Solvent composition, aerosol composition, cleaning agent, draining agent, foaming agent, heat transfer medium, organic Rankine cycle system, high-temperature heat pump cycle system, refrigeration cycle system, fire extinguisher composition, method for cleaning articles, and method for producing lubricant solution, all of which use the heat transfer medium.

Abstract

To provide a composition which is excellent in the solubility of various organic substances and is friendly to the Earth's environment, a method of cleaning articles using the composition, a method of producing a lubricant solution using the composition, and a method of producing an article with a lubricant coating film.SOLUTION: A solvent composition includes 1,2-dichloro-3,3-difluoro-1-propene, wherein 1,2-dichloro-3,3-difluoro-1-propene includes cis-1,2-dichloro-3,3-difluoro-1-propene, trans-1,2-dichloro-3,3-difluoro-1-propene, or both cis-1,2-dichloro-3,3-difluoro-1-propene and trans-1,2-dichloro-3,3-difluoro-1-propene.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing 1,2-dichloro-3,3-difluoro-1-propene (hereinafter also referred to as 1232xd), a method for co-producing 1232xd and 1,2,3-trichloro-3-fluoro-1-propene (hereinafter also referred to as 1231xd), a solvent composition containing 1232xd, a method for cleaning an article using the solvent composition, a method for producing a lubricant solution, and an article coated with a lubricant. [Background technology]

[0002] Hydrofluoroolefins (hereinafter referred to as HFO compounds) have a lower global warming potential (GWP) than hydrochlorofluorocarbons (HCFC compounds) such as 1,3-dichloro-1,1,2,2,2-pentafluoropropane (225ca), making them environmentally friendly, and are therefore being used as alternatives in a variety of applications. 1232xd and 1231xd are also types of HFO compounds.

[0003] Little is known about methods for producing 1232xd or 1231xd; the only disclosure in Non-Patent Document 1 is that 1232xd can be obtained by reacting 1,2,3,3-tetrachloro-1-propene (hereinafter also referred to as 1230xd) with one equivalent of antimony trifluoride at 100°C.

[0004] The reaction described in Non-Patent Document 1 requires an equivalent amount of antimony fluoride, which places a heavy burden on the environment and leaves room for improvement for mass production.

[0005] As such, methods for producing 1232xd are not fully developed, and there is a need for more efficient methods for producing 1232xd. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] AMWHLEY AND HWDAVIS J.Am.Chem.Soc.,1948,p.1026-1027 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention has been made in view of the above, and aims to provide an efficient method for producing 1,2-dichloro-3,3-difluoro-1-propene (1232xd). Another objective of the present invention is to provide a solvent composition containing 1232xd, which has excellent solubility for various organic substances and is environmentally friendly, a method for cleaning articles using the solvent composition, a method for producing a lubricant solution using the solvent composition, and a method for producing an article coated with a lubricant. [Means for solving the problem]

[0008] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, thereby completing the present invention. That is, the present invention includes the following inventions.

[0009] [Invention 1] A method for producing 1,2-dichloro-3,3-difluoro-1-propene, comprising the step of fluorinating 1,2,3,3-tetrachloro-1-propene with hydrogen fluoride.

[0010] [Invention 2] The method according to Invention 1, wherein hydrogen fluoride is used in an amount of 2 to 40 moles per mole of 1,2,3,3-tetrachloro-1-propene.

[0011] [Invention 3] 2. The method according to claim 1, wherein the fluorination is carried out in a liquid phase.

[0012] [Invention 4] The method according to Invention 3, wherein the fluorination is carried out at a temperature of 100°C or higher and 200°C or lower.

[0013] [Invention 5] 2. The method according to claim 1, wherein the fluorination is carried out in a gas phase.

[0014] [Invention 6] 6. The method according to claim 5, wherein the fluorination is carried out at a temperature of 100°C or higher and 500°C or lower.

[0015] [Invention 7] The method according to any one of Inventions 1 to 6, wherein the fluorination produces 1,2,3-trichloro-3-fluoro-1-propene together with 1,2-dichloro-3,3-difluoro-1-propene.

[0016] [Invention 8] The method according to Invention 7, wherein the produced 1,2,3-trichloro-3-fluoro-1-propene is subjected to the fluorination.

[0017] [Invention 9] A method for producing 1,2-dichloro-3,3-difluoro-1-propene by fluorinating a composition containing 1,2,3,3-tetrachloro-1-propene and 1,2,3-trichloro-3-fluoro-1-propene with hydrogen fluoride.

[0018] [Invention 10] A method for co-producing 1,2-dichloro-3,3-difluoro-1-propene and 1,2,3-trichloro-3-fluoro-1-propene, comprising the step of fluorinating 1,2,3,3-tetrachloro-1-propene with hydrogen fluoride.

[0019] [Invention 11] 11. The method according to claim 10, wherein hydrogen fluoride is used in an amount of 2 to 40 moles per mole of 1,2,3,3-tetrachloro-1-propene.

[0020] [Invention 12] 11. The method according to claim 10, wherein the fluorination is carried out in a liquid phase.

[0021] [Invention 13] 13. The method according to claim 12, wherein the fluorination is carried out at a temperature of 100°C or higher and 200°C or lower.

