one selected from the group consisting of 1,2-epoxy-3-phenoxypropane and diethylene glycol diglycidyl ether.
The pyrroles are at least one selected from the group consisting of pyrrole, N-methylpyrrole, and N-ethylpyrrole.
The proportion of the content of the phenols, ethers, epoxides or pyrroles in the solvent composition is 1% by mass to 10% by mass, respectively.
A method for cleaning an article, wherein the ratio of the content of (Z) -1-chloro-3,3,3-trifluoro-1-propene to the total amount of the solvent composition is 80% by mass or more.
[2] The method for cleaning an article according to [1], wherein the temperature of the solvent composition contained in the cleaning tank is less than 35 ° C.
[3] The method for cleaning an article according to [1] or [2], wherein the temperature of the solvent composition contained in the steam generation tank is 35 ° C. or higher.
[4] The method for cleaning an article according to any one of [1] to [3], which cleans the processing oil adhering to the article.
[5] The processing oil is one or more selected from the group consisting of cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press processing oil, punching oil, drawing oil, assembly oil and drawing oil. , [4] The method for cleaning the article.

According to the present invention, a method for cleaning an article and a method for using a cleaning device used for cleaning an article, which does not adversely affect the global environment and uses a solvent composition containing 1233 zd (Z) as a solvent and can sufficiently clean stains. And cleaning equipment can be provided. Further, it is possible to provide a method for cleaning an article that can sufficiently clean dirt, a method for using a cleaning device, and a cleaning device using a solvent composition containing 1233 zd (Z) that does not adversely affect the global environment and further contains a stabilizer.

It is a figure which shows roughly the structure of the cleaning apparatus used in the cleaning method of this embodiment. It is a figure which shows roughly the structure of the other cleaning apparatus used in the cleaning method of this embodiment.

[Washing method]
The cleaning method of the present invention includes a dipping step of immersing an article in a solvent composition containing 1233 zd (Z), generating steam of 1233 zd (Z) from the solvent composition, and exposing the article to the generated vapor. It is characterized by having a steam contact step.

In the cleaning method of the present invention, it is preferable that the dipping step and the steam contact step are performed in that order.
In the cleaning method of the present invention, the dipping step is preferably a step of immersing the article in the solvent composition contained in the cleaning tank, and the steam contact step is generated from the solvent composition contained in the steam generating tank. It is preferably a step of exposing the article to steam.

The cleaning method of the present invention is a method for cleaning deposits adhering to an article to be cleaned (hereinafter, “article to be cleaned”), for example, a cleaning tank containing a solvent composition containing 1233 zd (Z). It can be carried out by using the cleaning device of the present invention described later having a steam generation tank. Hereinafter, an example in which the cleaning device of the present invention is used in the cleaning method of the present invention will be described.

The article to be cleaned is first immersed in a solvent composition containing 1233 zd (Z) in the cleaning tank, and then moved above the steam generation tank. The article to be cleaned is then exposed above the steam generator to steam generated from the solvent composition containing 1233 zd (Z) contained in the steam generator. In the steam generation tank, the article to be cleaned is not immersed in the solvent composition containing 1233 zd (Z). If necessary, a rinsing tank containing a solvent composition containing 1233 zd (Z) is provided between the washing tank and the steam generating tank, and the article to be cleaned after being immersed in the washing tank is further immersed in the solvent composition. It may be immersed.

According to the cleaning method of this example, the article to be cleaned is immersed in the solvent composition containing 1233 zd (Z) in the washing tank, and then the solvent containing 1233 zd (Z) is contained when passing through the steam layer on the steam generation tank. It is washed by exposure to the vapor of the composition. In the above cleaning device, the entire inside of the device is filled with the vapor of the solvent composition containing 1233 zd (Z) up to the position of the cooling pipe. Hereinafter, the solvent composition containing 1233 zd (Z) is also referred to as a solvent composition L. Further, the process of immersing the article to be cleaned in the solvent composition L is also referred to as immersion cleaning, and the process of exposing the solvent composition L to steam is also referred to as steam cleaning.

Then, in the space above the steam generation tank, the steam of the solvent composition L is continuously generated from the steam generation tank, so that the steam flow of the solvent composition L from the steam generation tank toward the washing tank. Seems to have occurred. When the article to be cleaned reaches the space above the steam generation tank, the solvent composition L condenses one after another from the state of steam and becomes liquid on the surface of the article to be cleaned that has been subjected to the flow of the steam. The liquefied solvent composition L is considered to exert a cleaning effect on the surface of the article to be cleaned. Therefore, in the cleaning method of an article using a cleaning tank, a cleaning device having a steam generation tank, and a solvent composition containing 1233 zd (Z), the articles to be cleaned that have been immersed and washed in the cleaning tank remain uncleaned. It is considered that the dirt is reduced in the steam generation tank and washed to a level where there is no practical problem.

In the cleaning method of the present invention, the temperature of the cleaning tank when the article to be cleaned is immersed and washed is preferably less than 35 ° C. Within such a range, the amount of evaporation of the solvent composition L from the washing tank can be suppressed. The temperature of the washing tank means the temperature of the solvent composition L contained in the washing tank. Further, the temperature of the steam generating tank and the temperature of the rinsing tank, which will be described later, also mean the temperature of the solvent composition L contained in the steam generating tank and the rinsing tank, respectively.

The temperature of the washing tank is preferably 20 ° C. or higher and lower than 35 ° C., more preferably 25 ° C. or higher and lower than 34 ° C., and particularly preferably 28 ° C. or higher and lower than 33 ° C. If the temperature of the cleaning tank is too low, the cleaning efficiency may drop. If the temperature of the cleaning tank is higher than the above range, the cleaning efficiency may drop. This is because the amount of steam generated from the washing tank increases, the amount of steam generated from the steam generating tank relatively decreases, and steam is not efficiently supplied in the steam washing performed in the steam zone above the steam generating tank. It is thought that this is the case.

In the cleaning method of the present invention, it is preferable that the temperature of the steam generating tank when the article to be cleaned is steam-cleaned is 35 ° C. or higher. Within such a range, it is possible to perform cleaning with almost no stain left.

