JP2016210819A - Solvent composition, cleaning method and coating film formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solvent composition excellent in solubility of various organic article, having sufficient dryable property, having no adverse effects on global environment, being stabilized without decomposition and stable with suppressing metal corrosion in coexistence of a metal and capable of being used for an article of various material quality such as metal, plastic, elastomer without adverse effect in industrial applications such as cleaning or dilution applying applications.SOLUTION: The solvent composition is provided that contains (A) a solvent containing 1,1-dichloro-2,3,3,3-tetrafluoropropene, (B) a stabilizer composed of one or more kind selected from a group consisting of phenols, ethers, epoxides and pyrroles and (C) a nitro compound.SELECTED DRAWING: None

Description

  The present invention relates to a solvent composition, a cleaning method using the solvent composition, and a method for forming a coating film composed of a nonvolatile organic compound using the solvent composition as a diluted coating solvent.

  In the manufacture of ICs, electronic parts, precision machine parts, optical parts, etc., in the manufacturing process, assembly process, final finishing process, etc., the parts are washed with a cleaning solvent composition, and the flux, processing oil, wax adhered to the parts Removing mold release agents, dust and the like has been performed. In addition, as a method for producing an article having a coating film containing various non-volatile organic compounds such as a lubricant, for example, a solution in which the non-volatile organic compound is dissolved in a diluting solvent is prepared, and the solution is applied to the surface of an object to be coated. A method of forming a coating film by evaporating the diluent solvent after coating on the surface is known. The diluting solvent is required to sufficiently dissolve the organic compound and to have sufficient drying properties.

  Solvents used for such applications are nonflammable, less toxic, excellent in stability, do not attack metals, plastics, elastomers and other substrates, and are excellent in chemical and thermal stability. , 2-trichloro-1,2,2-trifluoroethane and other chlorofluorocarbons (hereinafter referred to as “CFCs”), 2,2-dichloro-1,1,1-trifluoroethane, 1,1 Hydro such as dichloro-1-fluoroethane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane Fluorinated solvents containing chlorofluorocarbons (hereinafter referred to as “HCFCs”) and the like have been used.

  However, since CFCs are chemically very stable, they have a long lifetime in the troposphere after vaporization and diffuse to reach the stratosphere. Therefore, there is a problem that CFCs reaching the stratosphere are decomposed by ultraviolet rays, generating chlorine radicals and destroying the ozone layer. For this reason, the production of CFCs is regulated worldwide, and production in developed countries has already been abolished.

  In addition, HCFCs also have chlorine atoms and have a slight adverse effect on the ozone layer, so production is scheduled to be abolished in developed countries in 2020.

  On the other hand, perfluorocarbons (hereinafter referred to as “PFCs”) are known as solvents that have no chlorine atom and do not adversely affect the ozone layer. In addition, hydrofluorocarbons (hereinafter referred to as “HFCs”), hydrofluoroethers (hereinafter referred to as “HFEs”) and the like have been developed as alternative solvents for CFCs and HCFCs. However, HFCs and PFCs are regulated substances under the Kyoto Protocol because of their large global warming potential.

  As a new solvent replacing the solvents of HFCs, HFEs and PFCs, halogenated olefins having a double bond between carbon atoms, for example, chlorofluoroolefins (hereinafter referred to as “CFOs”), Hydrochlorofluoroolefins (hereinafter referred to as “HCFOs”), hydrofluoroolefins (hereinafter referred to as “HFOs”), and the like have been proposed. Since these halogenated olefins are easily decomposed, they have excellent properties such as a short life in the atmosphere, a small ozone depletion coefficient and a global warming coefficient, and a small influence on the global environment. However, since it is easy to decompose, it is inferior in stability, and when used as a cleaning solvent or diluted coating solvent, it coexists with the solvent due to acidification of the solvent by decomposition during use, acid generated by decomposition, etc. Metal, such as storage containers, pipes, and devices that corrode.

  From such a problem, a technique for improving the stability of a halogenated olefin having a double bond between carbon atoms is required. As an example of a technique for stabilizing a conventional fluorinated solvent not containing a double bond, a general stabilizer is shown (for example, see Patent Documents 1, 2, and 3). Furthermore, an example of a technique for stabilizing a halogenated olefin having a double bond between carbon atoms is also disclosed. For example, Patent Documents 4, 5, and 6 disclose techniques for stabilizing HFOs and HCFOs. However, these are not techniques for stabilizing any halogenated olefin, and it is known that the stabilization technique varies depending on the type of halogenated olefin.

JP 11-293285 A Japanese Patent No. 4292348 Special table 2008-505212 Special table 2008-531836 gazette International Publication No. 2010-098451 Special table 2010-531924 gazette

  The present inventors are excellent in solubility of various organic substances, have sufficient drying properties, and do not adversely affect the global environment as 1,1-dichloro-2,3,3,3-tetrafluoro- It was found that 1-propene (hereinafter referred to as “CFO-1214ya” as necessary) is useful. CFO-1214ya is a halogenated olefin having a double bond between carbon atoms. Similar to the HFOs and HCFOs described in the above-mentioned prior art documents 4 to 6, stabilization technology is required for use. It is said.

  However, the stabilization techniques described in Prior Art Documents 4 to 6 relate to HFOs and HCFOs, and the stabilizing effect on CFO-1214ya has not been known. Furthermore, according to the knowledge of the present inventors, CFO-1214ya promotes metal corrosion when coexisting with a metal, but no technology has been known so far to suppress metal corrosion by CFO-1214ya.

The present invention was made from the above viewpoint, is a solvent composition containing a solvent that is excellent in solubility of various organic substances, has sufficient drying properties, and does not adversely affect the global environment, An object of the present invention is to provide a solvent composition which can be stored in a state where the solvent is stabilized and decomposition is suppressed, and corrosion of a metal in contact is suppressed.
An object of the present invention is to provide a stable and efficient method for cleaning an article to be cleaned, which does not adversely affect the global environment, suppresses metal corrosion, and is stable.
The present invention is a method for forming a coating film composed of a non-volatile organic compound, which does not adversely affect the global environment, suppresses metal corrosion, and can form a uniform coating film stably and easily. It aims to provide a method.