[0022] [Invention 14] 11. The method according to claim 10, wherein the fluorination is carried out in the gas phase.

[0023] [Invention 15] 15. The method according to claim 14, wherein the fluorination is carried out at a temperature of 100°C or higher and 500°C or lower.

[0024] [Invention 16] 16. The method according to any one of Inventions 1 to 15, comprising the step of contacting 1,1,2,3,3-pentachloropropane with an aqueous solution of an inorganic base in a liquid phase to obtain 1,2,3,3-tetrachloro-1-propene.

[0025] [Invention 17] 17. A method according to claim 16, comprising the step of reacting 1,2-dichloroethylene with chloroform in the presence of a Lewis acid catalyst to obtain 1,1,2,3,3-pentachloropropane.

[0026] [Invention 18] 18. The method according to claim 17, wherein more than 1 mole of chloroform is used per mole of 1,2-dichloroethylene.

[0027] [Invention 19] A solvent composition comprising cis-1,2-dichloro-3,3-difluoro-1-propene.

[0028] [Invention 20] A solvent composition comprising cis-1,2-dichloro-3,3-difluoro-1-propene and trans-1,2-dichloro-3,3-difluoro-1-propene.

[0029] [Invention 21] A solvent composition comprising trans-1,2-dichloro-3,3-difluoro-1-propene.

[0030] [Invention 22] 22. The solvent composition according to any one of Inventions 19 to 21, further comprising 1,2,3-trichloro-3-fluoro-1-propene.

[0031] [Invention 23] The solvent composition according to any one of Inventions 19 to 22, further comprising at least one organic compound selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, HFCs, and HFEs.

[0032] [Invention 24] 24. The solvent composition according to any one of Inventions 19 to 23, further comprising at least one additive selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators, and corrosion inhibitors.

[0033] [Invention 25] An aerosol composition comprising the solvent composition according to any one of Inventions 19 to 24 and a propellant gas.

[0034] [Invention 26] A method for cleaning an article, comprising the step of contacting the article with the solvent composition or aerosol composition according to any one of inventions 19 to 25.

[0035] [Invention 27] A method for producing a lubricant solution, comprising diluting a lubricant with the solvent composition or aerosol composition according to any one of Inventions 19 to 25 to obtain a lubricant solution.

[0036] [Invention 28] A method for producing a lubricated article, comprising applying a lubricant solution containing a lubricant and the solvent composition or aerosol composition according to any one of Inventions 19 to 25 to a surface of an article, and then volatilizing the solvent composition or aerosol composition from the article, thereby forming a coating film containing the lubricant on the surface of the article.

[0037] [Invention 29] A cleaning agent comprising the solvent composition or aerosol composition according to any one of Inventions 19 to 25.

[0038] [Invention 30] A draining agent comprising the solvent composition or aerosol composition according to any one of Inventions 19 to 25.

[0039] [Invention 31] A blowing agent comprising the solvent composition or aerosol composition according to any one of Inventions 19 to 25.

[0040] [Invention 32] A heat transfer medium comprising the solvent composition according to any one of Inventions 19 to 24.

[0041] [Invention 33] 33. An organic Rankine cycle system using the heat transfer medium according to claim 32.

[0042] [Invention 34] A high-temperature heat pump cycle system using the heat transfer medium according to invention 32.

[0043] [Invention 35] A refrigeration cycle system using the heat transfer medium according to invention 32.

[0044] [Invention 36] A fire extinguisher composition comprising at least 1,2-dichloro-3,3-difluoro-1-propene and a non-flammable gas other than 1,2-dichloro-3,3-difluoro-1-propene. [Effects of the Invention]

[0045] The present invention provides an efficient method for producing 1,2-dichloro-3,3-difluoro-1-propene (1232xd). The present invention also provides a solvent composition containing 1232xd, which has excellent solubility for various organic substances and is environmentally friendly, a method for cleaning articles using the solvent composition, a method for producing a lubricant solution using the solvent composition, and a method for producing an article coated with a lubricant. DETAILED DESCRIPTION OF THE INVENTION

[0046] (Terminology explanation) In this specification, unless otherwise specified, 1230xd refers to the cis-isomer, trans-isomer, or mixture thereof of 1,2,3,3-tetrachloro-1-propene. Also, unless otherwise specified, 1231xd refers to the cis-isomer, trans-isomer, or mixture thereof of 1,2,3-trichloro-3-fluoro-1-propene. Also, unless otherwise specified, 1232xd refers to the cis-isomer, trans-isomer, or mixture thereof of 1,2-dichloro-3,3-difluoro-1-propene. Also, unless otherwise specified, 1,2-dichloroethylene refers to the cis-isomer, trans-isomer, or mixture thereof.

[0047] As used herein, "co-production of 1232xd and 1231xd" means that at least 1232xd and 1231xd are produced by the reaction of the present invention, preferably 0.0001 moles or more of 1231xd is produced per mole of 1232xd, and particularly preferably 0.001 moles or more.

[0048] The present invention is described below. The present invention is not limited to the following embodiments, and any modifications or improvements to the following embodiments based on the ordinary knowledge of a person skilled in the art are also included in the present invention, provided that they do not deviate from the spirit of the present invention.