The temperature of the steam generation tank is preferably 35 ° C. or higher and lower than 40 ° C., more preferably 36 ° C. or higher and lower than 40 ° C., and particularly preferably 37 ° C. or higher and lower than 40 ° C. If the temperature of the steam generation tank is too low, the amount of steam generated from the steam generation tank decreases, and the steam cleaning performed in the steam zone above the steam generation tank does not efficiently supply steam, resulting in a decrease in cleaning efficiency. If the temperature of the steam generating tank is too high, the amount of steam generated increases, the steam loss increases, and the solvent composition L is likely to be decomposed by heat. In particular, the solvent composition L used in the present invention has low stability, and the composition generated by decomposition and the stabilizer added to suppress the decomposition tend to remain, and the efficiency of steam cleaning performed above the steam generation tank is finally high. It is important to obtain a high degree of cleaning.

In the cleaning method of the present invention, the temperature of the cleaning tank when cleaning the article to be cleaned is preferably less than 35 ° C., the temperature of the steam generating tank is preferably 35 ° C. or higher, and the temperature of the cleaning tank is 34 ° C. It is preferably less than, and the temperature of the steam generating tank is preferably 36 ° C. or higher, and it is particularly preferable that the temperature of the washing tank is less than 33 ° C. and the temperature of the steam generating tank is 37 ° C. or higher. Within this range, cleaning with almost no stain residue is possible.

As for the temperature difference between the washing tank and the steam generating tank, the temperature of the steam generating tank is preferably 5 ° C. or higher, more preferably 7 ° C. or higher, and particularly preferably 8 ° C. or higher. Within this range, cleaning with almost no stain residue is possible.

Examples of the article to be cleaned in the cleaning method of the present invention include processed parts such as metals, ceramics, glass, plastics, and elastomers in the precision machinery industry, the metal processing industry, the optical machinery industry, the electronics industry, the plastic industry, and the like. Specifically, automobile parts such as bumpers, gears, mission parts, radiator parts, printed boards, IC parts, lead frames, motor parts, electronic and electrical parts such as condensers, bearings, gears, gears made by Empra, watch parts, cameras. Parts, precision machine parts such as optical lenses, printing machines, printing machine blades, printing rolls, rolled products, construction machines, glass substrates, large machine parts such as large heavy machine parts, daily life products such as tableware, textile products, etc. Be done.

In the cleaning method of the present invention, the deposits to be cleaned and removed are flux, processing oil, for example, cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, and press processing oil adhering to the various objects to be cleaned. , Punching oil, drawing oil, assembly oil, drawing oil, etc., mold release agent, dust and the like. Since the solvent composition L used in the present invention is superior in solubility of the processing oil as compared with the conventional solvent compositions such as HFC and HFE, it is preferably used for cleaning the processing oil.

Further, the cleaning method of the present invention can be applied to cleaning articles to be cleaned of various materials such as metals, plastics, elastomers, glass, ceramics and composite materials thereof.

<Solvent composition L>
The cleaning method of the present invention, the method of using the cleaning apparatus of the present invention described later, and the solvent composition L used in the cleaning apparatus contain a solvent containing 1233 zd (Z) (hereinafter referred to as "solvent (A)"). do.

1233zd (Z) used in the solvent composition L is a kind of HCFO having a double bond between carbon atoms, has a short life in the atmosphere, and has a small ozone depletion potential and a global warming potential. Further, the boiling point of 1233 zd (Z) is about 40 ° C. (normal pressure), and the drying property is excellent. Further, even if it is boiled to become steam, the temperature is about 40 ° C., so that it is unlikely to have an adverse effect on parts that are easily affected by heat such as resin parts. Further, 1233zd (Z) does not have a flash point, has low surface tension and viscosity, and has excellent performance such as easy evaporation even at room temperature.

The solvent composition L used in the present invention contains the solvent (A). The solvent (A) may be composed of only 1233zd (Z), and the solubility of various substances as solutes may be increased, the volatilization rate may be adjusted, etc., as long as the above characteristics of 1233zd (Z) are not impaired. Depending on the purpose, a solvent other than 1233zd (Z) (hereinafter referred to as "solvent (a1)") may be contained.

The solvent (a1) is not particularly limited as long as it is a solvent soluble in 1233 zd (Z). The solvent soluble in 1233zd (Z) does not cause phase separation or turbidity by stirring at room temperature (25 ° C.) when 1233zd (Z) and the solvent are mixed at an arbitrary mixing ratio. It means a solvent that uniformly dissolves in 1233 zd (Z). The solvent is a substance that is liquid at room temperature (25 ° C). However, the stabilizer (B) in the present invention is excluded.

The content ratio of the solvent (A) in the solvent composition L used in the present invention is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, based on the total amount of the solvent composition L. , 99% by mass or more is particularly preferable. The larger the content ratio of the solvent (A) in the solvent composition L, the more preferable. Therefore, the upper limit of the content ratio of the solvent (A) in the solvent composition L is particularly preferably a value obtained by subtracting the lower limit value of the content ratio of the stabilizer (B) to be used.

The ratio of the content of 1233 zd (Z) to the total amount of the solvent (A), that is, the ratio of the content of 1233 zd (Z) to 100% by mass of the total amount of the total amount of the solvent (Z) and the solvent (a1) is 50% by mass or more. It is preferable that 80% by mass or more is more preferable, 90% by mass or more is further preferable, 95% by mass or more is further preferable, 99% by mass or more is particularly preferable, and 100% by mass is most preferable.

When the ratio of the content of 1233zd (Z) to the total amount of the solvent (A) is at least the above lower limit value, the excellent drying property of 1233zd (Z) is not impaired. The upper limit of the content ratio of 1233 zd (Z) is 100% by mass. When the ratio of the content of the solvent (a1) to the total amount of the solvent (A) is at least the above lower limit value, the effect of the solvent (a1) can be sufficiently obtained. When the ratio of the content of the solvent (a1) to the total amount of the solvent (A) is not more than the above upper limit value, the solvent composition L is excellent in drying property.

The ratio of the content of 1233 zd (Z) to the total amount of the solvent composition L is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 99% by mass or more. ..

Further, when the 1233zd (Z) and the solvent (a1) form an azeotropic composition, it can also be used in the azeotropic composition.

1233zd (Z) is, for example, the method described in paragraphs [0011] to [0012] of JP-A-2012-509324; the method described in JP-A-2015-505302; International Publication No. 2014/175403. The reaction product obtained by the method can be produced by a method of distillation purification or the like.