The present invention provides a solvent composition, a cleaning method, and a coating film forming method having the following configuration.
[1] From a solvent (A) containing 1,1-dichloro-2,3,3,3-tetrafluoropropene and at least one selected from the group consisting of phenols, ethers, epoxides, and pyrroles A solvent composition comprising the stabilizer (B) and the nitro compound (C).
[2] The content of the stabilizer (B) in the solvent composition is 1 mass ppm to 10 mass%, and the content of the nitro compound (C) is 1 mass ppm to 10 mass%. ] The solvent composition as described in.

[3] The content of the 1,1-dichloro-2,3,3,3-tetrafluoropropene in the solvent (A) is 80 to 100% by mass, according to [1] or [2]. Solvent composition.
[4] The phenol is a group consisting of phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol. The solvent composition according to any one of [1] to [3], which is at least one selected from the group consisting of more than one.

[5] The ethers are selected from the group consisting of ethyl phenyl ether, ethylene glycol monoethyl ether, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran and tetrahydrofuran. The solvent composition according to any one of [1] to [4], which is one or more selected.

[6] The epoxide is one or more selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether and diethylene glycol diglycidyl ether. The solvent composition according to any one of [1] to [5].

[7] The solvent composition according to any one of [1] to [6], wherein the pyrroles are one or more selected from the group consisting of pyrrole and N-methylpyrrole.
[8] The solvent according to any one of [1] to [7], wherein the nitro compound (C) is at least one selected from the group consisting of nitromethane, nitroethane, 1-nitropropane and 2-nitropropane. Composition.
[9] The solvent composition according to any one of [1] to [8], wherein the stabilizer (B) includes phenols and at least one selected from ethers, epoxides, and pyrroles.

[10] A cleaning method comprising bringing the solvent composition according to any one of [1] to [9] into contact with an article to be cleaned.
[11] The cleaning method according to [10], wherein the article to be cleaned is clothing.

[12] A non-volatile organic compound is dissolved in the solvent composition according to any one of [1] to [9] to prepare a coating film-forming composition, and the coating film-forming composition is coated A method of forming a coating film, comprising: applying the solvent composition to the solvent composition and evaporating the solvent composition to form a coating film made of the nonvolatile organic compound.

  According to the present invention, there is provided a solvent composition comprising a solvent that is excellent in solubility of various organic substances, has sufficient drying properties, and does not adversely affect the global environment, and the solvent is stabilized. It is possible to provide a solvent composition which can be stored in a state in which decomposition is suppressed, and in which corrosion of a metal in contact is suppressed.

According to the cleaning method of the present invention, it is possible to stably and efficiently clean an article to be cleaned without adversely affecting the global environment, suppressing metal corrosion.
The method for forming a coating film comprising a non-volatile organic compound of the present invention is a method in which corrosion of metals is suppressed without adversely affecting the global environment. According to the forming method, a uniform application of non-volatile organic compound is performed. The film can be stably and easily formed.

[Solvent composition]
The solvent composition of the present invention contains the following (A) to (C).
Solvent (A) containing 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) (hereinafter also referred to as “solvent (A)”)
Stabilizer (B) comprising at least one selected from the group consisting of phenols, ethers, epoxides, and pyrroles (hereinafter also referred to as “stabilizer (B)”).
Nitro compound (C)

  CFO-1214ya used in the solvent composition of the present invention is one of CFOs having a double bond between carbon atoms, has a short life in the atmosphere, and has an ozone depletion coefficient and a global warming coefficient. small. CFO-1214ya has a boiling point of about 46 ° C. (normal pressure) and excellent drying properties. In addition, even if it is boiled and becomes steam, it is about 46 ° C., so even parts that are easily affected by heat such as resin parts are unlikely to have an adverse effect. CFO-1214ya does not have a flash point, has a low surface tension and viscosity, and has excellent performance such as being easily evaporated at room temperature.

  CFO-1214ya is not stable enough, and even when stored at room temperature, it gradually decomposes and acidifies CFO-1214ya. Therefore, in the present invention, by combining the solvent (A) containing CFO-1214ya with at least one stabilizer (B) selected from the group consisting of phenols, ethers, epoxides, and pyrroles, It was found that the decomposition of CFO-1214ya is suppressed and can be used stably for a long period of time.

  Furthermore, in the present invention, in addition to the stabilizer (B) and the nitro compound (C) in addition to the solvent (A) containing CFO-1214ya, the corrosion of the metal caused by CFO-1214ya can be prevented. It was found that suppression is possible.

Hereinafter, (A) to (C) contained in the solvent composition of the present invention will be described.
<Solvent (A) containing CFO-1214ya>
The solvent composition of the present invention contains a solvent (A) containing CFO-1214ya. The solvent (A) may be composed of only CFO-1214ya, and for various purposes such as increasing the solubility of various solute substances and adjusting the volatilization rate, as long as the above characteristics of CFO-1214ya are not harmed. Accordingly, a solvent other than CFO-1214ya (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 CFO-1214ya. The solvent soluble in CFO-1214ya means that when CFO-1214ya and the solvent (a1) are mixed at an arbitrary mixing ratio, they are not phase-separated or turbid by stirring at room temperature (25 ° C.). Means a solvent that is uniformly dissolved in CFO-1214ya. The solvent means a substance that is liquid at normal temperature (25 ° C.).

  80 mass% or more is preferable with respect to the whole quantity of a solvent composition, and, as for content of the solvent (A) in the solvent composition of this invention, More preferably, it is 90 mass% or more. The higher the content of the solvent (A) in the solvent composition, the better. Therefore, the upper limit of the content of the solvent (A) in the solvent composition is preferably a value obtained by subtracting the lower limit of the content of the stabilizer (B) to be used and the lower limit of the content of the nitro compound (C). .

  Further, the content of CFO-1214ya in the solvent composition of the present invention is preferably 80% by mass or more, more preferably 90% by mass or more in terms of the mass ratio of CFO-1214ya to the total amount of the solvent composition. . The upper limit value of the content of CFO-1214ya in the solvent composition is the same as the upper limit value of the solvent (A).

  The content of CFO-1214ya in the solvent (A), that is, the amount of CFO-1214ya relative to 100% by mass of the total amount of CFO-1214ya and solvent (a1) is preferably 50% by mass or more, more preferably 80% by mass or more. 90 mass% or more is more preferable, and 100 mass% is most preferable. If the content of CFO-1214ya in the solvent (A) is not less than the lower limit, the excellent drying property of CFO-1214ya is not inhibited. The upper limit of the content of CFO-1214ya is 100% by mass.