[0049] <Fluorination of 1,2,3,3-tetrachloro-1-propene (1230xd)> In one embodiment of the present invention, 1230xd is fluorinated using hydrogen fluoride as a fluorinating agent, thereby producing 1232xd.

[0050] Additionally, in one embodiment, 1231xd can be produced by fluorination of 1230xd.

[0051] Additionally, in one embodiment, fluorination of 1230xd can co-produce 1232xd and 1231xd.

[0052] (1230xd) 1230xd is a known compound. A suitable example of a method for producing it will be described below, but this does not preclude the adoption of other methods for producing it.

[0053] In one embodiment of the present invention, in the fluorination of 1230xd to produce 1232xd, 1231xd may be subjected to fluorination along with 1230xd.

[0054] (hydrogen fluoride) In the fluorination of 1230xd, the amount of hydrogen fluoride used is not particularly limited as long as the desired product is obtained by fluorination of 1230xd. Typically, a stoichiometric amount or more is used per mole of 1230xd. There is no particular upper limit, but from the viewpoint of economical production, 40 moles or less is preferred. This amount of hydrogen fluoride used is expressed relative to the charged amount of 1230xd when the reaction method is batch or semi-batch, and is expressed relative to the steady amount of 1230xd present in the reactor when the reaction method is continuous.

[0055] In one embodiment, to produce 1232xd preferentially, 3 to 40 moles, preferably 4 to 30 moles, more preferably 8 to 20 moles of hydrogen fluoride are used per mole of 1230xd.

[0056] In one embodiment, in order to produce 1231xd preferentially, hydrogen fluoride is used in an amount of 1 mole to 20 moles, preferably 2 moles to 15 moles, more preferably 4 moles to 10 moles, per mole of 1230xd.

[0057] In one embodiment, in order to advantageously co-produce 1231xd and 1232xd, hydrogen fluoride is used in an amount of 2 to 40 moles, preferably 3 to 30 moles, more preferably 4 to 20 moles, and even more preferably 8 to 20 moles, per mole of 1230xd.

[0058] <Fluorination of 1230xd in the liquid phase> In one embodiment, the fluorination of 1230xd with hydrogen fluoride can be carried out in the liquid phase.

[0059] The fluorination of 1230xd in the liquid phase may be carried out by any of batch, semi-continuous flow, and continuous flow methods.

[0060] (temperature) The temperature for the fluorination of 1230xd in the liquid phase is not particularly limited as long as the target product can be produced. The fluorination of 1230xd is usually carried out at a temperature of 0°C or higher and 200°C or lower, preferably 100°C or higher and 200°C or lower.

[0061] In one embodiment, since 1232xd can be preferentially produced, the fluorination of 1230xd is carried out at 100°C or higher and 200°C or lower, preferably 110°C or higher and 200°C or lower, particularly preferably 130°C or higher and 200°C or lower, and even more preferably 150°C or higher and 200°C or lower.

[0062] Also, in one embodiment, when it is desired to produce 1231xd predominantly, the fluorination of 1230xd is carried out at a temperature of 0°C or higher and 180°C or lower, preferably 20°C or higher and 150°C or lower, particularly preferably 40°C or higher and 130°C or lower, and even more preferably 60°C or higher and 130°C or lower.

[0063] In one embodiment, when 1232xd and 1231xd are produced simultaneously, the fluorination of 1230xd is carried out at a temperature of 0°C or higher and 200°C or lower, preferably 40°C or higher and 180°C or lower, particularly preferably 80°C or higher and 180°C or lower, and even more preferably 100°C or higher and 150°C or lower.

[0064] (pressure) In the fluorination of 1230xd in the liquid phase, the pressure is not particularly limited as long as the desired product can be produced. Typically, the fluorination of 1230xd in the liquid phase is carried out either under normal pressure (atmospheric pressure) or under increased pressure, preferably under increased pressure. In one embodiment of the present invention, the fluorination of 1230xd is carried out at 0.1 MPaG to 10 MPaG (gauge pressure; the same applies throughout the specification), preferably at 1 MPaG to 6 MPaG, and more preferably at 3 MPaG to 6 MPaG. A pressure of 0.1 MPaG or higher is practical because it is easy to raise the reaction temperature to a suitable level by refluxing unreacted hydrogen fluoride. Furthermore, a pressure of 10 MPaG or lower is economical because the fluorination of 1230xd can be carried out in a general-purpose reactor. However, this does not preclude the fluorination of 1230xd from being carried out at a pressure less than 0.1 MPaG or more than 10 MPaG.

[0065] (solvent) The use of a solvent is not essential for the fluorination of 1230xd in the liquid phase, and it is usually preferable not to use a solvent from the standpoints of productivity and economy. On the other hand, the use of a solvent may be preferable from the standpoints of reaction uniformity and post-reaction operability. When a solvent is used, the type of solvent is not particularly limited as long as it can dissolve the 1230xd raw material. However, organic solvents with a boiling point higher than that of the target product and that are not fluorinated by hydrogen fluoride are preferred. Examples of such solvents include, but are not limited to, tetramethylene sulfone (sulfolane), perfluoroalkanes, perfluoroalkenes, and hydrofluorocarbons. The amount of solvent used is also not particularly limited as long as it can dissolve the 1230xd raw material. For example, the amount of solvent used is preferably 80% by mass or less, more preferably 40% by mass or less, of the 1230xd raw material (or the total amount of 1230xd and 1231xd if 1231xd is included in the raw material), but may be greater than these amounts if desired.