Specifically, 1,1,3,3-tetrachlorolopropene (HCO-1230za) and / or 1,1,1,3,3-pentachloropropane (HCC-240fa) in the presence or absence of a catalyst. A method of vapor phase fluorination in the presence of a method, or a method of liquid phase fluorination of HCO-1230za, 1,1,2-trichloro-3,3,3-trifluoropropane (233da) is treated with a dechlorinating agent. Method, 243fb is 5 mol relative to the total amount of 1,1-dichloro-3,3,3-trifluoropropane (243fa) and 1,1-dichloro-1,3,3-trifluoropropane (243fb). % Or less of the composition is subjected to a dehydrochlorination reaction or the like to obtain a reaction product containing 1233 zd (Z). The reaction product containing the obtained 1233 zd (Z) can be distilled and purified to produce 1233 zd (Z).

As the solvent (a1), at least one selected from the group consisting of hydrocarbons, alcohols, ketones, esters, chlorocarbons, HFCs and HFEs is preferable.

As the hydrocarbon as the solvent (a1), a hydrocarbon having 5 or more carbon atoms is preferable. As long as it is a hydrocarbon having 5 or more carbon atoms, it may be chain-like or cyclic, and may be a saturated hydrocarbon or an unsaturated hydrocarbon.

Specific examples of the hydrocarbon include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3 -Methyl hexane, 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane , 2-Methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2-methylheptan , 2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, 2-methyl-2-butene, 1-pentene, 2-pentene, 1-hexene , 1-octene, 1-nonen, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, tetralin, amylnaphthalene and the like. Of these, n-pentane, cyclopentane, n-hexane, cyclohexane, and n-heptane are preferable.

As the alcohol as the solvent (a1), an alcohol having 1 to 16 carbon atoms is preferable. Alcohols having 1 to 16 carbon atoms may be chain-like or cyclic, and may be saturated alcohols or unsaturated alcohols.

Specific examples of the alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-. Ethyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl -2-Pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5 5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, Examples thereof include 4-methylcyclohexanol, α-terpineol, 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol and the like. Of these, methanol, ethanol and isopropyl alcohol are preferable.

As the ketone as the solvent (a1), a ketone having 3 to 9 carbon atoms is preferable. A ketone having 3 to 9 carbon atoms may be chain-like or cyclic, and may be a saturated ketone or an unsaturated ketone.

Specifically, as a ketone, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, diisobutyl ketone, mesityl oxide, holon, 2- Examples thereof include octanone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentandione, 2,5-hexanedione, diacetone alcohol, acetophenone and the like. Of these, acetone and methyl ethyl ketone are preferable.

As the ester as the solvent (a1), an ester having 2 to 19 carbon atoms is preferable. As long as it is an ester having 2 to 19 carbon atoms, it may be chain-like or cyclic, and may be a saturated ester or an unsaturated ester.

Specific examples of the ester include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, and pentyl acetate. , Methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyl, butyl butylate, isobutyl isobutyrate , 2-Hydroxy-2-methylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, γ-butyrolactone, diethyl oxalate, dibutyl oxalate, dipentyl oxalate, malonic acid Examples thereof include diethyl, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethyl phthalate, and dibutyl phthalate. Of these, methyl acetate and ethyl acetate are preferable.

As the chlorocarbon as the solvent (a1), chlorocarbon having 1 to 3 carbon atoms is preferable. As long as it is a chlorocarbon having 1 to 3 carbon atoms, it may be chain-like or cyclic, and may be saturated chlorocarbon or unsaturated chlorocarbon.

Specific examples of chlorocarbon include methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2. -Tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, (Z) -1,2-dichloroethylene, (E) -1,2-dichloroethylene, trichlorethylene, tetrachloroethylene and the like can be mentioned. Of these, methylene chloride, (E) -1,2-dichloroethylene and trichlorethylene are preferable.

As the HFC as the solvent (a1), a chain or cyclic HFC having 4 to 8 carbon atoms is preferable, and a solvent contained in the HFC having a fluorine atom number in one molecule of hydrogen atom or more is more preferable.

Specifically, as HFC, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1, 2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3,3 , 4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,4,4,5,5,6,6-tridecafluorooctane, etc. Can be mentioned. Among them, 1,1,1,2,2,3,4,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1 , 1,1,2,2,3,4,4,5,5,6,6-tridecafluorohexane is preferred.

Examples of the HFE as the solvent (a1) include (perfluorobutoxy) methane, (perfluorobutoxy) ethane, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane and the like. Can be mentioned. Of these, (perfluorobutoxy) methane and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane are preferable.

The solvent (a1) contained in the solvent composition L used in the present invention may be one kind or two or more kinds.

The solvent (a1) is preferably a solvent having no flash point. Examples of the solvent (a1) having no flash point include 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3. HFCs such as 4,4-nonafluorohexane, 1,1,1,2,2,3,3,4,5,5,6,6-tridecafluorohexane, and (perfluorobutoxy) methane, 1 , 1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane and the like can be mentioned. When a solvent having a flash point is used as the solvent (a1), it is preferable to mix it with 1223 zd (Z) as long as the solvent composition L used in the present invention does not have a flash point.

In the solvent composition L, the solvent (a1) is (E) -1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd), which is a geometric isomer of 1233 zd (Z). E), hereinafter also referred to as "1233zd (E)") may be contained. 1233zd (E) is a by-product produced together with 1233zd (Z) when the above-mentioned 1233zd (Z) is produced. High purification is required to remove 1233zd (E) from the reaction product containing 1233zd (Z) and 1233zd (E). Therefore, when the solvent composition L contains 1233 zd (E) in the above ratio, advanced purification of 1233 zd (Z) can be omitted, leading to an improvement in productivity. The content ratio of 1233zd (E) is preferably 0.1% by mass or less with respect to the total amount of the solvent (A).

Further, in the solvent composition L used in the present invention, in addition to the solvent (A), at least one stabilizer (B) selected from the group consisting of phenols, ethers, epoxides, pyrroles and nitro compounds is used. It may be added.

(Phenols)
The phenols used as the stabilizer (B) are aromatic hydroxy compounds having one or more hydroxy groups in the aromatic hydrocarbon nuclei. As the phenols, a compound having high solubility in the solvent (A) is preferable. Benzene nuclei are preferable as the aromatic hydrocarbon nuclei. The number of hydroxy groups is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.

In addition to the hydrogen atom, one or more substituents may be bonded to the carbon atom other than the hydroxy group of the aromatic hydrocarbon nucleus. Examples of the substituent include a hydrocarbon group, an alkoxy group, an acyl group, a carbonyl group and the like. Further, one or more hydrogen atoms bonded to the aromatic hydrocarbon nucleus may be substituted with a halogen atom.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aromatic hydrocarbon group and an aralkyl group. Of these, the alkyl group, alkenyl group, alkoxy group, acyl group, and carbonyl group preferably have 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. The aromatic hydrocarbon group preferably has 6 to 10 carbon atoms, and the aralkyl group preferably has 7 to 10 carbon atoms. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is particularly preferable.