  CFO-1214ya is, for example, 1,1-dichloro-2,2,3,3,3-pentafluoropropane (hereinafter referred to as “HCFC-225ca”) as a raw material and an alkaline aqueous solution in the presence of a phase transfer catalyst. Manufactured by dehydrofluorination method (1) or HCFC-225ca as a raw material in the presence of a catalyst such as chromium, iron, copper, activated carbon, etc. (See Japanese Patent No. 3778298). In the methods (1) and (2), HCFC-225ca and 1,3-dichloro-1,2,2,3,3-pentafluoropropane (hereinafter referred to as “HCFC-225cb”) are used. It can also be produced by using a mixture of isomers as a raw material and dehydrofluorinating HCFC-225ca (see International Publication No. 2010/074254). The method using the isomer mixture is advantageous in that it is simple and economical.

CFO-1214ya obtained by the above-described manufacturing method contains unreacted impurities such as HCFC-225ca and HCFC-225cb. The content of impurities in CFO-1214ya to be used is preferably 1% by mass or less in order to reduce the burden on the global environment such as ozone layer destruction and global warming, and to obtain excellent detergency. 5 mass% or less is more preferable.
That is, the purity of CFO-1214ya is preferably 99% by mass or more, and more preferably 99.5% by mass or more.
The purity of CFO-1214ya can be increased by distillation or the like.

  When the solvent (A) contains the solvent (a1), the content of the solvent (a1) in the solvent (A), that is, the solvent (a1) relative to 100% by mass of the total amount of CFO-1214ya and the solvent (a1). The amount is preferably 0.1 to 50% by mass, more preferably 0.5 to 20% by mass, and still more preferably 1 to 10% by mass.

If content of the solvent (a1) in a solvent (A) is more than the said lower limit, the effect by a solvent (a1) will fully be acquired for a solvent composition. If content of the solvent (a1) in a solvent (A) is below the said upper limit, it will be excellent in drying property.
Moreover, when CFO-1214ya and the solvent (a1) form an azeotropic composition, the use with an azeotropic composition is also possible.

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

  As the hydrocarbons as the solvent (a1), hydrocarbons having 5 or more carbon atoms are preferable. If it is a hydrocarbon having 5 or more carbon atoms, it may be a chain or a ring, and may be a saturated hydrocarbon or an unsaturated hydrocarbon.

  Specifically, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 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-methylheptane, 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-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, Examples include tetralin and amyl naphthalene. Of these, n-pentane, cyclopentane, n-hexane, cyclohexane and n-heptane are preferred.

  As alcohol which is a solvent (a1), C1-C16 alcohol is preferable. As long as the alcohol has 1 to 16 carbon atoms, it may be a chain or a ring, and may be a saturated alcohol or an unsaturated alcohol.

  Specific examples of alcohols 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-de 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, Examples include 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol and the like. Of these, methanol, ethanol, and isopropyl alcohol are preferable.

  As ketones which are a solvent (a1), C3-C9 ketones are preferable. As long as the ketone has 3 to 9 carbon atoms, it may be a chain or a ring, and may be a saturated ketone or an unsaturated ketone.

  Specific examples of ketones include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, diisobutyl ketone, mesityl oxide, phorone, 2 -Octanone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanedione, 2,5-hexanedione, diacetone alcohol, acetophenone and the like. Of these, acetone and methyl ethyl ketone are preferable.

  As ester which is a solvent (a1), C2-C19 ester is preferable. As long as it is an ester having 2 to 19 carbon atoms, it may be a chain or a ring, and may be a saturated ester or an unsaturated ester.

  Specific examples of esters 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, acetic acid Pentyl, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyric acid Isobutyl, ethyl 2-hydroxy-2-methylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, γ-butyrolactone, diethyl oxalate, dibutyl oxalate, dipentyl oxalate , Diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate and the like. Of these, methyl acetate and ethyl acetate are preferred.

  As a chlorocarbon which is a solvent (a1), a C1-C3 chlorocarbon is preferable. The chlorocarbons having 1 to 3 carbon atoms may be chain-like or cyclic, and may be saturated chlorocarbons or unsaturated chlorocarbons.

  Specific examples of chlorocarbons include methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2, Examples include 2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene. Of these, methylene chloride, trans-1,2-dichloroethylene, and trichloroethylene are preferable.

  As the HFCs as the solvent (a1), chain or cyclic HFCs having 4 to 8 carbon atoms are preferable, and solvents included in HFCs having one or more fluorine atoms in one molecule being more than the number of hydrogen atoms are more preferable. .

  As HFCs, specifically, 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, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, etc. Is mentioned. Among these, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,2,2,3,3,4,4,5,5,6,6-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. Etc. Of these, (perfluorobutoxy) methane and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane are preferable.

  1 type may be sufficient as the solvent (a1) contained in the solvent composition of this invention, and 2 or more types may be sufficient as it.

  The solvent (a1) is preferably a solvent having no flash point. As the solvent (a1) having no flash point, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3, HFCs such as 4,4-nonafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, (perfluorobutoxy) methane, HFEs such as 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane may be mentioned. When a solvent having a flash point is used as the solvent (a1), it is mixed with CFO-1214ya, the component (B) and the component (C) as long as the solvent composition of the present invention does not have a flash point. And preferably used.

<Stabilizer (B)>
The solvent composition of this invention contains the stabilizer which consists of at least 1 sort (s) chosen from the group which consists of phenols, ethers, epoxides, and pyrroles as a stabilizer (B). The stabilizer in the present invention refers to a compound having an ability to suppress decomposition of CFO-1214ya by oxygen.

  Here, the ability of a compound to suppress the decomposition of CFO-1214ya by oxygen can be evaluated by measuring the acid produced by the decomposition of CFO-1214ya by oxygen. For example, a difference between an initial pH value in a test solution in which a specimen is dissolved in CFO-1214ya at a predetermined ratio and a pH value after the test solution is stored for a certain period can be evaluated as an index.

Specifically, the stabilizer (B) in the solvent composition of the present invention is characterized in that, in the following relational expression (1), the mass ratio (X mass%) of the stabilizer to CFO-1214ya has CFO-1214ya. When the mass ratio is an upper limit mass ratio that does not harm the stabilizer, the stabilizer (B) capable of setting the value of ΔpH to 4 or less is preferable, and the stabilizer (B) capable of setting the value of ΔpH to 0 is more preferable.
ΔpH = pH (β) −pH (α) (1)
pH (β): pH value immediately after preparing the test solution by dissolving the stabilizer at a predetermined mass ratio (X mass%) with respect to CFO-1214ya (100 mass%) (however, the predetermined mass ratio is , And a mass ratio that does not harm the characteristics of CFO-1214ya.)
pH (α): pH value after the test solution is stored at the boiling point (46 ° C.) of CFO-1214ya for 7 days immediately after preparation.