[0066] (catalyst) A catalyst may be used in the fluorination of 1230xd in the liquid phase. However, the use of a catalyst is not essential. When a catalyst is used, examples of the catalyst include Lewis acid catalysts containing metals such as tin and titanium (more specifically, tin chloride (SnCl4), titanium chloride (TiCl4), etc.). The amount of catalyst used is, for example, 0.01 mol % or more and 20 mol % or less based on the 1230xd raw material.

[0067] (Reactor) In the fluorination of 1230xd in a liquid phase, the reactor material used is preferably one that is inert to the raw materials, solvent, and reaction liquid components including the reaction product, and that is acid-resistant. Examples of such materials include stainless steel (e.g., SUS304 and SUS316), Hastelloy™, Inconel™, and Monel™. Such reactors are well known in the art.

[0068] (Example of operation procedure) An example of the procedure for fluorinating 1230xd in the liquid phase is shown below, but is not limited to this. In batch or semi-continuous flow operations, for example, a predetermined amount of a predetermined raw material is introduced into a reactor, and if desired, a predetermined amount of a solvent is introduced, and the reaction is carried out under predetermined conditions. When a catalyst is used, it is preferable to introduce the catalyst into the reactor beforehand or together with the raw material and solvent. The procedure for introducing the raw materials into the reactor is not particularly limited. For example, 1230xd may be introduced into the reactor, and then hydrogen fluoride may be introduced into the reactor. In this case, if a solvent is introduced as desired, some or all of the solvent may be introduced into the reactor before introducing hydrogen fluoride into the reactor, or may be introduced into the reactor simultaneously with the introduction of hydrogen fluoride, or a mixture of hydrogen fluoride and the solvent may be introduced into the reactor.

[0069] In a continuous flow operation, for example, 1230xd and hydrogen fluoride are introduced separately in predetermined amounts into a reactor, and the reaction is carried out under predetermined conditions. An optional solvent may be introduced into the reactor either as 1230xd and hydrogen fluoride separately, or as a 1230xd solution and / or hydrogen fluoride solution.

[0070] (purification) The method for purifying the target product from the reaction product obtained by the fluorination of 1230xd is not particularly limited, and known purification methods can be used. If necessary, the reaction product may be washed with water or alkali to remove chlorine and acid components that may be contained in the reaction product. Furthermore, the reaction product may be subjected to a dehydration treatment or the like to remove water, which may be performed in combination with the treatment to remove chlorine and acid components. Furthermore, distillation or other procedures may also be performed.

[0071] The following is an example of a method for purifying 1232xd or 1231xd from the reaction product obtained by the fluorination of 1230xd, but this is not limiting: For example, the reaction product can be condensed by passing it through a cooled condenser, washed with water and / or an alkaline solution to remove chlorine components, acid components, etc., dried with a desiccant such as zeolite or activated carbon, and then subjected to a conventional distillation procedure to obtain high-purity 1232xd or 1231xd, respectively.

[0072] In one embodiment of the present invention, the unreacted raw materials 1230xd and hydrogen fluoride may be recovered and used for the fluorination of 1230xd. In another embodiment, 1231xd produced by the fluorination of 1230xd may be recovered and used for the fluorination of 1230xd.

[0073] 1232xd and 1231xd exist as liquids at room temperature and pressure.

[0074] Although the above describes the fluorination of 1230xd in the liquid phase, in one embodiment, the fluorination of 1230xd with hydrogen fluoride may be carried out in the gas phase.

[0075] <Fluorination of 1230xd in the gas phase> (catalyst) The fluorination reaction of 1230xd in the gas phase can be carried out either in the presence or absence of a catalyst.

[0076] When fluorination of 1230xd is carried out in the gas phase in the presence of a catalyst, a metal catalyst can be used. Specifically, the metal catalyst contains at least one metal selected from aluminum, vanadium, chromium, titanium, magnesium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, zinc, lanthanum, tantalum, and tungsten. The metal catalyst is preferably a compound of the above metal, more preferably an oxide, halide, or oxyhalide of the above metal. The halogen in the halide may be iodine, bromine, chlorine, or fluorine. The metal catalyst is more preferably a partial or full halide of the above metal, and particularly preferably a partial or full fluoride of the above metal.

