JP2021143332A - Solvent composition, cleaning agent including the solent composition, and method for cleaning article - Google Patents

Abstract

To provide: a solvent composition which exerts no ill effect to the global environment and has excellent cleaning performance; and a method for cleaning articles with the solvent composition.SOLUTION: According to one embodiment, a solvent composition comprises chloro-trifluoropropene and 1,4-dichlorobutane (1,4-DCB). According to one embodiment, a cleaning method comprises a step of contacting the cleaning agent and an article to be cleaned having a lubricant for metal plastic working attached thereto. According to one embodiment, the lubricant for metal plastic working has a kinematic viscosity at 40°C of 50 mm2/s or more.SELECTED DRAWING: Figure 1

Description

The present invention relates to a novel solvent composition and a cleaning agent containing the solvent composition. The present invention also relates to a method for cleaning an article to which a lubricant for metal plastic working is attached.

Many metal parts such as automobile parts, electronic parts, and precision machine parts are manufactured by plastic working such as drawing, drawing, rolling, and forging of metal materials. When plastic working a metal material, the friction generated between the mold and the metal tube or metal plate to be processed is reduced to prevent seizure, and the wear of the mold due to friction is suppressed. , Metal plastic working lubricant is applied. Lubricants for metal plastic processing are made by blending lubricating oil base oils such as mineral oils and synthetic oils with oiliness improvers that reduce friction and wear, and additives such as extreme pressure additives that are useful for preventing seizure. There is.

The metal parts manufactured by plastic working are washed with a cleaning solvent composition in a manufacturing process, an assembly process, a final finishing process, etc., and the metal plastic working lubricant adhering to the metal parts is removed. Generally, when removing a water-insoluble lubricant for metal plastic processing, an organic solvent such as a hydrocarbon solvent, a chlorine solvent, a bromine solvent, or a fluorine solvent is used.

As the fluorine-based solvent, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), which is nonflammable, has low toxicity, and has excellent chemical stability, has been widely used. CFC-113 is designated as an ozone-depleting substance (ODS), and production in developed countries has been completely abolished. Hydrochlorofluorocarbons (HCFCs), which were developed as alternative compounds for CFC-113, also have an adverse effect on the ozone layer, so production was completely abolished in developed countries at the end of 2019.

Hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs) have been developed as solvents that do not adversely affect the ozone layer. HFCs and HFEs are a group of compounds that do not fall under ODS but have a large effect on global warming. In particular, HFCs are regulated substances under the Kyoto Protocol as compounds that have a large effect on global warming. In addition, since HFCs and HFEs hardly dissolve hydrocarbon-based lubricating oil base oils such as mineral oils, they have sufficient performance as cleaning agents used in the cleaning process of articles to which processing oils such as cutting oils are attached. It wasn't.

In recent years, since a fluorine-based solvent having a small impact on the global environment and excellent cleaning performance of processing oils and the like has been desired, the development of chlorofluoroolefins having a double bond and a chlorine atom in the molecule has been developed. It is being advanced. Such chlorofluoroolefins have a short life in the atmosphere due to their high reactivity with OH radicals, and have excellent environmental performance such as extremely low ozone depletion potential (ODP) and global warming potential (GWP). Have.

For example, as chlorofluoroolefins having detergency equivalent to that of HCFC solvents and having excellent environmental performance, cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) ). HCFO-1233zd (Z) alone has a cleaning ability against general hydrocarbon-based processing oils and silicone oils. However, HCFO-1233zd (Z) alone has a low cleaning ability for some sparingly soluble processing oils such as high-viscosity press oils.

Patent Document 1 discloses a degreasing detergent containing an unsaturated chlorinated fluorinated hydrocarbon having 3 carbon atoms as an active ingredient. Patent Document 1 shows that the unsaturated chlorinated fluorinated hydrocarbon has an excellent degreasing effect on a test piece to which spindle oil is attached.

Japanese Unexamined Patent Publication No. 2-221388

However, the spindle oil in Patent Document 1 is a normal lubricating oil composed of mineral oil having a low viscosity and containing no additives. On the other hand, lubricants for metal plastic processing are different from ordinary lubricating oils because they contain additives such as oiliness improvers and extreme pressure additives in lubricating oil base oils such as mineral oils and synthetic oils.

An object of the present invention is to provide a solvent composition having excellent cleaning performance that does not adversely affect the global environment, and a method for cleaning an article using the solvent composition.

The present inventors have conducted diligent studies to solve the above problems. As a result, the solvent composition containing chlorotrifluoropropene and 1,4-dichlorobutane (1,4-DCB) is excellent in being able to dissolve a processing oil that cannot be dissolved by chlorotrifluoropropene alone. The present invention has been completed by finding that it has a cleaning ability.

The present invention includes the following inventions.

[Invention 1]
A solvent composition comprising chlorotrifluoropropene and 1,4-dichlorobutane (1,4-DCB).

[Invention 2]
The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propen (HCFO-1233yd (E)), 2-chloro-3,3,3-trifluoro-1-propen (HCFO-1233xf) , E-1-chloro-trifluoropropene (HCFO-1233zd (E)), E-2-chloro-1,3,3-trifluoropropene (HCFO-1233xe (E)), Z-2-chloro-1 , 3,3-Trifluoropropene (HCFO-1233xe (Z)), E-1-chloro-1,3,3-trifluoropropene (HCFO-1233zb (E)), Z-1-chloro-1,3 , 3-Trifluoropropene (HCFO-1233zb (Z)), 3-Chloro-2,3,3-trifluoropropene (HCFO-1233yf), E-3-chloro-1,3,3-trifluoropropene ( HCFO-1233ze (E)), Z-3-chloro-1,3,3-trifluoropropene (HCFO-1233ze (Z)), E-1-chloro-1,2,3-trifluoropropene (HCFO- 1233yb (E)), Z-1-chloro-1,2,3-trifluoropropene (HCFO-1233yb (Z)), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 3 -Chloro-1,1,2-trifluoropropene (HCFO-1233yc), E-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)), Z-1,2- Dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1-dichloro-2,3 , 3-Trifluoropropene (HCFO-1223ya), E-1,2-dichloro-1,3,3-trifluoropropene (HCFO-1223xb (E)), Z-1,2-dichloro-1,3, 3-Trifluoropropene (HCFO-1223xb (Z)), E-1,3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd (E)), Z-1,3-dichloro-2, 3,3-Trifluoropropene (HCFO-1223yd (Z)), E-2,3-jik Lolo-1,3,3-trifluoropropene (HCFO-1223xe (E)), Z-2,3-dichloro-1,3,3-trifluoropropene (HCFO-1223xe (Z)), E-1, 3-Dichloro-1,3,3-trifluoropropene (HCFO-1223zb (E)), Z-1,3-dichloro-1,3,3-trifluoropropene (HCFO-1223zb (Z)), 1, 1,2-Trichloro-3,3,3-trifluoropropene (CFO-1213xa), 1,1,3-trichloro-2,3,3-trifluoropropene (CFO-1213ya), E-1,2, 3-Trichloro-1,3,3-trifluoropropene (CFO-1213xb (E)), Z-1,2,3-trichloro-1,3,3-trifluoropropene (CFO-1213xb (Z)), E-1,3,3-trichloro-1,2,3-trifluoropropene (CFO-1213yb (E)), Z-1,3,3-trichloro-1,2,3-trifluoropropene (CFO-) The solvent composition according to Invention 1, which is at least one selected from the group consisting of 1213yb (Z)) and 2,3,3-trichloro-1,1,3-trifluoropropene (CFO-1213xc).

[Invention 3]
The solvent composition according to Invention 1, wherein the chlorotrifluoropropene is at least one selected from the HCFO-1233 isomer having a molecular formula of C ₃ HClF _3.

[Invention 4]
The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (E)), which is at least one selected from the solvent composition according to Invention 1.

[Invention 5]
The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), which consists of Z-1-chloro-3,3,3-trifluoropropene and 1,4-dichlorobutane. The solvent composition according to Invention 1, wherein Z-1-chloro-3,3,3-trifluoropropene is 5% by mass or more based on 100% by mass of the total amount.