When having a substituent, the number thereof is preferably 1 to 5, and more preferably 1 to 3. The position of the substituent is not particularly limited. It is preferable that at least the ortho position is substituted with respect to the hydroxy group of the aromatic hydrocarbon nucleus.

Of these, a compound having a substituted or unsubstituted group, in which the aromatic hydrocarbon nucleus is a benzene nucleus and has 1 to 3 hydroxy groups, is preferable. As the phenol having a substituent, a compound having 1 to 3 substituents having an alkyl group having 1 to 4 carbon atoms and / or an alkoxy group at least in the ortho position with respect to the hydroxy group is preferable. As the alkyl group at the ortho position, a branched alkyl group such as a tertiary butyl group is preferable. When two ortho positions are present, an alkyl group may be present in any of them.

Specific examples of phenols include phenol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, 1,3,5-benzenetriol, and 2,6-ditercious butyl-4-. Methylphenol, 2,4,6-tritershally butylphenol, 2-tersial butylphenol, 3-tersary butylphenol, 4-tersary butylphenol, 2,4-ditersary butylphenol, 2,6-ditersary butylphenol, 4, 6-Different butylphenol, 1-cresol, 2-cresol, 3-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,3 6-trimethylphenol, 2,4,6-trimethylphenol, 2,5,6-trimethylphenol, 3-isopropylphenol, 2-isopropyl-5-methylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxy Examples thereof include phenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-propoxyphenol, 3-propoxyphenol, 4-propoxyphenol, 4-tertiary butyl catechol and α-tocopherol.

Of these, phenol, 1,2-benzenediol, 2,6-ditercious butyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol are preferable.
In the solvent composition L used in the present invention, one kind of phenols may be used as the stabilizer (B), or two or more kinds may be used in combination.

The ratio of the content of phenols in the solvent composition L used in the present invention is preferably 1% by mass to 10% by mass, more preferably 3% by mass to 7% by mass, and further to the total amount of the solvent composition L. It is preferably 5% by mass to 5% by mass.

When the ratio of the content of phenols in the solvent composition L is at least the lower limit of the above preferable range, a sufficient effect for stabilization is exhibited. When the content ratio is not more than the upper limit of the above preferable range, the surface tension and viscosity are low, the permeability is good, and the material easily evaporates even at room temperature.

(Ethers)
The ethers used as the stabilizer (B) are a chain ether in which two hydrocarbon groups are bonded to an oxygen atom and a cyclic ether having an oxygen atom as an atom constituting a ring (however, an epoxy ring which is a three-membered cyclic ether). Except for). Oxygen atoms sandwiched between the carbon atoms in ethers are called etheric oxygen atoms. In the present invention, compounds having both an etheric oxygen atom and an epoxy group are classified as epoxides.

As the ethers used as the stabilizer (B), a compound having high solubility in the solvent (A) is preferable. The number of etheric oxygen atoms in the chain ether and the cyclic ether may be 2 or more. The number of etheric oxygen atoms is preferably 1 to 3. Further, the ethers may be saturated ethers or unsaturated ethers. The number of carbon atoms of the ethers is preferably 2 to 12, more preferably 2 to 8. Further, the hydrocarbon group constituting the ether may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and even if a substituent such as a halogen atom or a hydroxy group is bonded to the carbon atom. good.

Specific examples of the chain ether include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, diallyl ether, ethyl methyl ether, ethylpropyl ether, ethyl isoprol ether, and ethyl isobutyl. Ether, ethyl isopentyl ether, ethyl vinyl ether, allyl ethyl ether, ethyl phenyl ether, ethyl naphthyl ether, ethyl propargyl ether, butyl vinyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether , Ethylene glycol monobenzyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, anisole, methyl anisole, anetol, phenetol, 1,1,1- Examples thereof include trimethoxy ethane, 1,1,2-trimethoxy ethane, 1,1,1-triethoxy ethane, 1,1,2-triethoxy ethane and the like.

The cyclic ether is preferably a 4- to 6-membered cyclic ether, specifically 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, tetrahydrofuran and the like. Can be mentioned.

The ethers used as the stabilizer (B) include ethylphenyl ether, which is a chain ether, ethylene glycol monoethyl ether, and 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane, which are cyclic ethers. , Furan, 2-methylfuran and tetrahydrofuran are preferred.
As the stabilizer (B), one kind of ethers may be used, or two or more kinds may be used in combination.

The ratio of the content of ethers in the solvent composition L used in the present invention is preferably 1% by mass to 10% by mass, more preferably 10% by mass to 7% by mass, and further to the total amount of the solvent composition L. It is preferably 0.01 to 5% by mass.

When the ratio of the content of ethers in the solvent composition L is at least the lower limit of the above preferable range, a sufficient effect for stabilization can be obtained. When the content ratio is not more than the upper limit of the above preferable range, the surface tension and viscosity are low, the permeability is good, and the material easily evaporates even at room temperature.

(Epoxides)
The epoxides used as the stabilizer (B) in the present invention refer to compounds having one or more epoxy groups which are 3-membered cyclic ethers. As the epoxides used as the stabilizer (B), a compound having high solubility in the solvent (A) is preferable. The epoxides may have two or more epoxy groups in one molecule. The number of epoxides contained in the epoxides is preferably 1 to 3. The epoxides may be aliphatic epoxides or aromatic epoxides. The epoxides may have a substituent such as a halogen atom, an etheric oxygen atom, or a hydroxy group. The number of carbon atoms of the epoxides is preferably 12 or less.

Specific examples of the epoxides include 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, methylglycidyl ether, ethylglycidyl ether, butyl glycidyl ether, and vinyl glycidyl ether. Examples thereof include allyl glycidyl ether, diethylene glycol diglycidyl ether, epichlorohydrin, d-limonene oxide and l-limonene oxide.

Of these, 1,2-propylene oxide, 1,2-butylene oxide, butyl glycidyl ether, 1,2-epoxy-3-phenoxypropane and diethylene glycol diglycidyl ether are preferable.
In the solvent composition L used in the present invention, one kind of epoxides may be used as the stabilizer (B), or two or more kinds may be used in combination.

The ratio of the content of epoxides in the solvent composition L is preferably 1% by mass to 10% by mass, more preferably 10% by mass to 7% by mass, and further preferably 0. It is 01 to 5% by mass.