[0077] The metal catalyst may be a supported catalyst or an unsupported catalyst. The support for a supported catalyst is not particularly limited, but it is preferable to use carbon, an oxide, an oxyhalide (preferably an oxyfluoride), a halide (preferably a fluoride), or the like of the aforementioned metal. Among such supports, activated carbon, or an oxide, an oxyhalide (particularly preferably an oxyfluoride), or a halide (particularly preferably a fluoride) of at least one metal selected from aluminum, chromium, zirconium, and titanium is particularly preferred. In the case of a supported catalyst, the material supported on the support is a compound of the aforementioned metal, such as a halide (e.g., a fluoride, a chloride, a fluorochloride), an oxyhalide (e.g., an oxyfluoride, an oxychloride, an oxyfluorochloride), or a nitrate of the aforementioned metal. Such metal compounds may be supported alone or in combination. Particularly preferred among the supports are halides and oxyhalides of at least one metal selected from aluminum, chromium, zirconium, and titanium. Specific supports that can be used include chromium nitrate, chromium trichloride, potassium dichromate, titanium trichloride, manganese nitrate, manganese chloride, ferric chloride, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, antimony pentachloride, magnesium chloride, magnesium nitrate, zirconium chloride, zirconium oxychloride, zirconium nitrate, copper(II) chloride, zinc(II) chloride, lanthanum nitrate, and tin tetrachloride. When the support and the support are metal compounds, the support and the support are different metal compounds.

[0078] The metal catalyst is preferably subjected to a fluorination treatment before use in the fluorination reaction of 1230xd. The method for fluorinating the metal catalyst is not particularly limited, but is generally carried out by contacting the metal catalyst with a fluorinating agent such as hydrogen fluoride, fluorinated hydrocarbons, or fluorinated chlorinated hydrocarbons. The fluorination treatment temperature is not particularly limited, but is typically carried out at 200°C or higher. There is no particular upper limit to the fluorination treatment temperature, but it is practically preferable to carry out the treatment at 600°C or lower. In this reaction, for example, fluorinated Al2O3, Cr2O3, Cr2O3 / Al2O3, Cr2O3 / AlF3, Cr2O3 / C, Ti2O3, Zr2O3, Zr2O3 / Ti2O3, CoCl2 / Cr2O3 / Al2O3, NiCl2 / Cr2O3 / Al2O3, CoCl2 / AlF3, NiCl2 / AlF3, FeCl3 / C, SnCl4 / C, TaCl5 / C, SbCl3 / C, AlCl3 / C, and AlF3 / C can be used.

[0079] In one embodiment, when it is desired to predominantly produce 1231xd, the fluorination of 1230xd is preferably carried out in the absence of a catalyst.

[0080] (filling material) The fluorination reaction of 1230xd in the gas phase may be carried out in the presence or absence of a filler. Examples of fillers include carbon such as activated carbon, heat-resistant plastics, ceramics, and zero-valent metals such as stainless steel. Of these, activated carbon is particularly preferred. For example, this reaction can be carried out in the presence of at least a filler selected from carbon, heat-resistant plastics, and ceramics.

[0081] (temperature) In the gas-phase fluorination reaction of 1230xd, the reaction temperature is not particularly limited as long as the target product can be produced. This reaction can be carried out at 100°C or higher, preferably 170°C or higher, and more preferably 220°C or higher. This reaction can also be carried out at 500°C or lower, preferably 480°C or lower, and more preferably 430°C or lower. For example, this reaction can be carried out at 100°C or higher and 500°C or lower, preferably 170°C or higher and 480°C or lower, and more preferably 220°C or higher and 430°C or lower.

[0082] (pressure) In the fluorination reaction of 1230xd in the gas phase, the reaction pressure is not particularly limited. This reaction may be carried out under reduced pressure, normal pressure (atmospheric pressure), or elevated pressure. This reaction can be carried out at 0.0 MPaG to 10 MPaG (gauge pressure, the same applies hereinafter), preferably 0.01 MPaG to 1 MPaG, and more preferably atmospheric pressure to prevent liquefaction of the raw materials and products. Pressures exceeding 10 MPaG are economically undesirable due to the increased cost of designing a pressure-resistant reactor.

[0083] (contact time) In gas-phase flow reactions, productivity is often discussed in terms of the value (seconds) obtained by dividing the reaction zone volume A (mL) by the raw material supply rate B (mL / sec), and this value is called the contact time. If a catalyst is installed in the reaction zone, the apparent volume (mL) of the catalyst is considered to be A above. The value of B indicates the "volume of raw material gas introduced into the reactor per second," but in this case, the raw material gas is considered to be an ideal gas, and the value of B is calculated from the number of moles of the raw material gas, pressure, and temperature. In the reactor, by-production of compounds other than the raw material and the target product, as well as changes in the number of moles, can occur, but these are not taken into account when calculating the "contact time."

[0084] The contact time depends on the raw materials used in the reaction, the reaction temperature, the type of catalyst, etc. Therefore, it is desirable to optimize the contact time by appropriately adjusting the raw material supply rate for each raw material, the set temperature of the reactor, and the type of catalyst.

[0085] In the fluorination reaction of 1230xd, the contact time can be from 0.1 to 300 seconds, preferably from 5 to 150 seconds, and more preferably from 10 to 100 seconds. This contact time may be appropriately changed depending on the reaction pressure.

[0086] (Reactor) In the gas-phase fluorination reaction of 1230xd, the reactor is not particularly limited, but it is preferable to use a reactor suitable for gas-phase reactions. The reactor is preferably made of a heat-resistant and acid-resistant material, such as, but not limited to, stainless steel, Hastelloy™, Monel™, platinum, nickel, carbon, fluororesin, or a material lined with these.