[Invention 6]
The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (E)), which is at least one selected.
The solvent composition according to Invention 1, wherein 1,4-dichlorobutane is 30% by mass or more and 70% by mass or less with respect to 100% by mass of the total amount of chlorotrifluoropropene and 1,4-dichlorobutane.

[Invention 7]
Invention 1 further comprises at least one solvent selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. The solvent composition according to any one of 6 to 6.

[Invention 8]
An aerosol composition containing the solvent composition according to any one of the inventions 1 to 7 and an injection gas.

[Invention 9]
A cleaning agent containing the solvent composition according to any one of the inventions 1 to 7 or the aerosol composition according to the invention 8.

[Invention 10]
The cleaning agent according to invention 9, wherein the cleaning agent is a cleaning agent for removing stains adhering to an article.

[Invention 11]
The cleaning agent according to invention 9, wherein the cleaning agent is a cleaning agent for removing a lubricant for metal plastic working adhering to an article.

[Invention 12]
The cleaning agent according to invention 11, wherein the article is a metal member.

[Invention 13]
The cleaning agent according to invention 11 or 12, wherein the lubricant for metal plastic working is a water-insoluble lubricant containing a lubricating oil base oil and an oiliness improver.

[Invention 14]
Invention 11 or Invention 12, wherein the lubricant for metal plastic processing is a water-insoluble lubricant containing at least one additive selected from the group consisting of extreme pressure additives, rust preventive additives and antioxidants. The cleaning agent described in.

[Invention 15]
The cleaning agent according to any one of Inventions 11 to 14, wherein the lubricant for metal plastic working has a kinematic viscosity of 50 mm ^{2 / s or more at 40 ° C.}

[Invention 16]
A method for cleaning an article, which comprises a step of bringing the cleaning agent according to the invention 10 into contact with an article to be cleaned to which dirt has adhered.

[Invention 17]
A method for cleaning an article, which comprises a step of bringing the cleaning agent according to any one of the inventions 11 to 15 into contact with an article to be cleaned to which a lubricant for metal plastic working is attached.

According to the present invention, it is possible to provide a solvent composition having excellent cleaning performance that does not adversely affect the global environment, and a method for cleaning an article using the solvent composition.

It is a figure which shows the gas-liquid equilibrium of the solvent composition which concerns on one Embodiment of this invention. It is a figure which shows the temperature (bottom temperature) of the tower bottom at the time of boiling of the solvent composition which concerns on one Embodiment of this invention.

Hereinafter, the present invention will be described in detail, but the present invention should not be construed as being limited to the embodiments shown below and the contents of the examples.

According to one aspect of the present invention, a novel solvent composition containing chlorotrifluoropropene (hereinafter, also referred to as the present solvent composition) is provided. The solvent composition contains chlorotrifluoropropene and 1,4-dichlorobutane (hereinafter, may be referred to as 1,4-DCB). This solvent composition is suitable as a cleaning agent, and is particularly preferably used for removing a metal plastic working lubricant adhering to an article.

Further, according to another aspect of the present invention, there is provided a cleaning method for removing the metal plastic working lubricant adhering to the article. In this cleaning method, the above-mentioned solvent composition is used.

According to yet another aspect of the invention, an aerosol composition is provided. The aerosol composition contains the present solvent composition containing chlorotrifluoropropene and 1,4-DCB.

In this specification, for chlorotrifluoropropene, 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. In the abbreviation, "HCFO-" may be omitted. 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 names and abbreviations of the compounds, the names and abbreviations mean E-forms, Z-forms, and generic names including a mixture of E-forms and Z-forms.

1. 1. Solvent composition The present solvent composition will be described below.

The solvent composition contains chlorotrifluoropropene as the first component. Chlorotrifluoropropene is a propene compound having one carbon-carbon double bond in the molecule, three fluorine atoms, one or more chlorine atoms, and optionally a hydrogen atom. be. Preferably, it is at least one species whose molecular formula is represented by C3HClF3, i.e. monochlorotrifluoropropene (also referred to as HCFO-1233 isomer). Specific examples of chlorotrifluoropropene include Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)) and Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-). 1233yd (Z)), E-1-chloro-2,3,3-trifluoro-1-propen (HCFO-1233yd (E)) 2-chloro-3,3,3-trifluoro-1-propen (HCFO) -1233xf), E-1-chloro-trifluoropropene (HCFO-1233zd (E)), E-2-chloro-1,3,3-trifluoropropene (HCFO-1233xe (E)), Z-2- Chloro-1,3,3-trifluoropropene (HCFO-1233xe (Z)), E-1-chloro-1,3,3-trifluoropropene (HCFO-1233zb (E)), Z-1-chloro- 1,3,3-trifluoropropene (HCFO-1233zb (Z)), 3-chloro-2,3,3-trifluoropropene (HCFO-1233yf), E-3-chloro-1,3,3-tri Fluoropropene (HCFO-1233ze (E)), Z-3-chloro-1,3,3-trifluoropropene (HCFO-1233ze (Z)), E-1-chloro-1,2,3-trifluoropropene (HCFO-1233yb (E)), Z-1-chloro-1,2,3-trifluoropropene (HCFO-1233yb (Z)), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc) ), 3-Chloro-1,1,2-trifluoropropene (HCFO-1233yc), E-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)), Z-1 , 2-Dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1-dichloro- 2,3,3-trifluoropropene (HCFO-1223ya), E-1,2-dichloro-1,3,3-trifluoropropene (HCFO-1223xb (E)), Z-1,2-dichloro-1 , 3,3-Trifluoropropene (HCFO-1223xb (Z)), E-1,3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd (E)), Z-1,3-dichloro -2,3,3-trifluoropropene (HCFO-1223yd (Z)), E-2,3 -Dichloro-1,3,3-trifluoropropene (HCFO-1223xe (E)), Z-2,3-dichloro-1,3,3-trifluoropropene (HCFO-1223xe (Z)), E-1 , 3-Dichloro-1,3,3-trifluoropropene (HCFO-1223zb (E)), Z-1,3-dichloro-1,3,3-trifluoropropene (HCFO-1223zb (Z)), 1 , 1,2-Trichloro-3,3,3-trifluoropropene (CFO-1213xa), 1,1,3-Trichloro-2,3,3-trifluoropropene (CFO-1213ya), E-1,2 , 3-Trichloro-1,3,3-trifluoropropene (CFO-1213xb (E)), Z-1,2,3-Trichloro-1,3,3-trifluoropropene (CFO-1213xb (Z)) , E-1,3,3-trichloro-1,2,3-trifluoropropene (CFO-1213yb (E)), Z-1,3,3-trichloro-1,2,3-trifluoropropene (CFO) It may be at least one selected from the group consisting of -1213yb (Z)) and 2,3,3-trichloro-1,1,3-trifluoropropene (CFO-1213xc), preferably Z-1. -Chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)), E-1-chloro-2, 3,3-Trifluoro-1-propene (HCFO-1233yd (E)) 2-chloro-3,3,3-trifluoro-1-propene (HCFO-1233xf), E-1-chloro-trifluoropropene (HCFO-1233xf) HCFO-1233zd (E)), E-2-chloro-1,3,3-trifluoropropene (HCFO-1233xe (E)), Z-2-chloro-1,3,3-trifluoropropene (HCFO-) 1233xe (Z)), E-1-chloro-1,3,3-trifluoropropene (HCFO-1233zb (E)), Z-1-chloro-1,3,3-trifluoropropene (HCFO-1233zb) Z)), 3-Chloro-2,3,3-trifluoropropene (HCFO-1233yf), E-3-chloro-1,3,3-trifluoropropene (HCFO-1233ze (E)), Z-3 -Chloro-1,3,3-trifluoropropene (HCFO-1233ze (Z)), E-1-chloro-1,2 , 3-Trifluoropropene (HCFO-1233yb (E)), Z-1-chloro-1,2,3-trifluoropropene (HCFO-1233yb (Z)), 2-chloro-1,1,3-tri At least one selected from the group consisting of fluoropropene (HCFO-1233xc) and 3-chloro-1,1,2-trifluoropropene (HCFO-1233yc), and particularly preferably Z-1-chloro-trifluoropropene. (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)) and E-1-chloro-2,3,3-trifluoro At least one selected from the group consisting of -1-propene (HCFO-1233yd (E)).