When the ratio of the content of epoxides in the solvent composition L is at least the lower limit of the above preferable range, a sufficient effect for stabilization can be obtained. When the content ratio is not more than the upper limit of the above preferable range, the surface tension and viscosity are low, the permeability is good, and the material easily evaporates even at room temperature.

(Pyrroles)
The pyrroles used as the stabilizer (B) refer to a heterocyclic 5-membered ring compound composed of carbon and nitrogen atoms. As the pyrroles, a compound having high solubility in the solvent (A) is preferable. Further, pyrroles may have a substituent at either a nitrogen atom or a carbon atom. When pyrroles have substituents, the number of substituents is preferably 1-5. As the substituent, an alkyl group having 1 to 3 carbon atoms is preferable.

Specific examples of pyrroles include pyrrole, N-methylpyrrole, N-ethylpyrrole and the like. Of these, pyrrole and N-methylpyrrole are preferable. In the solvent composition L used in the present invention, one kind of pyrroles may be used as the stabilizer (B), or two or more kinds may be used in combination.

The ratio of the content of pyrrols in the solvent composition L used in the present invention is preferably 1% by mass to 10% by mass, more preferably 3% by mass to 7% by mass, and further to the total amount of the solvent composition L. It is preferably 5% by mass to 5% by mass.

When the ratio of the content of pyrroles in the solvent composition L is at least the lower limit of the above preferable range, a sufficient effect for stabilization is exhibited. When the content ratio is not more than the upper limit of the above preferable range, the surface tension and viscosity are low, the permeability is good, and the material easily evaporates even at room temperature.

(Nitro compound)
The nitro compound used as the stabilizer (B) refers to an organic compound in which a nitro group-NO ₂ is bonded to a carbon atom of the organic compound. It is preferable that the nitro compound has solubility in the solvent (A) and is volatile by itself, so that it volatilizes together with the solvent (A) and does not easily remain on the surface of the article during cleaning or the like. From this point of view, as the nitro compound, an aliphatic nitro compound is preferable, and a compound having a boiling point of 100 ° C. to 150 ° C. is preferable.

Specific examples of such a nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, and nitroethylene. From the above viewpoint, nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane. Is more preferable. In the solvent composition L, one kind of nitro compound may be used as the stabilizer (B), or two or more kinds may be used in combination.

The ratio of the content of the nitro compound in the solvent composition L used in the present invention is preferably 1% by mass to 10% by mass, more preferably 0.01 to 7% by mass, and 0. It is more preferably 0.05% by mass to 5% by mass.

When the ratio of the content of the nitro compound in the solvent composition L is at least the lower limit of the above preferable range, a sufficient effect for preventing metal corrosion is exhibited. When the content ratio is not more than the upper limit of the above preferable range, the surface tension and viscosity are low, the permeability is good, and the material easily evaporates even at room temperature.

The solvent composition L used in the present invention can be prepared by weighing and mixing each component of the solvent (A) and the stabilizer (B) arbitrarily added.

[Washing equipment]
The cleaning apparatus of the present invention has a cleaning tank containing a solvent composition containing 1233 zd (Z) for immersing the article, and a steam generating tank for generating steam for exposing the article to steam. Is characterized by accommodating the solvent composition L and generating vapor from the solvent composition L. The cleaning device of the present invention is suitable as the above-mentioned device for cleaning of the present invention.

The cleaning device of the present invention is obtained, for example, by accommodating the solvent composition L in each of the cleaning tank and the steam generating tank of a known multi-tank one-component cleaning device having at least a cleaning tank and a steam generating tank. The multi-tank one-liquid cleaning device is a three-tank one-component cleaning device having three tanks of a cleaning tank, a rinse tank and a steam generating tank, and a two-tank one-liquid cleaning device having two tanks of a cleaning tank and a steam generating tank. Can be roughly divided into. The device can mainly clean electronic and electrical parts, precision machine parts, optical equipment parts and the like.

The cleaning device of the present invention will be described by taking a two-tank type one-component cleaning device as an example with reference to the drawings. However, as will be described later, in the present invention, a three-tank type one-component cleaning device having a rinsing tank may be used.

FIG. 1 is a diagram schematically showing the structure of a two-tank type one-liquid cleaning device 10 which is an example of the cleaning device of the present invention. The two-tank type one-liquid cleaning device 10 shown in FIG. 1 has a cleaning tank 1 and a steam generating tank 3 for containing the solvent composition L, a steam zone 4 filled with steam of the solvent composition L, and an evaporated solvent composition as main structures. It is provided with a cooling pipe 9 for cooling the object L, and a water separation tank 5 for statically separating the liquid of the solvent composition L condensed by the cooling pipe 9 and the water adhering to the cooling pipe. In the actual cleaning, the article D to be cleaned is placed in a dedicated jig, basket, or the like, and the cleaning is completed while moving the inside of the cleaning device 10 in the order of the inside of the cleaning tank 1 and the steam zone 4 above the steam generation tank 3.

A heater 7 and an ultrasonic vibrator 8 are provided in the lower part of the washing tank 1. In the washing tank 1, the solvent composition L is heated and heated by the heater 7, and while controlling to a constant temperature, physical force is applied to the object to be washed D by the cavitation generated by the ultrasonic vibrator 8 to be covered. The dirt adhering to the cleaning article D is washed and removed. At this time, as the physical force, in addition to ultrasonic waves, any method used in conventional washing machines such as rocking and jet of solvent composition L in liquid may be used. In the cleaning of the article D to be cleaned in the cleaning tank 1, ultrasonic vibration is not essential, and cleaning may be performed without ultrasonic vibration if necessary. In the two-tank type one-component cleaning device 10, when the article D to be cleaned is moved from the cleaning tank 1, the component L of the solvent composition adheres to the surface to be cleaned. Therefore, it is possible to move the article D to be cleaned onto the steam generation tank 3 while preventing the stain component from sticking to the surface of the article D to be cleaned due to drying. The cleaning device 10 is designed so that the overflow of the solvent composition L contained in the cleaning tank 1 flows into the steam generation tank 3.