[0087] In this reaction, from the viewpoint of suppressing side reactions and maintaining or improving the activity of the metal catalyst, an inert gas such as nitrogen, argon, or helium, or an oxidizing gas such as chlorine, oxygen, or air may be supplied to the reactor. Such gases may be supplied to the reactor alone or together with the reaction raw materials. These gases may be supplied alone or in the form of a mixed gas. The amount of gas supplied to the reactor is not particularly limited, but is preferably 0.0001 mol % or more and 200 mol % or less, more preferably 0.001 mol % or more and 100 mol % or less, and particularly preferably 0.1 mol % or more and 10 mol % or less, based on the reaction raw materials.

[0088] (Example of operation procedure) An example of the procedure for the fluorination reaction of 1230xd in the gas phase is shown below. The reaction raw materials are introduced into a reactor, and the gas phase reaction is carried out under the conditions described above. The raw materials are preferably in gaseous form when introduced into the reactor. If necessary, the raw materials are gasified in a vaporizer and then introduced into the reactor. When a catalyst is used, it is preferable to prepare it in the reactor in advance.

[0089] The method for purifying the target substance from the reaction product obtained by this reaction is not particularly limited. If necessary, treatment to remove chlorine components, acid components, and the like that may be contained in the reaction product may be performed. Furthermore, water may be removed by a dehydration treatment or the like, or the dehydration treatment may be performed in combination with the treatment to remove chlorine components and acid components. For example, the reaction product may be condensed by passing it through a cooled condenser, washed with water and / or an alkaline solution to remove chlorine components, acid components, and the like, dried with a desiccant such as zeolite or activated carbon, and then distilled to obtain a highly pure target substance.

[0090] As explained above, the fluorination reaction of 1230xd can be carried out not only in the liquid phase but also in the gas phase.

[0091] <Fluorination of 1231xd> In one embodiment of the present invention, 1231xd is fluorinated using hydrogen fluoride as a fluorinating agent. Fluorination of 1231xd can be carried out under the same conditions as for fluorination of 1230xd described above. This allows the production of 1232xd.

[0092] In one embodiment, 1230xd may be fluorinated to produce 1231xd, which may then be fluorinated to produce 1232xd.

[0093] <1230xd manufacturing method> [240da dechlorination oxidation process] As mentioned above, 1230xd is a known compound and can be produced by various methods. However, by adopting the following method for producing 1230xd, it can be efficiently produced using 1,1,2,3,3-pentachloropropane (hereinafter also referred to as 240da) as a starting material. 1230 xd can be manufactured.

[0094] 1230xd can be produced by a method of dehydrochlorinating 240da in the liquid phase in the presence of an aqueous solution of an inorganic base (hereinafter, this method may be referred to as the "240da dechlorination oxidation process").

[0095] (240da) 240da is a known compound and can be produced by various methods, but it can be produced efficiently by the "alkylation step" described below. However, this does not preclude the production of 240da by other methods.

[0096] (aqueous solution of inorganic base) In the dechlorination oxidation step of 240da, the inorganic base is not particularly limited as long as it can dehydrochlorinate 240da. Specific examples include hydroxides of alkali metals and alkaline earth metals, and among these, at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide is preferred.

[0097] The amount of inorganic base used is not particularly limited. It is usually 1 equivalent or more per 240 da. There is no particular upper limit, but it is usually 10 equivalents or less, preferably 5 equivalents or less, more preferably 3 equivalents or less, and particularly preferably 2 equivalents.

[0098] The concentration of the inorganic base in the aqueous solution of the inorganic base is not particularly limited. It is usually 5% by mass or more, preferably 10% by mass. There is no upper limit, but it is usually 40% by mass or less, preferably 30% by mass.

[0099] In one embodiment, the concentration of the inorganic base in the aqueous solution of the inorganic base is, for example, 5% by mass or more and 40% by mass or less, 5% by mass or more and 30% by mass or less, 10% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less.

[0100] In one embodiment, the concentration of the inorganic base in the aqueous solution of the inorganic base is 5% by mass or more and 40% by mass or less, preferably 10% by mass or more and 30% by mass or less.

[0101] When a phase transfer catalyst is used, which will be described later, the aqueous solution of the inorganic base and the phase transfer catalyst may be fed to the reaction system in separate streams, but it is preferable to mix them in advance.

[0102] (phase transfer catalyst) The dechlorination oxidation step of 240 da is preferably carried out in the presence of a phase transfer catalyst. Examples of such a phase transfer catalyst include water-soluble organic compounds such as alcohols, ethers, ketones, and amide compounds, as well as amine salts. These phase transfer catalysts may be used alone or in combination.

[0103] Examples of alcohols used as phase transfer catalysts include alcohols having 1 to 4 carbon atoms.

[0104] Furthermore, examples of ethers that can be used as phase transfer catalysts include 18-crown-6-ether.

[0105] Ketones used as phase transfer catalysts include, for example, acetone and ethyl methyl ketone.

[0106] Examples of the amide compound used as a phase transfer catalyst include DMF and DMAc.

[0107] Examples of the amine salt used as a phase transfer catalyst include tetrabutylammonium salt, trioctylmethylammonium salt, and benzyldimethyloctadecylammonium salt.