In this solvent composition, the content of chlorotrifluoropropene is 5% by mass or more and 95% by mass or less with respect to 100% by mass of the total amount of chlorotrifluoropropene and 1,4-DCB which is the second component described later. It may be 30% by mass or more and 70% by mass or less, and 50% by mass or more and 70% by mass or less is particularly preferable. 1,4-DCB is a solvent having a flash point of 53 ° C., but when chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), HCFO-1233zd (Z) and 1 If the content of HCFO-1233zd (Z) is 5% by mass or more with respect to 100% by mass of the total amount of 4-DCB, this solvent composition has no flash point. Further, if the content of chlorotrifluoropropene is 30% by mass or more with respect to 100% by mass of the total amount of chlorotrifluoropropene and 1,4-DCB, this solvent composition has excellent cleaning ability. , Excellent solubility and detergency of lubricant for metal plastic working. In one aspect of the present invention, the content of chlorotrifluoropropene in the solvent composition is preferably 35% by mass or more and 65% by mass or less, and further preferably 35% by mass or more and 55% by mass or less. preferable.

This solvent composition contains 1,4-DCB as a second component together with the above-mentioned chlorotrifluoropropene. As described above, when the chlorotrifluoropropene is HCFO-1233zd (Z), in this solvent composition, HCFO-1233zd ( If the content of Z) is 5% by mass or more, that is, the content of 1,4-DCB is 95% by mass or less, the solvent composition has no flash point. In this solvent composition, the content of 1,4-DCB is preferably 30% by mass or more and 70% by mass or less with respect to 100% by mass of the total amount of chlorotrifluoropropene and 1,4-DCB. When the chlorotrifluoropropene is HCFO-1233zd (Z), the content of 1,4-DCB is 30% by mass or more and 70% by mass based on 100% by mass of the total amount of HCFO-1233zd (Z) and 1,4-DCB. By setting the content in the range of mass% or less, the boiling point of the solvent composition can be raised in the range of about 50 ° C. to about 70 ° C. A solvent that does not have a flash point and exhibits a boiling point region of about 50 ° C to about 70 ° C is one of the preferred embodiments in use at a cleaning work site.

<Other ingredients>
In one aspect of the present invention, the solvent composition may contain other components. Other components include hydrocarbons, alcohols, ketones, ethers, esters, chlorine-based solvents, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), hydrofluoroethers (HFEs). ), Hydrofluorocarbons (HFKs), perfluoroketones (PFKs) and hydrofluoroolefins (HFOs). Examples of hydrocarbons include pentane, hexane, isopentane, n-heptane, cyclopentane, cyclohexane and the like. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and the like. Examples of ketones include acetone, methyl ethyl ketone and the like. Examples of ethers include diethylene glycol monobutyl ether and the like. Examples of the esters include ethyl acetate. Examples of the chlorine-based solvent include methylene chloride, trichloroethane, trichlorethylene, tetrachlorethylene, E-1,2-dichloroethylene and the like. Hydrochlorofluorocarbons (HCFCs) include dichlorofluoroethane, dichlorodifluoroethane, dichlorotrifluoroethane, chlorofluoropropane, chlorodifluoropropane, chlorotrifluoropropane, chlorotetrafluoropropane, dichlorofluoropropane, dichlorodifluoropropane, and dichloro. Examples thereof include trifluoropropane, dichlorotetrafluoropropane, dichloropentafluoropropane, trichlorofluoropropane, trichlorodifluoropropane and trichlorotrifluoropropane. Hydrofluorocarbons (HFCs) include fluoropropane, difluoropropane, trifluoropropane, tetrafluoropropane, pentafluoropropane, hexafluoropropane, heptafluoropropane, fluorobutane, difluorobutane, trifluorobutane, tetrafluorobutane, Pentafluorobutane, hexafluorobutane, heptafluorobutane, octafluorobutane, nonafluorobutane, fluoropentane, difluoropentane, trifluoropentane, tetrafluoropentane, pentafluoropentane, hexafluoropentane, heptafluoropentane, octafluoropentane, Examples thereof include nonafluoropentane, decafluoropentane, and undecafluoropentane. Hydrofluoroethers (HFEs) include heptafluoropropylmethyl ether, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1,1,1,2,2,3,4,5,5,5-deca. Fluoro-3-methoxy-4- (trifluoromethyl) -pentane, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (HFE-347pc-f), 1,1, Examples thereof include 1,3,3,3-hexafluoro-2-methoxypropane (HFE-356 mmz). Hydrofluoroketones (HFKs) include 3,3,4,4-tetrafluoro-2-butanone (HFK-354pc) and 1,1,1,2,2-pentafluoro-3-pentanone (HFK-). 465 mc), 3,3,4,4,5,5,5-heptafluoro-2-pentanone (HFK-447 mcc), 3,4,4,5-tetrafluoro-3- (trifluoromethyl) -2- Butanone (HFK-447mmy), 3,3,4,4,5,5,6,6,6-nonafluoro-2-hexanone (HFK-549mccc), 3,3,4,5,5,5,6 Examples thereof include 6,7,7,7-undecafluoro-2-heptanone (HFK-64-11 mcccc). Examples of perfluoroketones (PFKs) include 1,1,1,2,2,4,5,5,5-nonafluoro-4- (trifluoromethyl) -3-pentanone. Examples of the hydrofluoroolefins are hydrochlorofluoroolefins and hydrofluoroolefins other than chlorotrifluoropropene, and for example, Z-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz). (Z)), E-1-chloro-2,3,3,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc (E)), Z-1-chloro-2,3 3,4,5,4,5-Heptafluoro-1-pentene (HCFO-1437dycc (Z)), Z-1,1,1,2,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz (Z)), E-1,1,1,2,4,5,5,5-nonafluoro-2-pentene (HFO-1429myz (E)), Z-1,1,1 , 3,4,4,5,5,5-nonafluoro-2-pentene (HFO-1429mzy (Z)), E-1,1,1,1,3,4,5,5,5-nonafluoro-2 -Penten (HFO-1429mzy (E)), Z-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)), E-1-chloro-2,3,3,3 -Tetrafluoropropene (HCFO-1224yd (E)), Z-2-chloro-1,3,3,3-tetrafluoropropene (HCFO-1224xe (Z)), E-2-chloro-1,3,3 , 3-Tetrafluoropropene (HCFO-1224xe (E)), methoxyperfluoroheptene and the like. Other than that, other than chlorotrifluoropropene and 1,4-DCB, there is no particular limitation, but for example, raw materials and by-products used in the synthesis process of chlorotrifluoropropene and 1,4-DCB. Examples include, but are not limited to, impurities and stabilizers.

Further, the other components may be water, and in one aspect of the present invention, the content of water in the solvent composition is less than or equal to the saturated water content with respect to the solvent composition (total components excluding water). It may be. In one aspect of the present invention, the water content may cause stains such as watermarks on the surface of the object to be cleaned. Therefore, the smaller the water content in the solvent composition, the better. In one aspect of the present invention, the content of water in the solvent composition is preferably 200 ppm or less by mass ratio, more preferably 100 ppm or less by mass ratio, and particularly preferably 50 ppm or less with respect to the present solvent composition. Further, the other component may be an acid content, but the acid content may adversely affect the article itself or the usage environment of the article depending on the article to be applied and the use of the article. Therefore, the smaller the acid content, the better. In one aspect of the present invention, the content of the acid content in the solvent composition is preferably less than 20 ppm by mass ratio, more preferably 10 ppm or less by mass ratio, and particularly preferably 1 ppm or less with respect to the present solvent composition. .. Further, in one aspect of the present invention, the smaller the content of water and acid in the solvent composition, the more preferable, and it is more preferable that the solvent composition does not contain water and acid. The acid content can be removed by a method such as washing with water, and the water content can be removed by a method such as drying with a desiccant such as molecular sieve.