  Specifically, the content of the stabilizer (B) in the solvent composition is preferably 1 mass ppm or more in the solvent composition, and 10 mass% or less from the viewpoint of sufficiently exerting the ability of CFO-1214ya. Is preferred. More preferably, it is 3 mass ppm-7 mass%, Most preferably, it is 5 mass ppm-5 mass%.

  The stabilizer (B) used in the present invention comprises at least one selected from the group consisting of phenols, ethers, epoxides and pyrroles. That is, the stabilizer (B) may be composed of one kind selected from these four kinds of compounds, or may be composed of two or more kinds. When the stabilizer (B) is composed of two or more compounds, all the compounds may be selected from the same compounds, for example, phenols, or different compounds, for example, phenols and ethers, respectively. It may be.

  Here, it is considered that the mechanisms by which these four types of compounds stabilize CFO-1214ya are different. Therefore, in the solvent composition of the present invention, it is preferable to use a combination of two or more compounds selected from the four types of compounds as the stabilizer (B). For example, it is speculated that phenols and pyrroles suppress oxidative degradation of CFO-1214ya due to an antioxidant action. In the solvent composition of the present invention, the stabilizer (B) is particularly preferably a combination of at least one selected from phenols and at least one selected from three types of compounds other than phenols.

(Phenols)
The phenol used as the stabilizer (B) refers to an aromatic hydroxy compound having one or more hydroxy groups in the aromatic hydrocarbon nucleus. As the phenols, compounds having high solubility in the solvent (A) are preferable. A benzene nucleus is preferred as the aromatic hydrocarbon nucleus. 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 hydroxyl group bonded to the aromatic hydrocarbon nucleus. Examples of the substituent include a hydrocarbon group, an alkoxy group, an acyl group, and a carbonyl group. 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. Among these, 1-6 are preferable and, as for carbon number of an alkyl group, an alkenyl group, an alkoxy group, an acyl group, and a carbonyl group, 1-4 are more preferable. 6-10 are preferable and, as for carbon number of an aralkyl group, 7-10 are preferable. As the hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is particularly preferable.

  When it has a substituent, the number 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.

  Among these, a substituted or unsubstituted compound in which the aromatic hydrocarbon nucleus is a benzene nucleus and has 1 to 3 hydroxy groups is preferable. As the phenols 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 ortho to the hydroxy group is preferable. The alkyl group at the ortho position is preferably a branched alkyl group such as a tertiary butyl group. 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-ditertiarybutyl-4- Methylphenol, 2,4,6-tritertiary butylphenol, 2-tertiary butylphenol, 3-tertiary butylphenol, 4-tertiary butylphenol, 2,4-ditertiary butylphenol, 2,6-ditertiary butylphenol, 4, 6-ditertiary butylphenol, 1-cresol, 2-cresol, 3-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2,3 6-trimethylphenol, , 4,6-trimethylphenol, 2,5,6-trimethylphenol, 3-isopropylphenol, 2-isopropyl-5-methylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol , 3-ethoxyphenol, 4-ethoxyphenol, 2-propoxyphenol, 3-propoxyphenol, 4-propoxyphenol, 4-tertiarybutylcatechol and the like.

Of these, phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol are preferable.
In the solvent composition of this invention, 1 type of phenols may be used as a stabilizer (B), and 2 or more types may be used together.

  The content of phenols in the solvent composition of the present invention is preferably 1 mass ppm to 10 mass%, more preferably 3 mass ppm to 7 mass%, and still more preferably 5 mass ppm, with respect to the total amount of the solvent composition. ˜5 mass%.

  If the content of phenols in the solvent composition is not less than the lower limit of the above preferred range, a sufficient effect for stabilization is exhibited, for example, the value of ΔpH represented by the above formula (1) is 4 or less. And can. If the content is less than or equal to the upper limit of the above preferred range, the surface tension and viscosity are low and the permeability is good, and it 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 the ring (however, an epoxy ring which is a 3-membered cyclic ether) Is excluded). An oxygen atom sandwiched between the carbon atoms in ethers is referred to as an etheric oxygen atom. In the present invention, compounds having both an etheric oxygen atom and an epoxy group are classified as epoxides.

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

  Specific examples of chain ethers include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, diallyl ether, ethyl methyl ether, ethyl propyl ether, ethyl isopropyl ether, 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, methylanisole, anethole, phenetole, 1,1,1-trimethoxyethane, 1,1 , 2-trimethoxyethane, 1,1,1-triethoxyethane, 1,1,2-triethoxyethane and the like.

  As the cyclic ether, a 4- to 6-membered cyclic ether is preferable, and specifically, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, tetraphenyl. Examples include drofuran.

Ethers used as the stabilizer (B) include chain ethers such as ethyl phenyl ether, ethylene glycol monoethyl ether, and cyclic ethers such as 1,4-dioxane, 1,3-dioxane and 1,3,5-trioxane. , Furan, 2-methylfuran and tetrahydrofuran are preferred.
One kind of ethers may be used as the stabilizer (B), or two or more kinds may be used in combination.

  The content of the ethers in the solvent composition of the present invention is preferably 1 mass ppm to 10 mass%, more preferably 10 mass ppm to 7 mass%, still more preferably 0.01 mass% with respect to the total amount of the solvent composition. ˜5 mass%.

  If the content of ethers in the solvent composition is not less than the lower limit of the above preferred range, a sufficient effect for stabilization can be obtained. For example, the value of ΔpH represented by the above formula (1) is 4 or less. And can. When the content is not more than the upper limit of the above preferred range, the surface tension and viscosity are low, the permeability is good, and it is easily evaporated even at room temperature.

(Epoxides)
The epoxide used as the stabilizer (B) in the present invention refers to a compound having one or more epoxy groups which are 3-membered cyclic ethers. As the epoxide used as the stabilizer (B), a compound having high solubility in CFO-1214ya is preferable. Epoxides may have two or more epoxy groups in one molecule. The number of epoxy groups possessed by the epoxide is preferably 1 to 3. Epoxides may be aliphatic epoxides or aromatic epoxides. Epoxides may have a substituent such as a halogen atom, an etheric oxygen atom, or a hydroxy group. Epoxides preferably have 12 or less carbon atoms.