[0108] Among these, alcohols having 1 to 4 carbon atoms, 18-crown-6-ether, acetone, and ethyl methyl ketone are preferred as the phase transfer catalyst.

[0109] The amount of the phase transfer catalyst used is not particularly limited as long as the effect of the phase transfer catalyst is obtained. Usually, the amount of the phase transfer catalyst used relative to 240 da is 0.01% by mass or more, preferably 0.1% by mass or more. There is no particular upper limit, but it is usually 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less.

[0110] In one embodiment, the amount of the phase transfer catalyst used may be, for example, 0.01% by mass or more and 40% by mass or less, 0.01% by mass or more and 20% by mass or less, 0.01% by mass or more and 10% by mass or less, 0.01% by mass or more and 0.1% by mass or less, 0.1% by mass or more and 40% by mass or less, 0.1% by mass or more and 20% by mass or less, or 0.1% by mass to 10% by mass or less, relative to 240 da.

[0111] In one embodiment, the amount of the phase transfer catalyst used is 0.01% by mass or more and 40% by mass or less, preferably 0.1% by mass or more and 20% by mass or less, relative to 240 da.

[0112] (temperature) In the 240 da dechlorination oxidation step, the temperature is not particularly limited as long as the target product can be produced under liquid-phase conditions. The temperature is usually 0°C or higher, preferably 5°C or higher, and more preferably 10°C or higher. There is no particular upper limit, but the temperature is usually 150°C or lower, preferably 100°C or lower, and more preferably 60°C or lower.

[0113] In one aspect, the 240 da dechlorination oxidation step is carried out at, for example, 0°C or higher and 150°C or lower, 0°C or higher and 100°C or lower, 0°C or higher and 60°C or lower, 5°C or higher and 150°C or lower, 5°C or higher and 100°C or lower, 5°C or higher and 60°C or lower and 10°C or higher and 150°C or lower, 10°C or higher and 100°C or lower, 10°C or higher and 60°C or lower, 60°C or higher and 150°C or lower, or 60°C or higher and 100°C or lower.

[0114] In one embodiment, the dechlorination oxidation step of 240 da is carried out at a temperature of 0°C or higher and 150°C or lower, preferably 5°C or higher and 100°C or lower, and more preferably 10°C or higher and 60°C or lower.

[0115] (pressure) In the dechlorination-oxidation step at 240 da, the pressure is not particularly limited as long as the target product can be produced under liquid-phase conditions. Typically, the pressure in the dechlorination-oxidation step at 240 da is preferably atmospheric pressure or higher and 10 MPaG or lower, more preferably atmospheric pressure or higher and 1 MPaG or lower. In order to reduce the cost of the reactor, atmospheric pressure is most preferred for the pressure in the dechlorination-oxidation step at 240 da.

[0116] (solvent) The use of a solvent is not essential in the dechlorination oxidation step. This does not prevent the dechlorination oxidation step from being carried out in the presence of a solvent, but when a solvent is used, it is preferable to use one that does not adversely affect the reaction.

[0117] (Reaction method) The dechlorination oxidation step may be carried out by any of a batch system, a semi-continuous flow system, and a continuous flow system.

[0118] (Reactor) In the dechlorination oxidation step, the material of the reactor is not particularly limited. Base-resistant materials are preferred. Specifically, reactors made of glass or stainless steel are preferred. Reactors lined with glass or resin are also preferred. Furthermore, the reactor is preferably equipped with various equipment such as a stirring equipment and a reflux tower.

[0119] When the dehydrochlorination step and the alkylation step described below are carried out in the same reactor, it is preferable that the reactor be equipped with an inlet pipe through which a liquid can be introduced.

[0120] (Example of operation procedure) An example of the operating procedure for the dehydrochlorination step is shown below, but is not limited to this. A phase transfer catalyst and 240 da are charged into a reactor equipped with a reflux tower through which a coolant (e.g., water) flows. An aqueous solution of an inorganic base is introduced into the reactor through a liquid inlet pipe, and the reaction is carried out under specified conditions. The reaction is terminated when 240 da is almost consumed, as determined by gas chromatographic analysis of the sampled reaction product.

[0121] (purification) The resulting 1230xd can be purified by a common purification procedure, for example, by distillation, preferably vacuum distillation, to easily separate raw materials from 1230xd.

[0122] [Alkylation step] 240da can be efficiently produced by reacting 1,2-dichloroethylene with chloroform in the presence of a Lewis acid catalyst (hereinafter, this method may be referred to as the "alkylation step").

[0123] (raw materials) In the alkylation step, the amounts of 1,2-dichloroethylene and chloroform used are not particularly limited as long as 240 da can be produced. Usually, 1 mole or more of chloroform is used per mole of 1,2-dichloroethylene, or 1 mole or more of 1,2-dichloroethylene is used per mole of chloroform.

[0124] In one embodiment, chloroform is used in an amount greater than the stoichiometric amount relative to 1,2-dichloroethylene. This can suppress the production of by-products such as heptachloropentane. Specifically, more than 1 mole, preferably 2 moles or more, and more preferably 3 moles or more of chloroform is used per mole of 1,2-dichloroethylene. There is no particular upper limit, but from the viewpoint of economical production, chloroform is used in an amount of 20 moles or less, preferably 10 moles or less, per mole of 1,2-dichloroethylene.