Since this solvent composition contains chlorotrifluoropropene and 1,4-DCB, it is suitable as a cleaning agent for removing a lubricant for metal plastic working, which was difficult to clean with chlorotrifluoropropene alone. .. Further, when the chlorotrifluoropropene is monochlorotrifluoropropene (HCFO-1233 isomer), the monochlorotrifluoropropene has a low boiling point (for example, HCFO-1233zd (Z) has a boiling point of 39 ° C. and has a boiling point of HCFO-1233xf. The boiling point is 15 ° C.), and in the dipping cleaning and steam cleaning steps, dirt components such as a lubricant for metal plastic processing adhering to the article to be cleaned can be heated only to the boiling point of monochlorotrifluoropropene. Therefore, it has been a problem that the viscosity of the dirt component cannot be sufficiently lowered and the cleaning cannot be completed. Further, since HCFO-1233zd (Z) alone has high volatility, there is a problem that a large amount of evaporation loss occurs when it is used in an open cleaning facility. Further, since 1,4-DCB has a boiling point of 155 ° C., it has poor drying property and has a flash point, so that it needs to be handled with care. However, the solvent composition obtained by mixing monochlorotrifluoropropene and 1,4-DCB has an appropriate boiling point () for cleaning dirt components such as lubricants for metal plastic working attached to the article to be cleaned. It has about 40 ° C to about 80 ° C). Therefore, this solvent composition has a higher cleaning ability than monochlorotrifluoropropene alone while having an appropriate drying property, and can further reduce evaporation loss during use. When the chlorotrifluoropropene is HCFO-1233zd (Z), HCFO-1233zd (Z) is based on 100% by mass of the total amount of HCFO-1233zd (Z) and 1,4-DCB in the solvent composition. If the content of the solvent composition is 5% by mass or more, the solvent composition does not have a flash point. Therefore, the safety of this solvent composition is improved and it is easy to handle.

2. Lubricant for metal plastic working The following describes the lubricant for metal plastic working.

<Lubricant for metal plastic working>
In the present specification, the lubricant for metal plastic working is a tool that reduces friction between a metal material and a tool in plastic working such as rolling, extrusion, drawing, forging, shearing, drawing, and bending of a metal material. It is a lubricant used to prevent wear and seizure. The lubricant for metal plastic processing contains at least an oiliness improver together with a lubricating oil base oil such as mineral oil and synthetic oil. Further, the lubricant for metal plastic processing may further contain a processing oil additive such as an extreme pressure additive, a rust preventive additive, and an antioxidant, and in addition, a solid lubricant, an anticorrosive agent, and a colorant. , Antifoaming agents, fragrances and other known additives may be included. Further, the lubricant for metal plastic working may be water-insoluble or water-soluble, but is preferably water-insoluble. The type of lubricant for metal plastic working is not particularly limited, but it may be referred to as rolling oil, extrusion oil, drawing oil, punching oil, drawing oil, forging oil, press working oil, or the like.

<Lubricating oil base oil>
In the present specification, the lubricating oil base oil is a substance that uniformly and stably dissolves additives such as an oiliness improver and sends them to a place necessary for lubrication. As the lubricating oil base oil, a lubricating oil base oil known in metal plastic working can be adopted. In one aspect of the present invention, examples of the lubricating oil base oil include mineral oils or synthetic oils such as polybutenes, α-olefin oligomers, alkylbenzenes, polyethylene glycols, and polyol esters, which are used in mixtures. You may. Further, in one aspect of the present invention, the lubricating oil base oil is preferably a hydrocarbon-based base oil (hydrogen-based mineral oil or synthetic oil), and particularly preferably a hydrocarbon-based mineral oil. Since the lubricating oil base oil does not have a strong polar group and has poor lubricity, it cannot be used alone as a lubricant in metal plastic working. Therefore, it is used as a lubricant together with at least an oiliness improver.

<Oil improver>
In the present specification, the oiliness improver is a compound that is sent to a metal friction surface requiring lubrication by a lubricating oil base oil and is adsorbed to exert a lubricating effect. Examples of the oiliness improver include fats and oils such as rapeseed oil, palm oil and lard, higher fatty acids such as lauric acid, oleic acid and stearic acid, higher aliphatic alcohols such as lauryl alcohol and oleyl alcohol, methyl oleate and stearic acid. Higher fatty acid esters such as acid butyl ester, higher aliphatic amines such as stearylamine, magnesium stearate, calcium stearate, zinc stearate, barium stearate, aluminum stearate, lithium stearate, zinc laurate, barium laurate, etc. Metal soap, etc. can be mentioned. The oiliness improver is a long-chain compound with a large molecular weight and has a strong polar group at one end of the molecule, and the polar group strongly adsorbs and arranges it on the metal surface to form an adsorption film and adsorb. It exerts a strong lubricating effect due to the mutual attraction between the long molecular chains in which the membranes are arranged.

<Extreme pressure additive>
In the present specification, the extreme pressure additive is sent to the metal friction surface requiring lubrication by the lubricating oil base oil, and the contact region between the work material and the tool increases to become a high temperature and high pressure extreme pressure state. It is a compound that sometimes chemically reacts with metal to form a film on the surface of the metal, reducing wear, preventing seizure, and improving the seizure resistance of the lubricant. Examples of the extreme pressure additive include sulfur compounds such as isobutene sulfide, dibenzyldisulfide and sulfide oils and fats, phosphorus compounds such as tributyl phosphate and tricresyl phosphate, and chlorinated compounds such as chlorinated paraffin. be able to. In metal processing generally called difficult processing, which involves a particularly high processing pressure and high frictional heat, a lubricant for metal plastic working containing a sulfur-based extreme pressure agent is often used.

<Rust preventive additive>
In the present specification, the rust preventive additive is a compound that is sent to a metal surface by a lubricating oil base oil, adsorbs to the metal surface, and prevents contact with a corrosive substance such as water. Examples of the rust preventive additive include sulfonates, carboxylates, amine salts, and the like.

<Antioxidant>
In the present specification, the antioxidant is a compound that is uniformly dissolved in a lubricating oil base oil and prevents oxidative deterioration of components contained in a lubricant for metal plastic working. Examples of the antioxidant include phenolic compounds such as 2,6-di-tert-butyl-p-cresol, amine compounds such as styrenated diphenylamine, and the like.

3. 3. Method for cleaning articles to which a lubricant for metal plastic working has adhered The method for cleaning articles to which a lubricant for metal plastic working has adhered will be described below.

The method for cleaning an article using this solvent composition is not particularly limited except that the solvent composition is used as a cleaning agent for an article to which a lubricant for metal plastic working is attached. In one aspect of the present invention, the metal plastic working lubricant is removed from the article by bringing the solvent composition into contact with an article to which the metal plastic working lubricant is attached by a method well known in the art. be able to. For example, hand-wiping cleaning, immersion cleaning, spray cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, boiling cleaning, steam cleaning, and a method combining these can be adopted, but the method is not limited thereto.

In one aspect of the present invention, metal plastic processing with high viscosity (for example, the kinematic viscosity at 40 ° C. is 50 mm ² / s or more, preferably the kinematic viscosity at 40 ° C. is 50 mm ² / s or more and 500 mm ² / s or less). When cleaning the article to which the lubricant is attached, boiling cleaning by immersing the article in the boiled solvent composition and immersion ultrasonic cleaning by irradiating low frequency ultrasonic waves of 26 kHz to 40 kHz are effective. be. In addition, when cleaning articles by combining immersion cleaning, boiling cleaning, immersion ultrasonic cleaning, immersion rinse cleaning, shower rinse cleaning, steam cleaning, etc., cleaning that is compatible with fluorine-based solvents, chlorine-based solvents, and bromine-based solvents. It is desirable to fill the machine with this solvent composition before use.

In one aspect of the present invention, after cleaning the article using the solvent composition by the method as described above, rinse cleaning and / or steam cleaning may be performed. When rinsing and / or steam cleaning is performed, for example, HCFO-1233zd (Z) may be used as the rinsing agent used in the rinsing cleaning and the solvent used in the steam cleaning, but the present invention is not limited thereto. Instead, known rinsing agents and solvents used for steam cleaning can be used. The rinsing wash may be, but is not limited to, a dip rinsing wash and / or a shower rinsing wash. The pressure of steam washing is not particularly limited, but it may be carried out under atmospheric pressure or under reduced pressure. The article may be vacuum dried after rinsing and / or steam cleaning.