  As epoxides, specifically, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, vinyl glycidyl ether, Examples 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 of this invention, 1 type of epoxides may be used as a stabilizer (B), and 2 or more types may be used together.

  The content of the epoxides in the solvent composition of the present invention is preferably 1 mass ppm to 10 mass%, more preferably 10 mass ppm to 7 mass%, still more preferably 0.01 mass% with respect to the total amount of the solvent composition. ˜5 mass%.

  If the content of epoxides in the solvent composition is at least the lower limit of the above preferred range, a sufficient effect for stabilization can be obtained. For example, the value of ΔpH represented by the above formula (1) is 4 or less. And can. When the content is not more than the upper limit of the above preferred range, the surface tension and viscosity are low, the permeability is good, and it is easily evaporated even at room temperature.

(Pyrrole)
The pyrrole used as the stabilizer (B) refers to a heterocyclic 5-membered compound composed of carbon and nitrogen atoms. As the pyrroles, compounds having high solubility in the solvent (A) are preferable. In addition, pyrroles may have a substituent on either a nitrogen atom or a carbon atom. When pyrrole has a substituent, the number of substituents is preferably 1 to 5. As the substituent, an alkyl group having 1 to 3 carbon atoms is preferable.

  Specific examples of pyrroles include pyrrole, N-methylpyrrole, and N-ethylpyrrole. Of these, pyrrole and N-methylpyrrole are preferred. In the solvent composition of this invention, 1 type of pyrroles may be used as a stabilizer (B), and 2 or more types may be used together.

  The content of pyrroles in the solvent composition of the present invention is preferably 1 mass ppm to 10 mass%, more preferably 3 mass ppm to 7 mass%, and even more preferably 5 mass ppm with respect to the total amount of the solvent composition. ˜5 mass%.

  When the content of pyrroles in the solvent composition is not less than the lower limit of the above preferred range, a sufficient effect for stabilization is exhibited. For example, the value of ΔpH represented by the above formula (1) can be 4 or less. When the content is not more than the upper limit of the above preferred range, the surface tension and viscosity are low, the permeability is good, and it is easily evaporated even at room temperature.

<Nitro compound (C)>
The solvent composition of this invention contains a nitro compound (C) in order to suppress metal corrosion with the said stabilizer (B). Since the nitro compound has an orientation to the metal surface, the nitro compound is aligned on the metal surface, and it is possible to suppress the corrosive action on the metal surface by oxygen contained in the solvent composition or a substance that promotes corrosion. .

The nitro compound (C) in the present invention refers to an organic compound in which a nitro group —NO ₂ is bonded to a carbon atom of the organic compound. The nitro compound (C) is preferably soluble in the solvent (A) and has volatility by itself so that it is volatilized together with the solvent (A) and hardly remains on the surface of the article during cleaning or the like. From this viewpoint, as the C) 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 (C) include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitroethylene, etc. From the above viewpoint, nitromethane, nitroethane, 1-nitropropane, 2 -Nitropropane is more preferred. In the solvent composition of this invention, 1 type of a nitro compound (C) may be used, and 2 or more types may be used together.

  The content of the nitro compound (C) in the solvent composition of the present invention is preferably 1 mass ppm to 10 mass%, more preferably 0.01 to 7 mass% with respect to the total amount of the solvent composition, 0.05 More preferably 5% by mass.

  If content of the nitro compound (C) in a solvent composition is more than the lower limit of the said preferable range, sufficient effect for metal corrosion prevention will be exhibited. When the content is not more than the upper limit of the above preferred range, the surface tension and viscosity are low, the permeability is good, and it is easily evaporated even at room temperature.

The solvent composition of the present invention can be produced by weighing and mixing the components of the solvent (A), stabilizer (B) and nitro compound (C).
The solvent composition of the present invention described above is excellent in solubility of various organic substances, has sufficient drying properties, has a short life in the atmosphere, does not adversely affect the global environment, is stabilized and does not decompose, It is a stable solvent composition that suppresses metal corrosion.

  The solvent composition of the present invention is a solvent composition for cleaning, coating film formation, and dry cleaning that does not adversely affect objects to be processed in a wide range of materials such as metals, plastics, elastomers, glass, and ceramics. Can be used as a thing.

[Cleaning method]
The cleaning method of the present invention is characterized by bringing the solvent composition of the present invention into contact with an article to be cleaned.
Examples of cleaning applications using the solvent composition of the present invention are cleaning of flux, processing oil, wax, mold release agent, dust, etc. adhering to various objects to be cleaned such as ICs, electronic parts, precision machine parts, optical parts, etc. Removal.

  The solvent composition of the present invention can be applied to cleaning articles to be cleaned of various materials such as metal, resin, rubber, and composite materials thereof.

  The cleaning method of the article to be cleaned using the solvent composition of the present invention is not particularly limited except that the solvent composition of the present invention and the article to be cleaned are brought into contact with each other. For example, hand wiping cleaning, immersion cleaning, spray cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, steam cleaning, and a combination of these may be employed. Cleaning conditions such as the time and number of times of contact, the temperature of the solvent composition of the present invention at that time, and a cleaning apparatus can be appropriately selected.

  Furthermore, the solvent composition of the present invention can be used for washing to remove stains on various clothes made of natural fiber or synthetic fiber fabrics.

  The method for cleaning an article to be cleaned using the solvent composition of the present invention is not particularly limited except that the solvent composition of the present invention is used. For example, hand wiping cleaning, immersion cleaning, spray cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, steam cleaning, and a combination of these may be employed. A cleaning device, cleaning conditions, and the like can also be selected as appropriate. If the solvent composition of the present invention is used as a cleaning solvent, it can be used repeatedly for a long time without being decomposed.

The solvent composition of the present invention is suitable as a washing solvent for clothes, that is, a dry cleaning solvent.
The dry cleaning application using the solvent composition of the present invention includes washing and removing dirt adhered to clothing such as shirts, sweaters, jackets, skirts, trousers, jumpers, gloves, mufflers, and stalls.

  Furthermore, the solvent composition of the present invention can be applied to clothing made of fibers such as cotton, hemp, wool, rayon, polyester, acrylic, nylon, etc., and clothing attached with parts such as metal fittings, buttons, fasteners, and sequins. It can be applied to dry cleaning.