A heater 6 for heating the solvent composition L in the steam generating tank 3 is provided in the lower portion of the steam generating tank 3. The solvent composition L containing the overflow from the washing tank 1 contained in the steam generation tank 3 is heated and boiled by the heater 6, and a part or all of the composition becomes steam in the direction indicated by the arrow 13, that is, It rises above the steam generation tank 3 and a steam zone 4 filled with the steam of the solvent composition L is formed above the steam generation tank 3. The article D to be cleaned, which has been immersed and washed in the washing tank 1, is transferred to the steam zone 4 above the steam generating tank 3 and exposed to the steam of the solvent composition L for steam washing. In the steam cleaning, the component in which the vapor of the solvent composition L is aggregated and liquefied on the surface of the article D to be cleaned cleans the article D to be cleaned. Since the steam of the solvent composition L used in steam cleaning does not contain any stain components, it is effective as a finish cleaning at the end of the cleaning process.

In the cleaning device 10, the space above each tank is commonly used as the steam zone 4. The steam generated from the cleaning tank 1 and the steam generating tank 3 is cooled and condensed by the cooling pipe 9 provided on the upper part of the wall surface of the two-tank type one-component cleaning device 10 to form the solvent composition L from the steam zone 4. Will be recovered. The aggregated solvent composition L is then housed in the water separation tank 5 via a pipe 14 connecting the cooling pipe 9 and the water separation tank 5. In the water separation tank 5, the water mixed in the solvent composition L is separated. The solvent composition L from which water has been separated is returned to the cleaning tank 1 through a pipe 12 connecting the water separation tank 5 and the cleaning tank 1. In the cleaning device 10, such a mechanism makes it possible to suppress the evaporation loss of the solvent composition L.

In this way, by circulating the solvent composition L in the two-tank type one-liquid cleaning device 10 while changing the state to a liquid or gas, the dirt components brought into the cleaning tank 1 are continuously transferred to the steam generation tank 3. It accumulates and enables steam cleaning in the steam zone 4.

In the cleaning device 10, the temperature of the cleaning tank 1 when cleaning the article to be cleaned is preferably less than 35 ° C. Within such a range, the amount of evaporation of the solvent composition L from the washing tank 1 can be suppressed.

The temperature of the washing tank 1 is preferably 20 ° C. or higher and lower than 35 ° C., more preferably 25 ° C. or higher and lower than 34 ° C., and particularly preferably 28 ° C. or higher and lower than 33 ° C. If the temperature of the cleaning tank 1 is too low, the cleaning efficiency may decrease. If the temperature of the cleaning tank 1 is too high, the cleaning efficiency may decrease. As the amount of steam generated from the washing tank 1 increases, the amount of steam generated from the steam generating tank 3 relatively decreases, and steam is efficiently supplied in the steam washing performed in the steam zone 4 above the steam generating tank 3. It is thought that it is not done.

The temperature of the steam generation tank 3 is preferably 35 ° C. or higher. The temperature of the steam generation tank 3 is preferably 35 ° C. or higher and lower than 40 ° C., more preferably 36 ° C. or higher and lower than 40 ° C., and particularly preferably 37 ° C. or higher and lower than 40 ° C. If the temperature of the steam generation tank 3 is too low, the amount of steam generated from the steam generation tank 3 decreases, and the steam is not efficiently supplied in the steam cleaning performed in the steam zone 4 above the steam generation tank 3. Efficiency drops. If the temperature of the steam generation tank 3 is too high, the amount of steam generated increases, the steam loss increases, and the solvent composition L is likely to be decomposed by heat. In particular, the solvent composition L used in the present invention has low stability, and the composition generated by decomposition and the stabilizer added to suppress the decomposition tend to remain, and the efficiency of steam cleaning performed above the steam generation tank 3 is final. It is important to obtain a high degree of cleaning.

In the cleaning device 10, the temperature of the cleaning tank 1 when cleaning the article D to be cleaned is preferably less than 35 ° C., the temperature of the steam generating tank 3 is preferably 35 ° C. or higher, and the temperature of the cleaning tank 1 is 34 ° C. It is preferable that the temperature is less than 36 ° C. and the temperature of the steam generating tank 3 is 36 ° C. or higher, and it is particularly preferable that the temperature of the washing tank 1 is less than 33 ° C. and the temperature of the steam generating tank 3 is 37 ° C. or higher. Within this range, cleaning with almost no stain left is possible.

The temperature difference between the washing tank 1 and the steam generating tank 3 is preferably 5 ° C. or higher, more preferably 7 ° C. or higher, and particularly preferably 8 ° C. or higher. Within this range, cleaning with almost no stain left is possible.

The cleaning device of the present invention can be realized by a two-tank type one-component cleaning device that does not have a rinsing tank 2, but from the viewpoint of enhancing the cleaning effect by the article D to be cleaned, for example, a rinsing tank as shown in FIG. A three-tank type one-component cleaning device 20 having 2 is preferable.

FIG. 2 is a diagram schematically showing a three-tank type one-component cleaning device 20, which is another example of the cleaning device of the present invention. The three-tank type one-component cleaning device 20 is different from the two-tank type one-component cleaning device 10 in that the two-tank type one-component cleaning device 10 shown in FIG. 1 is further provided with a rinse tank 2 for accommodating the solvent composition L. There is. Along with this, the three-tank type one-component cleaning device 20 is designed so that the overflow of the solvent composition L contained in the rinsing tank 2 flows into the cleaning tank 1. The washing tank 1 is provided with a pipe 11 for sending the solvent composition L to the steam generating tank 3 for the purpose of preventing the liquid level from becoming higher than a predetermined height. Further, in the two-tank type one-liquid cleaning device 10, the pipe 12 connects the water separation tank 5 and the cleaning tank 1, whereas in the three-tank type one-liquid cleaning device 20, the pipe 12 is the water separation tank 5 and the rinse tank. The solvent composition L, which connects 2 and is separated from water in the water separation tank 5, is returned to the rinse tank 2 through the pipe 12. Regarding other configurations, the three-tank type one-component cleaning device 20 is the same as the two-tank type one-component cleaning device 10. In the three-tank type one-liquid cleaning device 20, the same reference numerals are given to the configurations having the same functions as the two-tank type one-liquid cleaning device 10, and duplicate description will be omitted.

In the three-tank type one-liquid cleaning device 20, the article D to be cleaned is moved in the order of the cleaning tank 1, the rinsing tank 2, and the steam zone 4 above the steam generation tank 3 to complete the cleaning. In the rinsing tank 2, the article D to be cleaned is immersed in the solvent composition L to remove the dirt component dissolved in the solvent composition L adhering to the article D to be cleaned when it is pulled up from the cleaning tank 1. .. The rinsing tank 2 may have a means for applying a physical force to the article D to be cleaned, similarly to the cleaning tank 1.