In the uniform state of the present invention, the method of using the solvent composition to clean an article to which a stain component such as a lubricant for metal plastic processing is attached is a first step of cleaning an article using the solvent composition. The second step of rinsing the article and the third step of steam cleaning the article are included. The cleaning in the first step may be a dipping cleaning in which the article is immersed in the solvent composition. The immersion cleaning may be a boiling cleaning in which the solvent composition is heated and boiled, or an ultrasonic immersion cleaning in which an ultrasonic wave is irradiated. The cleaning may be a hand-wiping cleaning in which the solvent composition is impregnated into a waste cloth or the like and the surface is wiped off instead of the immersion cleaning. After spraying the composition, it may be washed by hand with a waste cloth or the like. Further, the rinse cleaning in the second step may be an immersion rinse cleaning, an ultrasonic immersion rinse cleaning irradiated with ultrasonic waves, or a shower rinse cleaning. In the uniform state of the present invention, the method of cleaning an article using the solvent composition may include at least the first step and may be a cleaning method of only the first step and the second step (the third step is omitted). , Or the cleaning method of only the first step and the third step (the second step is omitted), or only the first step (the second step and the third step are omitted). In the uniform of the present invention, the solvent composition is used only in the first step, and chlorotrifluoropropene alone (for example, monochlorotrifluoropropene such as HCFO-1233zd (Z)) in the second and / or third steps. May be used, but the present invention is not limited to this.

<Article>
This solvent composition is suitably used as a cleaning agent in a cleaning step of an article for removing the metal plastic working lubricant from an article to which the metal plastic working lubricant is attached. The article to which the lubricant for metal plastic working, which is the object to be cleaned, is attached is composed of a metal member. Here, examples of the metal include, but are not limited to, carbon steel, stainless steel, titanium, titanium alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, chromium molybdenum steel, and the like.

Articles to be cleaned are made of metal or a composite material of metal and resin, such as bodies, brake parts, suspensions, wheels, and other vehicles, aircraft, railroad vehicles, ships, and other vehicle parts and control devices. And so on. In particular, when assembling and manufacturing various vehicles and transportation facilities, when resin or paint is applied to metal and processed, if a small amount of oil or the like remains on the metal surface, the resin or paint will be stable. The quality of the product may be significantly deteriorated due to peeling or deterioration without adhering. In addition, parts and devices that are particularly important for ensuring safety during operation, such as brakes, suspensions, and wheels, have a reduced coefficient of friction if even a small amount of oil adheres to them, and if they are assembled as they are, braking performance will be impaired. , The desired performance cannot be stably exhibited. Therefore, when assembling and manufacturing various vehicles and transportation means, it is necessary to thoroughly clean and remove the oil slightly adhering to the metal surface of each part in advance.

In a preferred embodiment of the present invention, an article to which the metal plastic working lubricant is attached is washed with the solvent composition, and then the article is dried to remove the metal plastic working lubricant. Can be obtained.

The method for drying the article, that is, the method for removing the solvent composition from the article is not particularly limited, and those skilled in the art can appropriately adopt a conventionally known method. For example, a method of volatilizing a component such as a solvent by leaving it at room temperature or under heating can be mentioned, but the present invention is not limited to this.

The removed solvent composition may be recovered and can be reused as the solvent composition. Alternatively, it can be reused for other purposes. The recovered solvent composition may be purified and then reused.

4. Aerosol composition Hereinafter, the aerosol composition will be described.

<Injection gas>
The aerosol composition contains the present solvent composition containing chlorotrifluoropropene and 1,4-DCB, and an injection gas. As the injection gas, liquefied gas or compressed gas can be used. For example, liquefied petroleum gas (LPG), dimethyl ether (DME), nitrogen, carbon dioxide, compressed air, argon, fluorine-based gas and the like can be mentioned. These may be used alone or in a mixture of two or more. Examples of the fluorogas include difluoromethane (HFC-32), 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1. 2,2-Pentafluoroethane (HFC-125), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea) , E-1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), 2,3,3,3-tetrafluoropropene (HFO-1234yf) and the like, but are not limited thereto. Among fluorogas, difluoromethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 1 , 1,1,2,3,3,3-heptafluoropropane, E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene are preferable, and the global warming potential ( E-1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, E-1,3,3,3-tetrafluoropropene because GWP) is small and toxicity is low. And 2,3,3,3-tetrafluoropropene are particularly preferred. Then, the solvent composition of the present invention and the above-mentioned propellant gas can be mixed to obtain an aerosol composition, which can be filled in a pressure-resistant can and provided.

<How to use the aerosol composition>
An aerosol composition obtained by mixing the solvent composition with a liquefied gas as an injection gas can be filled in a pressure-resistant can and used. In addition, the solvent composition can be put into a pail, a mobile small filling machine can be installed in the workplace where it is used, and the solvent composition put in the pail can be aerosolized with compressed air before use. Such an aerosol composition can be used as an aerosol by spraying it on a member made of various materials such as a metal, a resin and an elastomer to be cleaned.

The solvent composition and the aerosol composition can be used for degreasing cleaning, flux cleaning, precision cleaning, drain cleaning, rinsing cleaning, in addition to the above-mentioned cleaning agents for cleaning articles to which the metal plastic processing lubricant is attached. It is preferably used as a cleaning agent for dry cleaning and the like. That is, in addition to the lubricant for metal plastic processing, the stains adhering to the article include grease, processing oil, silicone oil, rust preventive oil, flux, wax, ink, mineral oil, mold release agent containing silicone oil, pitch, etc. Oils and fats such as asphalt, dust, etc. may be used. Examples of the processing oil include cutting oil, grinding oil, quenching oil, lubricating oil, machine oil, and assembly oil. The solvent composition and the aerosol composition are also suitably used as a cleaning agent for cleaning articles with such stains. In this case, the article may be an optical component, a medical instrument, an electric device, a precision machine, a textile product, or a component thereof, in addition to the above-mentioned article. Specific examples of electrical equipment, precision machinery, optical articles and their parts include ICs, capacitors, printed circuit boards, micromotors, relays, bearings, optical lenses, glass substrates and the like. Examples of the material to which the solvent composition and the aerosol composition are applicable include metals, plastics, elastomers, glass, ceramics, fibers and composite materials thereof. Among these, metals such as iron, copper, nickel, gold, silver and platinum, metal sintered bodies, glass, fluororesins and engineering plastics such as PEEK are suitable. In this case, in the method of cleaning an article using the present solvent composition (or the method of cleaning the article using the present aerosol composition), the present solvent composition (or the present aerosol composition) is brought into contact with the article to bring the article into contact with the article. This is a method of removing stains adhering to the solvent.

1. 1. Measurement of boiling point of solvent composition The boiling point of this solvent composition will be described below.

The solvent composition having the composition shown in Table 1 below in which the mass ratio of 1,4-DCB to 100% by mass of HCFO-1233zd (Z) as chlorotrifluoropropene and the total amount of 1,4-DCB is above the top. The solvent composition was refluxed by heating in a hot water bath, and the boiling point was measured by measuring the temperature of the liquid phase portion of the solvent composition when the reflux state became stable. The measurement results are shown in Table 1. Using the measured data, an approximate curve between the mass ratio of 1,4-DCB of the solvent composition and the boiling point of the solvent composition was calculated. In the approximate curve, the mass ratio of 1,4-DCB at a boiling point of 50 ° C. is 35% by mass, and the mass ratio of 1,4-DCB at a boiling point of 70 ° C. is 68% by mass. rice field.

As shown in Table 1, in this solvent composition, the content of 1,4-DCB is 30% by mass or more and 70% by mass or less with respect to 100% by mass of the total amount of HCFO-1233zd (Z) and 1,4-DCB. In this case, the boiling point of the solvent composition is in the range of about 50 ° C to about 70 ° C. In this solvent composition, by mixing HCFO-1233zd (Z) and 1,4-DCB, the boiling point can be appropriately raised as compared with HCFO-1233zd (Z) alone, and it is an open-type washing machine. It is possible to suppress the amount of solvent consumed (the amount of solvent volatilization loss) when used in such cases.