  As conventional dry cleaning solvents, petroleum solvents, perchlorethylene, HCFCs, HFCs and HFEs are used as fluorinated solvents. Among them, fluorinated solvents are nonflammable and have a good texture when finished. For dry cleaning with fluorinated solvents, HCFCs such as dichloropentafluoropropane (HCFC-225), 1, 1, HFCs such as 1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2,2,3,4,5,5,5-decafluoropentane (HFC-43-10mee), (Perfluorobutoxy) methane (HFE-449s), (perfluorobutoxy) ethane (HFE-569sf), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (HFE- HFEs such as 347pc-f) are used.

  However, it is known that the fluorine-based solvent affects parts such as buttons, modified products such as sequins, urethane-processed fabrics, clothing pattern print portions, and the like.

  As an effect on the button, discoloration, cracking or deformation may occur. The buttons that are easily affected are buttons made of resin. Of these, those made of acrylic resin are susceptible to discoloration, deformation, and cracking, so care must be taken in dry cleaning. Moreover, the influence to a back foot button is also known among resin buttons which have various shapes. The back foot button is a button having a hole through which the thread is passed on the clothing side of the button. Back foot buttons can be further classified by how to attach the back foot. There are two types of back foot buttons: an adhesive type in which the back foot is bonded and combined with another button part, and a one-push type in which the back foot is combined and fixed through a hole in the button part. With such a back foot button, stress during processing remains in the resin portion of the back foot, and cracking may occur due to dry cleaning. Because of these effects, a step of removing the resin button before the dry cleaning process and attaching it after the dry cleaning process is required, and a solvent that has a small influence on the resin is required.

  In addition, in a garment with a modified sequin, in addition to discoloration of the resin material of the sequin, if the sequin is adhered to the garment with an adhesive, the sequin may be peeled off by dry cleaning. In clothing made of urethane processed fabric or clothing printed with a pattern, discoloration of the urethane processed fabric or printed portion or deterioration of the resin may occur due to dry cleaning.

  CFO-1214ya, which is the main component of the solvent composition of the present invention, has a smaller influence on resin materials, including acrylic resins, than conventional dry cleaning solvents. It has performance superior to that of fluorinated solvents.

  In addition, CFO-1214ya contained in the solvent composition of the present invention contains chlorine atoms in the molecule and has high solubility of dirt, so that it has a wide range of dissolving power and has little influence on the material, 1,1,2-trichloro-1 , 2,2-trifluoroethane (CFC-113) and other CFCs have been found to have the same level of detergency against oil stains.

  Furthermore, in order to use the solvent composition of the present invention as a solvent for dry cleaning, a soap can be blended in order to improve removal performance of water-soluble dirt such as sweat and mud. Soap refers to a surfactant used for dry cleaning, and it is preferable to use a cationic, nonionic, anionic or amphoteric surfactant. CFO-1214ya is known to have a wide solubility in various organic compounds because it has a chlorine atom in its molecule, and it is not necessary to optimize the soap with a solvent like HFEs and HFCs. Soap can be used. As described above, the solvent composition of the present invention can contain at least one surfactant selected from the group consisting of cationic, nonionic, anionic, and amphoteric surfactants.

  Specific examples of the soap include quaternary ammonium salts such as dodecyldimethylammonium chloride and trimethylammonium chloride as the cationic surfactant. Nonionic surfactants include polyoxyalkylene nonyl phenyl ether, polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, phosphoric acid and fatty acid ester, etc. An activator is mentioned. Examples of the anionic surfactant include alkyl sulfates such as polyoxyethylene alkyl sulfates, carboxylates such as fatty acid salts (soap), and sulfonates such as α-olefin sulfonates and lauryl sulfates. Examples of amphoteric surfactants include betaine compounds such as alkyl betaines.

  The content of the soap in the dry cleaning solvent composition is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.2 to 2% by mass, based on the total amount of the solvent composition. %.

  According to the cleaning method of the present invention, by using the solvent composition of the present invention, decomposition of the solvent composition is suppressed, and repeated cleaning over a long period of time becomes possible. Moreover, if the solvent composition of the present invention is used, regeneration operations such as distillation regeneration and filtration regeneration, gas recovery for recovering the vapor of the scattered solvent composition, and the like can be appropriately combined without any problem.

[Formation method of coating film]
The solvent composition of the present invention can be used as a solvent for dilution coating of a nonvolatile organic compound. That is, the method for forming a coating film of the present invention comprises preparing a coating film forming composition by dissolving a non-volatile organic compound in the solvent composition of the present invention, and applying the coating film forming composition on an object to be coated. After coating, the solvent composition is evaporated to form a coating film made of the nonvolatile organic compound.

  Here, the non-volatile organic compound in the present invention refers to a compound having a boiling point higher than that of the solvent composition of the present invention and the organic compound remaining on the surface even after the solvent composition evaporates. Specific examples of the non-volatile organic compound include lubricants such as perfluoropolyether, alkylbenzene, polyol ether, polyol ester, mineral oil, and silicone oil, and rust inhibitors.

The method for forming a coating film of the present invention will be described below by taking as an example the case of forming a lubricant coating film on an object to be coated.
When the solvent composition of the present invention is used as a solvent for diluting a lubricant, the lubricant is dissolved in the solvent composition of the present invention to form a lubricant composition, and the lubricant composition is coated. It is applied onto an object, the solvent composition is evaporated, and a lubricant film is formed on the object to be coated.

  Lubricant means what is used to reduce friction at the contact surface and prevent heat generation and wear damage when the two members move with their surfaces in contact. The lubricant may be in any form of liquid (oil), semi-solid (grease), and solid.

  As the lubricant, a fluorine-based lubricant or a silicone-based lubricant is preferable from the viewpoint of excellent solubility in CFO-1214ya. In addition, a fluorine-type lubricant means the lubricant which has a fluorine atom in a molecule | numerator. Further, the silicone-based lubricant means a lubricant containing silicone.

  The lubricant contained in the lubricant composition may be one type or two or more types. Each of the fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination.

  The content of the lubricant in the lubricant composition (100% by mass) is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and further preferably 0.1 to 20% by mass. . The remainder of the lubricant composition excluding the lubricant is the solvent composition. If the content of the lubricant is within the above range, the film thickness of the coating film when the lubricant composition is applied onto the object to be coated and the thickness of the lubricant film after drying are adjusted to an appropriate range. Cheap.