Further, in order to enhance the cleaning effect, a cooling device is installed in the rinse tank 2 by using the three-tank type one-component cleaning device 20, whereby the temperature of the solvent composition L in the rinse tank 2 is kept at a low temperature and immersed. By keeping the temperature of the article to be cleaned D low, it is effective to widen the temperature difference from the steam temperature and increase the amount of condensation of the solvent composition L in the article D to be cleaned.

Even when the three-tank type one-liquid cleaning device 20 is used, the temperatures of the cleaning tank 1 and the steam generation tank 3 can be set in the same manner as in the two-tank type one-liquid cleaning device 10. The temperature of the rinsing tank 2 is preferably less than 30 ° C, more preferably less than 20 ° C, and particularly preferably less than 10 ° C. If the temperature of the rinse tank 2 is high, the temperature of the article D to be cleaned does not cool sufficiently, and the temperature difference between the steam temperature and the article D to be cleaned becomes small in the steam cleaning performed in the steam zone 4 above the steam generation tank 3. The cleaning efficiency tends to decrease due to a decrease in the condensed amount of the solvent composition L in the article D to be cleaned.

The solvent composition containing 1233 zd (Z) used in the cleaning apparatus of the present invention is as described above. Further, the articles to be cleaned, the material thereof and the deposits to be cleaned and removed by the cleaning device of the present invention are the same as the articles to be cleaned, the materials thereof and the deposits to be washed and removed in the cleaning method of the present invention.

[How to use the cleaning device]
The method of using the cleaning device of the present invention has a cleaning tank containing the first cleaning liquid and a steam generating tank containing the second cleaning liquid and generating steam from the second cleaning liquid, and the first cleaning liquid has a steam generation tank. A method of using a cleaning device for cleaning an article by immersing the article and exposing the article to steam generated from the second cleaning solution, wherein 1233zd (Z) is used as the first cleaning solution and the second cleaning solution. It is characterized in that a solvent composition containing the solvent composition (solvent composition L) is used.

The method of using the cleaning device of the present invention is applied to, for example, the cleaning device of the present invention. Specifically, the method of using the cleaning device of the present invention is to use the above-mentioned cleaning device of the present invention having a cleaning tank containing the solvent composition L and a steam generating tank, respectively, in the cleaning tank and in the steam generating tank. It is a method of using a cleaning device that cleans the deposits adhering to the articles to be cleaned by moving the articles to be cleaned in the order above.

The article to be cleaned is first immersed in the solvent composition L in the cleaning tank, and then moved above the steam generation tank. The article to be cleaned is then exposed above the steam generator tank to the steam generated from the solvent composition L contained in the steam generator tank. In the steam generation tank, the object to be cleaned is not immersed in the solvent composition L. When a cleaning device provided with a rinsing tank for accommodating the solvent composition L between the cleaning tank and the steam generating tank is used, the article to be cleaned after being immersed in the cleaning tank is immersed in the solvent composition L in the rinsing tank. As a result, further immersion cleaning can be performed.

In the method of using the cleaning device of the present invention, it is preferable that the temperature of the cleaning tank when the article to be cleaned is immersed and washed is less than 35 ° C. Within such a range, the amount of evaporation of the solvent composition L from the washing tank can be suppressed.

The temperature of the washing tank is preferably 20 ° C. or higher and lower than 35 ° C., more preferably 25 ° C. or higher and lower than 34 ° C., and particularly preferably 28 ° C. or higher and lower than 33 ° C. If the temperature of the cleaning tank is too low, the cleaning efficiency may drop. If the temperature of the cleaning tank is higher than the above range, the cleaning efficiency may drop. This is because the amount of steam generated from the washing tank increases, the amount of steam generated from the steam generating tank relatively decreases, and steam is not efficiently supplied in the steam washing performed in the steam zone above the steam generating tank. It is thought that this is the case.

In the method of using the cleaning device of the present invention, it is preferable that the temperature of the steam generating tank when cleaning the article to be cleaned is 35 ° C. or higher. Within such a range, it is possible to perform cleaning with almost no stain left.

The temperature of the steam generation tank is preferably 35 ° C. or higher and lower than 40 ° C., more preferably 36 ° C. or higher and lower than 40 ° C., and particularly preferably 37 ° C. or higher and lower than 40 ° C. If the temperature of the steam generation tank is too low, the amount of steam generated from the steam generation tank will decrease, and the cleaning efficiency will drop due to the inefficient supply of steam in the steam cleaning performed in the steam zone above the steam generation tank. There is. If the temperature of the steam generating tank is too high, the amount of steam generated increases, the steam loss increases, and the solvent composition L is likely to be decomposed by heat. In particular, the solvent composition L used in the present invention has low stability, and the composition generated by decomposition and the stabilizer added to suppress the decomposition tend to remain, and the efficiency of steam cleaning performed above the steam generation tank is finally high. It is important to obtain a high degree of cleaning.

In the cleaning method of the present invention, the temperature of the cleaning tank when cleaning the article to be cleaned is preferably less than 35 ° C., the temperature of the steam generating tank is preferably 35 ° C. or higher, and the temperature of the cleaning tank is 34 ° C. It is preferably less than, and the temperature of the steam generating tank is preferably 36 ° C. or higher, and it is particularly preferable that the temperature of the washing tank is less than 33 ° C. and the temperature of the steam generating tank is 37 ° C. or higher. Within this range, cleaning with almost no stain left is possible.

As for the temperature difference between the washing tank and the steam generating tank, the temperature of the steam generating tank is preferably 5 ° C. or higher, more preferably 7 ° C. or higher, and particularly preferably 8 ° C. or higher. Within this range, cleaning with almost no stain left is possible.

The solvent composition containing 1233 zd (Z) in the method of using the cleaning device of the present invention is as described above. Further, the articles to be cleaned, the material thereof and the deposits to be cleaned and removed, which are the targets of the method of using the cleaning device of the present invention, are the same as the articles to be cleaned, the materials thereof and the deposits to be cleaned and removed in the cleaning method of the present invention. Is.

Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited to these examples.

[Examples 1 to 20]
(Synthesis of 1233zd (Z))
By further distilling and purifying the post-distillation kettle residue obtained by the method of Example 3 of International Publication No. 2014/175403, a composition containing 1233 zd (Z) having a purity of 99.9% by mass (hereinafter referred to as "1233 zd (Z)"). (1) "is obtained. That is, a raw material composition containing HCFC-243fa and HCFC-243fb in the presence of tetra n-butylammonium chloride (TBAC), and HCFC-243fb is 5 mol% or less based on the total of HCFC-243fa and HCFC-243fb. Sodium hydroxide is added to obtain a reaction product containing 1233 zd (Z), which is distilled and purified to obtain 1233 zd (Z) (1). The component of 0.1% by mass other than 1233zd (Z) in 1233zd (Z) (1) is (E) -1-chloro-3,3,3-trifluoro-1-propene (1233zd (E)). Is.