2. Evaporation rate of solvent composition The evaporation rate of this solvent composition will be described below.

A magnetic stirrer capable of controlling the number of revolutions and a water bath capable of controlling the temperature were placed on the electronic balance, and a tall beaker having a capacity of 500 mL was placed in the water bath. A solvent composition (400 g) composed of HCFO-1233zd (Z) as chlorotrifluoropropene and 1,4-DCB was placed in a tall beaker, and water was added to a water bath as a heating medium. In order to prevent the evaporation of water in the water bath, the water surface was covered by floating an aluminum-deposited heat insulating sheet on the water surface. Set the water temperature of the water bath to 30 ° C, measure the mass loss for 30 minutes after the temperature of the solvent composition in the tall beaker stabilizes at about 28 ° C, and calculate the evaporation rate of the solvent composition every minute. bottom.

Table 2 shows a single product of HCFO-1233zd (Z), a mixed solvent of HCFO-1233zd (Z) and 1,4-DCB (mass ratio = 75/25), and a mixture of HCFO-1233zd (Z) and 1,4-DCB. The result of the solvent (mass ratio = 50/50) is shown. As shown in Table 2, in the present solvent composition, when the content of 1,4-DCB is 25% by mass with respect to 100% by mass of the total amount of HCFO-1233zd (Z) and 1,4-DCB, HCFO-1233zd. (Z) The relative evaporation rate was reduced by 6% as compared with the single product. That is, the solvent composition having a content of 1,4-DCB of 25% by mass was able to reduce the amount of evaporation loss by 6% as compared with the HCFO-1233zd (Z) alone. Further, when the content of 1,4-DCB is 50% by mass with respect to the total amount of 100% by mass of HCFO-1233zd (Z) and 1,4-DCB, relative evaporation is performed as compared with the HCFO-1233zd (Z) alone. The speed was reduced by 18%. That is, the solvent composition having a content of 1,4-DCB of 50% by mass was able to reduce the amount of evaporation loss by 18% as compared with the HCFO-1233zd (Z) alone. In this solvent composition, by mixing HCFO-1233zd (Z) and 1,4-DCB, the evaporation rate can be lowered as compared with HCFO-1233zd (Z) alone, and an open-type washing machine or the like can be used. It is possible to suppress the amount of solvent consumed (the amount of solvent volatilization loss) when used in.

3. 3. Solubility test of the metal plastic working lubricant for the solvent composition A predetermined amount of the metal plastic working lubricant was added to the solvent according to the following method, and the solubility test was performed.

This solvent composition containing HCFO-1233zd (Z) as chlorotrifluoropropene and 1,4-DCB in the mixing ratio shown in Table 3 below, and the lubricant for metal plastic working shown in Table 3 (in Table 3, in Table 3). (Denoted as oil) was placed in a glass sample bottle having a capacity of 50 mL, shaken, and mixed. This was allowed to stand in a laboratory controlled at 23 ° C., and the state of the solution was visually observed after 30 minutes. If the solution is colorless and transparent (no turbidity) and uniform, it is marked with "○", if it is turbid, and if it is separated into two layers or clearly insoluble, it is marked with "x". Judged. The results of each are shown in Table 3.

In Table 3, PG-3740 and G-3641 of the oils are water-insoluble lubricants for metal plastic working sold by Nihon Kohsakuyu Co., Ltd. The main components of PG-3740 are petroleum hydrocarbons (mineral oil), oiliness improvers, and rust preventive additives. The liquid density at 15 ° C is 0.90 g / mL, and the kinematic viscosity at 40 ° C is 432 mm ² / s. , Appearance is green liquid. The main components of G-3641 are petroleum hydrocarbons (mineral oil), oiliness improvers, sulfur-based extreme pressure additives, and rust preventive additives, and the liquid density at 15 ° C. is 0.95 g / mL and at 40 ° C. It has a kinematic viscosity of 234 mm ² / s and is a brown transparent liquid in appearance.

As shown in Table 3, this solvent composition satisfactorily dissolved various lubricants for metal plastic working. It is shown that this solvent composition dissolves not only the lubricating oil base oil but also additive components such as an oiliness improver, an extreme pressure additive and a rust preventive additive satisfactorily. Referring to the results in Table 3, the solvent composition, that kinematic viscosity at 40 ° C. is favorably dissolve the water-insoluble metal plastic working lubricant for a high viscosity which is 234mm ² / s~432mm ² / s It is shown and is suitable as a cleaning agent for articles to which these lubricants for metal plastic processing are attached. This solvent composition is not only a high-viscosity metal plastic processing lubricant as tested in Examples, but also a metal plastic processing lubricant having a lower viscosity than these metal plastic processing lubricants (movement at 40 ° C.). metal plastic working lubricant viscosity is less than 234 mm ² / s, for example, kinematic viscosity at 40 ° C. is ^{1mm 2} / s~233mm 2 / s, or a kinematic viscosity at 40 ° C. is 50mm ² / s~233mm ² / s It is also excellent in solubility of the metal plastic processing lubricant), and is also suitable as a cleaning agent for articles to which the metal plastic processing lubricant is attached. In addition, since this solvent composition dissolves coal tar well, it is suitable as a cleaning agent for articles to which coal tar is attached.

4. Flash point of solvent composition The flash point of this solvent composition will be described below.

[Examples 4-1 to 4-4, Comparative Examples 4-1 to 4-2]
The flash point of this solvent composition containing HCFO-1233zd (Z) as chlorotrifluoropropene and 1,4-DCB at the mixing ratio shown in Table 4 below is measured according to the JIS tag closed flash point measurement method. bottom.

As shown in Comparative Example 4-1, 1,4-DCB is flammable (flash point: 53 ° C.), and as shown in Comparative Example 4-2, HCFO-1233zd (Z) is nonflammable (flash point). : None). As a result of measuring the flash point by the tag closed type, surprisingly, the flash point of the 1,4-DCB-1233zd (Z) mixed solution was observed by containing only 5 wt% of HCFO-1233zd (Z). There wasn't. This solvent composition can be suitably used as a non-flammable detergent having no flash point by mixing HCFO-1233zd (Z) and 1,4-DCB.

[Examples 5-1 to 5-3, Comparative Example 5-1 and Comparative Example 5-2]
Using 1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd) and 1,4-DCB as chlorotrifluoropropene according to the JIS tag closed flash point measurement method, The flash point of this solvent composition contained in the mixing ratio shown in Table 5 of the above was measured. Here, 1233yd is a mixture of a cis (Z) form and a trans (E) form, and refers to a mixture of 1233yd (Z): 1233yd (E) = 92: 8 (molar ratio).

As shown in Comparative Example 5-1, 1,4-DCB is flammable (flash point: 53 ° C.), and as shown in Comparative Example 5-2, HCFO-1233yd is nonflammable (flash point: none). Is. As shown in Examples 5-1 to 5-3, no flash point was observed in the mixed solution of 1,4-DCB-1233yd. This solvent composition can be suitably used as a non-flammable detergent having no flash point by mixing HCFO-1233yd and 1,4-DCB.

5. Cleaning test The cleaning test of this solvent composition will be described below.

(Preparation for cleaning test)
After cutting a shim plate (tape-shaped stainless steel plate, manufactured by Hayashi Co., Ltd., material: SUS301, thickness: 0.15 mm, width: 12.7 mm) to a length of about 70 mm, ultrasonic cleaning in carbon tetrachloride 30 The test piece was dried for 1 minute and then ultrasonically washed in acetone for 30 minutes to prepare a test piece for evaluation (hereinafter, also referred to as “work”). A total of two evaluation test pieces were prepared by the same operation. Press oil G-3641 manufactured by Nihon Kohsakuyu Co., Ltd. was applied to these two workpieces and weighed with a precision balance. As a result, 4.70 mg of oil was applied to the two workpieces.

A magnetic stirrer bar and a cleaning solvent (400 g) were charged into a 500 cc tall beaker of A to D to serve as a model of a cleaning tank. The cleaning solvents charged in the beakers A to D are shown in Table 6 below. In Table 6, 1233yd is a mixture of geometric isomers with E / Z = 8/92 (molar ratio). Further, in Table 6, the mixture of 1233 zd (Z) and 1,4-DCB is described as "1233 zd (Z) -1,4-DCB". Similarly, a mixture of 1233yd and 1,4-DCB is described as "1233yd-1,4-DCB". This notation is also the same below.