  According to the method for forming a coating film of the present invention, when used for forming a lubricant coating film, either in the state of the solvent composition of the present invention before dissolving the lubricant, or in the state of the lubricant composition, They can be prevented from being decomposed during storage or use, and the occurrence of metal corrosion can be suppressed even in the presence of metals. Thereby, in the present invention, a highly productive coating can be formed without adversely affecting the global environment.

  Similar to the dilute application of the lubricant, a rust inhibitor is dissolved in the solvent composition of the method of the present invention, applied onto the object to be coated, and the solvent composition of the present invention is evaporated, A rust preventive coating film can also be formed. The same applies to the case where a coating film of other nonvolatile organic compound is formed.

  As the object to be coated, it is possible to adopt objects to be coated of various materials such as metal, plastic, elastomer, glass, ceramics and the like.

  Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited to these examples. Examples 1-14, Examples 21-30, Examples 33-38, Examples 40-44, Examples 46-57 are examples of solvent compositions, Examples 15-20, Examples 31, 32, 39, 45, 58, 59 It is a comparative example of a solvent composition.

[Examples 1 to 59]
(Synthesis of CFO-1214ya)
1,1-dichloro-2,3,3,3-tetrafluoro-1-propene (CFO-1214ya) was obtained by the method of Example 1 of WO2010 / 074254.

  Specifically, 3 g of tetrabutylammonium bromide as a phase transfer catalyst, 83 g (1.485 mol) of potassium hydroxide, and 180 g of water were placed in a 1 L glass reactor equipped with a Dimroth cooled to 0 ° C. And 609 g (3 mol) of a product name “Asahi Klin AK-225” (a mixture of 48 mol% of HCFC-225ca and 52 mol% of HCFC-225cb, manufactured by Asahi Glass Co., Ltd.), and gradually while stirring. The reaction was carried out at 45 ° C. for 1 hour. After the reaction, the organic phase is separated from the reaction crude liquid separated into two phases, an organic phase and an aqueous phase, and the organic phase is distilled by a distillation column having a capacity of 1 L in a kettle and a theoretical plate number of 10 to obtain a crude CFO. -1214ya was obtained.

The obtained crude CFO-1214ya had a purity of 99.5% by mass and a water content of 70 ppm by mass. Thereafter, dehydration treatment was further performed with Molecular Sieves 3A (manufactured by Union Carbide Co., Ltd.) to obtain CFO-1214ya having a water content of 3 mass ppm and a purity of 99.9 mass% (hereinafter referred to as CFO-1214ya (1)). .)
This was repeated until a total amount of CFO-1214ya (1) required for the preparation of the following solvent composition was obtained.

(Preparation of solvent composition)
Stabilizer (B) and nitro compound (C) were added to CFO-1214ya (1) so as to have mass ratios shown in Tables 1 to 5 when used as solvent compositions. 150 g of the solvent compositions of 21 to 30, Examples 33 to 38, Examples 40 to 44, and Examples 46 to 57 were prepared. Moreover, Examples 15-20, Example 31, 32, 39, 45 which does not contain CFO-1214ya (1) shown in Table 1-Table 5, but contains a stabilizer (B) and / or a nitro compound (C), 150 g of solvent compositions 58 and 59 were prepared. In addition, the mass ratio of the stabilizer (B) and the nitro compound (C) shown in Tables 1 to 5 is a mass ratio with respect to the total amount of the solvent composition.

[Evaluation]
1. Stability Test / Metal Corrosion Resistance Test 100 g of the solvent composition of Examples 1 to 59 obtained above was put in a heat-resistant glass bottle containing a test piece of a general cold rolled steel plate (SPCC), and the boiling point of CFO-1214ya ( (46 ° C.) for 7 days. Tables 1 to 5 show the results of measuring the pH immediately after preparation and after storage for 7 days, and the evaluation results of appearance observation of the SPCC surface after storage for 7 days (after the test).

(PH measurement)
40 g of the solvent composition of each example and 40 g of pure water adjusted to pH 7 were placed in a 200 ml separatory funnel and shaken for 1 minute. Thereafter, the upper aqueous layer which was allowed to stand and separated into two layers was separated, and the pH of the aqueous layer was measured with a pH meter (model number: HM-30R, manufactured by Toa DKK Corporation).

  The change in the metal surface before and after the test was visually evaluated by comparing untested products of each metal as comparison targets. The evaluation criteria are as follows.

A: No change before and after the test.
○: The gloss was lost.
Δ: The surface is slightly rusted.
X: Rust is recognized on the entire surface.

  As can be seen from Tables 1 to 5, all of the examples of the present invention show suppression of acidification and suppression of corrosion of metal test pieces with respect to the comparative example. It was revealed that the solvent composition of the present invention can suppress metal corrosion as well as an excellent stabilizing effect of the solvent composition.

2. Accelerated Oxidation Test Solvent compositions of Example 47 (Example), Example 59, and Example 16 (Comparative Example) are further prepared, and the reflux time is 72 in accordance with the accelerated oxidation test of Japanese Industrial Standard JIS K 1508-1982. A test to confirm stability, corrected for time, was performed. Passing oxygen bubbles saturated with water through the 200 ml solvent composition of each of Examples 47, 59, and 16 under the condition that the carbon steel for mechanical structure (S20C) specimen coexists in the gas phase and the liquid phase. The light was irradiated with a light bulb and refluxed by the heat generated by the light bulb.

Table 6 shows the acid content before and after the test and the appearance of the mild steel pieces.
In addition, the evaluation criteria of the test piece after a test were as follows.

A: No change before and after the test.
○: The gloss was lost.
Δ: The surface is slightly rusted.
X: Rust is recognized on the entire surface.

  The solvent composition of Example 47, which is an example of the present invention, was stable without generation of an acid content meaning decomposition, and had no influence on the test pieces in the gas phase and the liquid phase. On the other hand, in Comparative Examples 59 and 16, since the surface of the test piece was rusted, the solvent composition of the present invention has not only an excellent stabilizing effect even under accelerated oxidation test conditions, but also metal corrosion. It became clear that can be suppressed.

3. Evaluation of Cleaning Performance The solvent compositions of Examples 5, 41, 47, 49, 53 (Examples) and Example 16 (Comparative Examples) were further prepared, and the following cleaning tests were performed.