(Preparation of solvent composition L)
Stabilizer (B) is added to 1233 zd (Z) (1) so as to have the mass ratio shown in Table 1 when the solvent composition is prepared, and 50 kg of each of the solvent compositions 1 to 4 is prepared. Further, 50 kg of the solvent composition 5 containing 1233 zd (Z) (1) but not the stabilizer (B) shown in Table 1 is prepared. The mass ratio of the stabilizer (B) shown in Table 1 is the mass ratio to the content of 1233 zd (Z) in the solvent composition.

(Cleaning performance evaluation test with cleaning equipment)
Using the same cleaning device as the three-tank type one-component cleaning device 20 shown in FIG. 2, 50 kg of the solvent compositions 1 to 5 are placed in the cleaning tank 1, the rinse tank 2, and the steam generation tank 3, and the cleaning tank 1 and steam are generated. Adjust each of the tanks 3 to the temperature shown in Table 2 and perform each of the following cleaning tests.

[Washing test A]
After immersing a test piece (25 mm x 30 mm x 2 mm) of stainless steel SUS304 in the product name "Daphne Marg Plus HT-10" (manufactured by Idemitsu Kosan Co., Ltd.), which is a cutting oil, the solvent compositions 1 to 5 are respectively. It is introduced into the charged cleaning device, and is in the order of the solvent composition in the cleaning tank 1, the solvent composition in the rinse tank 2, and the solvent composition in the steam generation tank 3 above the steam generation tank 3. After holding in each tank for 1 minute, take it out and observe the presence or absence of residue such as cutting oil. The detergency is evaluated according to the following criteria.

"S": Almost no dirt such as cutting oil is seen.
"A": Almost no dirt such as cutting oil remains.
"B": A small amount of dirt such as cutting oil remains, but there is no problem in practical use.
"X": Dirt such as cutting oil remains considerably.

[Washing test B]
The test is performed in the same manner as the cleaning test A except that the product name "Daphne Marg Plus AM20" (manufactured by Idemitsu Kosan Co., Ltd.) is used as the cutting oil, and the cleaning property is evaluated based on the same criteria.

[Washing test C]
The test is conducted in the same manner as the cleaning test A except that the product name "Daphne Marg Plus HM25" (manufactured by Idemitsu Kosan Co., Ltd.) is used as the cutting oil, and the cleaning property is evaluated based on the same criteria.

[Washing test D]
The test is carried out in the same manner as the cleaning test A except that the product name "G-6318FK" (manufactured by Nihon Kohsakuyu Co., Ltd.) is used as the cutting oil, and the cleaning property is evaluated according to the same criteria.

The composition of each solvent composition is shown in Table 1, and the temperature conditions and test results of the washing tank 1 and the steam generating tank 3 in each washing test are shown in Table 2. The temperature of the washing tank 1 and the steam generating tank 3 is the same as the temperature of the solvent composition contained in each tank.

From Table 2, Examples 1, 5, 9, and 13 are cleaning methods in which the temperature of the steam generating tank 3 is 5 ° C. or higher higher than the temperature of the washing tank 1 using the solvent composition containing 1233 zd (Z). In the embodiment of the present invention, it can be seen that the cutting oil is sufficiently washed and removed in any of the washing tests, the residue is at a level where there is no practical problem, and a high degree of washing can be obtained.

In the present invention, a method for efficiently obtaining a high degree of cleaning using a solvent composition containing 1233 zd (Z) that does not adversely affect the global environment, a cleaning tank using the solvent composition, and the like. It is possible to provide a method for efficiently obtaining a high degree of cleaning by a cleaning device having a steam generating tank and a method of using the cleaning device using the solvent composition.

1 ... washing tank, 2 ... rinsing tank, 3 ... steam generating tank, 4 ... steam zone, 5 ... water separation tank, 6 ... heater, 7 ... heater, 8 ... ultrasonic transducer, 9 ... cooling pipe, 10 ... two Tank type one-component cleaning device, 20 ... Three-tank type one-component cleaning device, 11, 12, 14 ... Piping, 13 ... Arrow, D ... Article to be cleaned, L ... Solvent composition.

Claims (5)

A dipping step of immersing the article in a solvent composition containing (Z) -1-chloro-3,3,3-trifluoro-1-propene contained in a washing tank.
Steam that generates steam of (Z) -1-chloro-3,3,3-trifluoro-1-propene from the solvent composition contained in the steam generation tank and exposes the article to the generated steam. Has a contact process and
The temperature of the steam generation tank is 5 ° C. or higher higher than the temperature of the washing tank,
The solvent composition comprises the (Z) -1-chloro-3,3,3-trifluoro-1-propene and phenols, ethers, epoxides or pyrroles as stabilizers.
The phenols are selected from the group consisting of phenol, 1,2-benzenediol, 2,6-ditercious butyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol. At least one species,
The ethers are at least one selected from the group consisting of ethylphenyl ether, ethylene glycol monoethyl ether and diethylene glycol monoethyl ether.
The epoxides are at least one selected from the group consisting of 1,2-epoxy-3-phenoxypropane and diethylene glycol diglycidyl ether.
The pyrroles are at least one selected from the group consisting of pyrrole, N-methylpyrrole, and N-ethylpyrrole.
The proportion of the content of the phenols, ethers, epoxides or pyrroles in the solvent composition is 1% by mass to 10% by mass, respectively.
A method for cleaning an article, wherein the ratio of the content of (Z) -1-chloro-3,3,3-trifluoro-1-propene to the total amount of the solvent composition is 80% by mass or more. The method for cleaning an article according to claim 1, wherein the temperature of the solvent composition contained in the cleaning tank is less than 35 ° C. The method for cleaning an article according to claim 1 or 2, wherein the temperature of the solvent composition contained in the steam generation tank is 35 ° C. or higher. The method for cleaning an article according to any one of claims 1 to 3, wherein the processing oil adhering to the article is washed. Claimed that the processing oil is at least one selected from the group consisting of cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press processing oil, punching oil, drawing oil, assembly oil and drawing oil. 4. The method for cleaning an article according to 4.

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