(Washing test 1: Stirring and washing at room temperature with 1233 zd (Z) -1,4-DCB)
[Example 7-1, Comparative Example 7-1]
As a cleaning step, beaker A (1233zd (Z) -1,4-DCB) is stirred at 800 rpm, one piece of work prepared in preparation for the above-mentioned cleaning test is put therein, and the mixture is left for 60 seconds for cleaning. It was taken out with tweezers and shaken lightly to drain the liquid. As a rinsing step, the beaker B (1233zd (Z)) being stirred at room temperature at 800 rpm was immersed for 10 seconds for rinsing and washing. It was taken out with tweezers, shaken lightly to drain the liquid, washed with 1233 zd (Z) using a washing bottle, and dried in a dryer at 50 ° C. for 3 minutes. This operation was also performed on another work to obtain two washed works.

(Measurement of removal rate)
The washed work (press oil G-3641 applied as a stain component, weighing, washing, rinsing, over-washing, dried product) obtained by stirring washing is immersed in approximately 110 g of carbon tetrachloride that has been accurately weighed, and at room temperature. The oil remaining on the work was extracted by ultrasonic irradiation. The carbon tetrachloride was analyzed by FT-IR, and the residual oil content for two workpieces was determined by the calibration curve of the peak height and the oil concentration prepared in advance (Example 7-1). As a result of determining the removal rate [(coating amount-residual amount) / coating amount x 100], it was 99.1%, which was better than the system without addition of 1,4-DCB (Comparative Example 7-1). was gotten.

[Examples 7-2 to 7-6, Comparative Examples 7-2 to 7-6]
The same cleaning test as in cleaning test 1 was performed by changing the type of oil (dirt component) applied to the work and the type of cleaning solvent, and the removal rate of the oil applied to the work was determined. The type of oil (dirt component) applied to the work, the type of cleaning solvent used, and the oil removal rate in Examples 7-2 to 7-6 and Comparative Examples 7-2 to 7-6 were determined. It is summarized in Table 8 below. In Table 8, 1233yd is a mixture of 1233yd (Z): 1233yd (E) = 92: 8 (molar ratio).

Hereinafter, the stain components (oils such as metal plastic working oil, cutting oil, grinding oil, cutting grinding oil, lubricating oil, etc.) used in the examples will be described.

Tapping paste C-101 is a water-insoluble lubricant for cutting and grinding sold by Nihon Kohsakuyu Co., Ltd., and is a non-fluid paste at room temperature. Hangster Fur 42 1/4 XX is a plastic working oil sold by Hangster Fur, which has a kinematic viscosity at 40 ° C. of 30,000 mm ² / s. Daphne Milkur BL, Daphne Hermetic Oil 90PX and Daphne Marg Plus ST25H are sold by Idemitsu Kosan Co., Ltd. Daphne Milkool BL is an emulsifying emulsion type water-soluble cutting oil. Daphne Hermetic Oil 90PX is a lubricating oil containing mineral oil (90% by mass or more) and a lubricating oil additive. Daphne Marg Plus ST25H contains hydrogenated low-viscosity paraffin, sulfide 2,4,4-trimethylpentene, sulfide oil and fat, hydrogenated medium-viscosity paraffin, solvent-refined paraffin oil, and 2,6-di-tert-butyl-4-cresol. It is a cutting oil containing a lubricating oil additive and has a kinematic viscosity at 40 ° C. of 12 mm ² / s. Sugicut CE-14A and Sugicut CS-58XJ are sold by Sugimura Chemical Industrial Co., Ltd. and are water-soluble cutting and grinding oils containing mineral oil, diethanolamine and triethanolamine. Fine Cut CFS-95A is a water-soluble cutting and grinding oil containing hydrocarbons, amines, alcohols, organic acid amine salts, organic acids, defoaming agents, corrosion inhibitors, surfactants, and water sold by Neos Co., Ltd. Is. Sunfoam 350 is a plastic working oil containing mineral oil and additives sold by Nippon Grease Co., Ltd., and has a kinematic viscosity at 40 ° C. of 78 mm ² / s. Tapping compound A-3 is a metal processing oil containing refined mineral oil, an anti-wear agent and an oiliness improver sold by Sato Tokushu Seiyu Co., Ltd., and has a kinematic viscosity of 38 mm ² / s at 40 ° C. Yushiro Former CF200 is a lubricant for plastic working that contains a large amount of oily agent (oil and fat) sold by Yushiro Chemical Industry Co., Ltd., and has a kinematic viscosity at 40 ° C. of 42 mm ² / s.

Comparing Examples 7-2 to 7-6 and Comparative Examples 7-2 to 7-6, this solvent composition is a system to which 1,4-DCB is not added (Comparative Examples 7-2 to 7-6). Better cleaning results than in Example 7-6) were obtained. Therefore, it was shown that this solvent composition has an excellent cleaning ability against various stains and is suitable as a cleaning agent.

As the oil (dirt component), tapping paste C-101, hangster fur 42 1/4 XX, Daphne milkle BL, fine cut CFS-95A, sunfoam 350, Daphne hermetic oil 90PX, or tapping compound A-3 was used. In the case as well, the same operation as in Example 7-1 was performed. As a result, this solvent composition showed the same or better cleaning results as the chlorotrifluoropropene alone.

(Cleaning test 2: Ultrasonic cleaning at room temperature with 1233 zd (Z) -1,4-DCB)
[Example 8-1, Comparative Example 8-1]
As a cleaning step, instead of stirring the beaker A (1233zd (Z) Z-1,4-DCB) at 800 rpm, the same operation as in the above-mentioned cleaning test 1 is performed except that ultrasonic waves are irradiated for 30 seconds without stirring. went.

For the washed work (press oil G-3641 applied, weighed, washed, rinsed, washed with water, dried product) obtained by ultrasonic cleaning, the oil remaining on the work is the same as the above-mentioned method for measuring the removal rate. (Dirt component) was extracted, carbon tetrachloride was analyzed by FT-IR, and the residual oil content for two workpieces was determined from the calibration curve of the peak height and oil concentration prepared in advance (Example 8-1). ). As a result of determining the removal rate [(coating amount-residual amount) / coating amount x 100], the cleaning result was 100%, which was better than that of the system without addition of 1,4-DCB (Comparative Example 8-1). Was done.

[Examples 8-2 to 8-6, Comparative Examples 8-2 to 8-6]
The same cleaning test as in cleaning test 2 was performed by changing the type of oil (dirt component) applied to the work and the type of cleaning solvent, and the removal rate of the oil applied to the work was determined. The type of oil (dirt component) applied to the work, the type of cleaning solvent used, and the oil removal rate in Examples 8-2 to 8-6 and Comparative Examples 8-2 to 8-6 were determined. It is summarized in Table 10 below. In Table 10, 1233yd is a mixture of 1233yd (Z): 1233yd (E) = 92: 8 (molar ratio).

Comparing Examples 8-2 to 8-6 and Comparative Examples 8-2 to 8-6, this solvent composition is a system to which 1,4-DCB is not added (Comparative Examples 8-2 to 8-2). Better cleaning results than in Example 8-6) were obtained. Therefore, it was shown that this solvent product has an excellent cleaning ability against various stains and is suitable as a cleaning agent.

Further, comparing Examples 7-2 to 7-6 and 8-2 to 8-6, this solvent product has better cleaning ability when used in ultrasonic cleaning than in stirring cleaning. Is shown. Therefore, it is particularly preferable to use this solvent product in ultrasonic cleaning.

Examples also when tapping paste C-101, Daphne milkle BL, Sugicut CS-58XJ, Sunfoam 350, Yushiron Former CF200, Daphne Marg Plus ST25H, or Daphne Hermetic Oil 90PX are used as the oil (dirt component). The same operation as in 8-1 was performed. As a result, this solvent composition showed the same or better cleaning results as the chlorotrifluoropropene alone.