[Cleaning test A]
After immersing a test piece (25 mm × 30 mm × 2 mm) of stainless steel SUS304 in the product name “Daffney Marg Plus HT-10” (made by Idemitsu Kosan Co., Ltd.), which is a cutting oil, in 50 mL of the solvent composition of each example For 1 minute and then pulled up to observe the degree of removal of the cutting oil. Detergency was evaluated according to the following criteria.

“◎ (excellent)”: the cutting oil is completely removed.
“◯ (good)”: Cutting oil is almost removed.
“Δ (somewhat poor)”: A small amount of cutting oil remains.
“× (defect)”: A considerable amount of cutting oil remains.

[Cleaning test B]
The test was conducted in the same manner as the cleaning test A except that the product name “Daphne Marg Plus AM20” (manufactured by Idemitsu Kosan Co., Ltd.) was used as the cutting oil, and the cleaning performance was evaluated according to the same criteria.

[Cleaning test C]
The test was performed in the same manner as the cleaning test A, except that the product name “Daphne Marg Plus HM25” (manufactured by Idemitsu Kosan Co., Ltd.) was used as the cutting oil.

[Cleaning test D]
The cleaning performance was evaluated in the same manner as in the cleaning test A, except that the product name “G-6318FK” (manufactured by Nippon Tool Oil Co., Ltd.) was used as the cutting oil.
The results after each cleaning test are shown in Table 7.

  As shown in Table 7, the solvent compositions of the examples of the present invention of Examples 5, 41, 47, 49, and 53 were applied with cutting oil in the same manner as in Example 16 in which no stabilizer was added in any cleaning test. It was able to be sufficiently removed by washing and showed excellent cleaning properties.

4). Evaluation of Lubricant as Dilution Coating Solvent The solvent compositions of Examples 5, 41, 46, 47, 53 (Examples) and Example 16 (Comparative Examples) were further prepared, and each solvent composition and fluorine-based lubrication were used. The product name “Crytox (registered trademark) GPL102” (manufactured by DuPont Co., Ltd., fluorinated oil) is mixed, and the content of the fluorinated lubricant is 0.5 mass% with respect to the total amount of the solution. A lubricant solution was prepared.

  Next, the obtained lubricant solution is applied in a thickness of 0.4 mm on the surface of an aluminum vapor deposition plate obtained by vapor-depositing aluminum on an iron plate, and air-dried under conditions of 19 to 21 ° C. A lubricant coating was formed on the surface. Evaluation of the solvent composition of the present invention as a lubricant dilution coating solvent was performed as follows.

[Evaluation method]
[Dissolved state]
The dissolution state of the lubricant solution in each example was visually confirmed and evaluated according to the following criteria.
“◎ (excellent)”: immediately dissolves uniformly and becomes transparent.
“◯ (good)”: When shaken, it dissolves uniformly and becomes transparent.
“△ (somewhat bad)”: Slightly cloudy.
“× (defect)”: cloudiness or phase separation.

[Coating state]
The state of the lubricant coating in each example was visually confirmed and evaluated according to the following criteria.
“◎ (excellent)”: A uniform coating film.
“◯ (good)”: An almost uniform coating film.
“Δ (somewhat poor)”: Unevenness is partially observed in the coating film.
“X (defect)”: The coating film is considerably uneven.

[Drying]
The dryness of the lubricant solution at the time of forming the lubricant coating in each example was evaluated based on the following criteria.
“◎ (excellent)”: The solvent evaporates immediately.
“◯ (good)”: The solvent evaporates within 10 minutes.
“Δ (Yes)”: The solvent evaporates in more than 10 minutes within 1 hour.
"X (defect)": The solvent remains even after 1 hour.

  As shown in Table 8, the solvent compositions of the inventive examples of Examples 5, 41, 46, 47, and 53 were soluble in the lubricant in the same manner as in Example 16 without the stabilizer in any application test. It was found that a uniform lubricant coating film can be easily formed because of excellent resistance and sufficient drying properties.

  The solvent composition of the present invention is excellent in the solubility of various organic substances, has sufficient drying properties, does not adversely affect the global environment, is stable and does not decompose, and is resistant to metal corrosion in the presence of metals. It is a stable solvent composition that suppresses and adversely affects articles made of various materials such as metals, plastics, elastomers, and fabrics in a wide range of industrial applications such as cleaning solvents, diluted coating solvents, and propellant compositions. It can be used without.

Claims (12)

  Stabilizer comprising a solvent (A) containing 1,1-dichloro-2,3,3,3-tetrafluoropropene and at least one selected from the group consisting of phenols, ethers, epoxides, and pyrroles A solvent composition comprising (B) and a nitro compound (C).   The content of the stabilizer (B) in the solvent composition is 1 mass ppm to 10 mass%, and the content of the nitro compound (C) is 1 mass ppm to 10 mass%. Solvent composition.   The solvent composition according to claim 1 or 2, wherein a content of the 1,1-dichloro-2,3,3,3-tetrafluoropropene in the solvent (A) is 80 to 100% by mass.   The phenols are selected from the group consisting of phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol and 2-methoxyphenol. The solvent composition according to any one of claims 1 to 3, wherein the solvent composition is one or more.   The ether is 1 selected from the group consisting of ethyl phenyl ether, ethylene glycol monoethyl ether, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran and tetrahydrofuran. The solvent composition according to any one of claims 1 to 4, which is a seed or more.   The epoxide is at least one selected from the group consisting of 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether and diethylene glycol diglycidyl ether. The solvent composition according to any one of claims 1 to 5.   The solvent composition according to any one of claims 1 to 6, wherein the pyrrole is one or more selected from the group consisting of pyrrole and N-methylpyrrole.   The solvent composition according to any one of claims 1 to 7, wherein the nitro compound (C) is at least one selected from the group consisting of nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane.   The solvent composition according to any one of claims 1 to 8, wherein the stabilizer (B) includes phenols and at least one selected from ethers, epoxides, and pyrroles.   A cleaning method, wherein the solvent composition according to any one of claims 1 to 9 is brought into contact with an article to be cleaned.   The cleaning method according to claim 10, wherein the article to be cleaned is clothing.   A non-volatile organic compound is dissolved in the solvent composition according to claim 1 to prepare a coating film-forming composition, and the coating film-forming composition is applied onto an object to be coated. Then, the solvent composition is evaporated to form a coating film made of the non-volatile organic compound.