6. Vapor-liquid equilibrium and boiling temperature [Vapor-liquid equilibrium and boiling temperature of 1233 zd (Z) -1,4-DCB solution]
Using an Othmer-type gas-liquid equilibrium device, the gas-liquid equilibrium of 1233 zd (Z) -1,4-DCB solutions having various compositions and the temperature of the bottom of the column at the time of boiling (bottom temperature) were measured. The vapor-liquid equilibrium of the 1233zd (Z) -1,4-DCB solution is shown in FIG. 1, and the bottom temperature of the 1233zd (Z) -1,4-DCB solution at boiling is shown in FIG. In the region where the 1,4-DCB concentration was less than 60 wt%, the 1,4-DCB vapor in the vapor phase portion was less than 1% even under boiling conditions. It is supported that the sweet odor peculiar to 1,4-DCB is alleviated in this region. Further, when 50 wt% of 1,4-DCB was added as compared with the case of 1233 zd (Z) alone, the boiling point increased by about 20 ° C. Although the upper limit of the cleaning temperature in the liquid state is 39 ° C. with 1233 zd (Z) alone, it is shown that high temperature cleaning is possible by adding 50 wt% of 1,4-DCB.

[Vapor-liquid equilibrium and boiling temperature of 1233yd-1,4-DCB solution]
Using an Othmer-type gas-liquid equilibrium device, the gas-liquid equilibrium of the 1233yd-1,4-DCB solution and the bottom temperature at the time of boiling were measured. Here, the composition of the 1233yd-1,4-DCB solution is 50 wt% -50 wt%. The results are shown in Table 11 below. In Table 11, the gas-liquid equilibrium of the 1233yd-1,4-DCB solution and the measurement result of the bottom temperature at the time of boiling are shown as Example 9-1, and the vapor-liquid equilibrium of only 1233yd only as Comparative Example 9-1. And the measurement result of the bottom temperature at the time of boiling is shown. Here, 1233yd is a mixture of a cis (Z) form and a trans (E) form, and refers to a mixture of 1233yd (Z): 1233yd (E) = 92: 8 (molar ratio).

Similar to 1233 zd (Z), in the case of 1233 yd, the boiling point increased by about 20 ° C. by adding 50 wt% of 1,4-DCB, and high temperature cleaning became possible. Further, referring to the composition ratio of the 1233yd-1,4-DCB solution in the gas phase, it can be seen that most of the vapor phase vapor is 1233yd, and the odor of 1,4-DCB is alleviated.

Since this solvent composition contributes extremely little to ozone layer depletion and global warming and has excellent solubility of lubricants for metal plastic working, it can be used for metal parts such as automobile parts, electronic parts, and precision machine parts. It can be suitably used for cleaning after plastic working. Further, since the present solvent composition dissolves coal tar, it can be suitably used as a solvent composition for dissolving, washing, diluting and applying coal tar. Further, this solvent composition is excellent not only in high viscosity (for example, kinematic viscosity at 40 ° C. is 50 mm ² / s or more) lubricant for metal plastic working, but also in solubility of lower viscosity processing oil. Therefore, it can be suitably used as a cleaning agent for articles to which processing oil is attached. Further, the solvent composition can be suitably used as a cleaning agent for removing various stains adhering to the article, in addition to the above-mentioned lubricant for metal plastic working.

Claims (17)

A solvent composition comprising chlorotrifluoropropene and 1,4-dichlorobutane (1,4-DCB). The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propen (HCFO-1233yd (E)), 2-chloro-3,3,3-trifluoro-1-propen (HCFO-1233xf) , E-1-chloro-trifluoropropene (HCFO-1233zd (E)), E-2-chloro-1,3,3-trifluoropropene (HCFO-1233xe (E)), Z-2-chloro-1 , 3,3-Trifluoropropene (HCFO-1233xe (Z)), E-1-chloro-1,3,3-trifluoropropene (HCFO-1233zb (E)), Z-1-chloro-1,3 , 3-Trifluoropropene (HCFO-1233zb (Z)), 3-Chloro-2,3,3-trifluoropropene (HCFO-1233yf), E-3-chloro-1,3,3-trifluoropropene ( HCFO-1233ze (E)), Z-3-chloro-1,3,3-trifluoropropene (HCFO-1233ze (Z)), E-1-chloro-1,2,3-trifluoropropene (HCFO- 1233yb (E)), Z-1-chloro-1,2,3-trifluoropropene (HCFO-1233yb (Z)), 2-chloro-1,1,3-trifluoropropene (HCFO-1233xc), 3 -Chloro-1,1,2-trifluoropropene (HCFO-1233yc), E-1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (E)), Z-1,2- Dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)), 1,1-dichloro-3,3,3-trifluoropropene (HCFO-1223za), 1,1-dichloro-2,3 , 3-Trifluoropropene (HCFO-1223ya), E-1,2-dichloro-1,3,3-trifluoropropene (HCFO-1223xb (E)), Z-1,2-dichloro-1,3, 3-Trifluoropropene (HCFO-1223xb (Z)), E-1,3-dichloro-2,3,3-trifluoropropene (HCFO-1223yd (E)), Z-1,3-dichloro-2, 3,3-Trifluoropropene (HCFO-1223yd (Z)), E-2,3-jik Lolo-1,3,3-trifluoropropene (HCFO-1223xe (E)), Z-2,3-dichloro-1,3,3-trifluoropropene (HCFO-1223xe (Z)), E-1, 3-Dichloro-1,3,3-trifluoropropene (HCFO-1223zb (E)), Z-1,3-dichloro-1,3,3-trifluoropropene (HCFO-1223zb (Z)), 1, 1,2-Trichloro-3,3,3-trifluoropropene (CFO-1213xa), 1,1,3-trichloro-2,3,3-trifluoropropene (CFO-1213ya), E-1,2, 3-Trichloro-1,3,3-trifluoropropene (CFO-1213xb (E)), Z-1,2,3-trichloro-1,3,3-trifluoropropene (CFO-1213xb (Z)), E-1,3,3-trichloro-1,2,3-trifluoropropene (CFO-1213yb (E)), Z-1,3,3-trichloro-1,2,3-trifluoropropene (CFO-) The solvent composition according to claim 1, which is at least one selected from the group consisting of 1213yb (Z)) and 2,3,3-trichloro-1,1,3-trifluoropropene (CFO-1213xc). The solvent composition according to claim 1, wherein the chlorotrifluoropropene is at least one selected from the HCFO-1233 isomer having a molecular formula of C ₃ HClF _3. The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (E)), which is at least one selected from the solvent composition according to claim 1. The chlorotrifluoropropene is Z-1-chloro-trifluoropropene, and the total amount of the Z-1-chloro-3,3,3-trifluoropropene and the 1,4-dichlorobutane is 100% by mass. The solvent composition according to claim 1, wherein the Z-1-chloro-3,3,3-trifluoropropene is 5% by mass or more. The chlorotrifluoropropene is Z-1-chloro-trifluoropropene (HCFO-1233zd (Z)), Z-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (Z)). ), E-1-chloro-2,3,3-trifluoro-1-propene (HCFO-1233yd (E)), which is at least one selected.
The solvent composition according to claim 1, wherein the 1,4-dichlorobutane is 30% by mass or more and 70% by mass or less with respect to 100% by mass of the total amount of the chlorotrifluoropropene and the 1,4-dichlorobutane. thing. Claims further comprising at least one solvent selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. The solvent composition according to any one of 1 to 6. An aerosol composition containing the solvent composition according to any one of claims 1 to 7 and an injection gas. A cleaning agent containing the solvent composition according to any one of claims 1 to 7 or the aerosol composition according to claim 8. The cleaning agent according to claim 9, wherein the cleaning agent is a cleaning agent for removing stains adhering to an article. The cleaning agent according to claim 9, wherein the cleaning agent is a cleaning agent for removing a lubricant for metal plastic working adhering to an article. The cleaning agent according to claim 11, wherein the article is a metal member. The cleaning agent according to claim 11 or 12, wherein the lubricant for metal plastic working is a water-insoluble lubricant containing a lubricating oil base oil and an oiliness improver. 11. The lubricant for metal plastic processing is a water-insoluble lubricant containing at least one additive selected from the group consisting of extreme pressure additives, rust preventive additives and antioxidants. 12. The cleaning agent according to 12. The cleaning agent according to any one of claims 11 to 14, wherein the lubricant for metal plastic working has a kinematic viscosity of 50 mm ^{2 / s or more at 40 ° C.} A method for cleaning an article, which comprises a step of bringing the cleaning agent according to claim 10 into contact with an article to be cleaned to which dirt has adhered. A method for cleaning an article, which comprises a step of bringing the cleaning agent according to any one of claims 11 to 15 into contact with the article to be cleaned to which the lubricant for metal plastic working is attached.

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