[0125] In the alkylation process, heptachloropentane is a type of alkylation product of 240da, and is produced as a by-product as the proportion of 240da in the reaction system increases. Therefore, if the raw material chloroform is present in greater amounts than 1,2-dichloroethylene in the reaction system, the production of heptachloropentane as a by-product can be suppressed.

[0126] (Lewis acid catalyst) In the alkylation step, a metal halide can be used as the Lewis acid catalyst. Here, the term "metal halide" refers to a compound having a bond between a metal atom and a halogen atom. The metal atom-halogen atom bond can be confirmed by infrared spectroscopy (IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), or the like. Specifically, such metal halides are preferably halides of at least one metal selected from the group consisting of aluminum, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, tin, antimony, tantalum, and tungsten. Furthermore, the metal halides may be fluorides, chlorides, bromides, or iodides of the above metals, with chlorides of the above metals being preferred. In some embodiments, the Lewis acid catalyst is particularly preferably a chloride of at least one metal selected from the group consisting of aluminum, iron, tin, and antimony. Among these, aluminum chloride and iron chloride are more preferred, and among the iron chlorides, ferric chloride is preferred.

[0127] As the Lewis acid catalyst, it is preferable to use an anhydrous one because of its high catalytic activity. Lewis acid catalyst The anhydride may be used as is, or the hydrate may be treated with a dehydrating agent such as thionyl chloride to obtain the anhydride.

[0128] When a chloride of the above metal is used as the Lewis acid catalyst, the chloride of the metal can be derived by treating the nitrate, carbonate, or the like of the metal or a zero-valent metal powder with hydrogen chloride in advance. Therefore, the nitrate, carbonate, or the like of the above metal or a zero-valent metal powder that has been treated with hydrogen chloride can also be used as the Lewis acid catalyst.

[0129] Furthermore, since the chloroform raw material in the alkylation step has the effect of activating and / or chlorinating zero-valent metals, the Lewis acid catalyst may be zero-valent metal powder.

[0130] In the alkylation step, the amount of Lewis acid catalyst used is not particularly limited as long as it is an effective amount as a catalyst. The optimum amount depends on the type of catalyst, reaction temperature, and other operating conditions. amount Although the amount of Lewis acid catalyst used varies, the amount is usually 0.01% by mass or more, preferably 0.1% by mass or more, based on the 1,2-dichloroethylene raw material. There is no particular upper limit, but it is usually 40% by mass or less, preferably 20% by mass or less.

[0131] In one embodiment, the amount of the Lewis acid catalyst used may be 0.01% by mass or more and 40% by mass or less, 0.01% by mass or more and 20% by mass or less, 0.1% by mass or more and 40% by mass or less, or 0.1% by mass or more and 20% by mass or less, relative to 1,2-dichloroethylene.

[0132] In one embodiment, the amount of the Lewis acid catalyst used is 0.01% by mass or more and 40% by mass or less, and preferably 0.1% by mass or more and 20% by mass or less, relative to 1,2-dichloroethylene. Within this range, the reaction proceeds at a good reaction rate and unexpected side reactions are unlikely to occur.

[0133] (temperature) The temperature in the alkylation step is not particularly limited as long as the target product can be produced under liquid phase conditions. The alkylation step is usually carried out at 0°C or higher, preferably 20°C or higher, and more preferably 40°C or higher. There is no particular upper limit, but the alkylation step is usually carried out at 100°C or lower, preferably 80°C or lower, and more preferably 70°C or lower.

[0134] In one embodiment, the alkylation step is carried out at a temperature of from 0°C to 100°C, from 0°C to 80°C, from 0°C to 70°C, from 20°C to 100°C, from 20°C to 80°C, from 20°C to 70°C, from 40°C to 100°C, from 40°C to 80°C, or from 40°C to 70°C.

[0135] In some embodiments, the alkylation step is carried out at a temperature of 0°C to 100°C, preferably 20°C to 80°C, and more preferably 20°C to 70°C.

[0136] (pressure) In the alkylation step, the pressure is not particularly limited as long as the target product can be produced under liquid phase conditions. The alkylation step is usually carried out at a pressure of 0 MPaG to 1 MPaG, preferably 0 MPaG to 0.5 MPaG, and particularly preferably at atmospheric pressure.

[0137] (solvent) The use of a solvent is not essential in the alkylation step. Alkylation Although the process may be carried out in the presence of a solvent, when a solvent is used, it is preferable to use one that does not adversely affect the reaction.

[0138] (Reaction method) The alkylation step may be carried out by any of batch, semi-continuous flow, and continuous flow methods. Furthermore, since a Lewis acid catalyst is used in the alkylation step, it is preferable to keep the water content as low as possible. In one embodiment, the water content is preferably kept at 1% by mass or less, more preferably 0.1% by mass or less, based on the total mass of the reaction materials.

[0139] (Reactor) In the alkylation step, the material of the reactor is not particularly limited. Since chlorine gas or hydrogen chloride gas may be by-produced, albeit in small amounts, a reactor made of glass or stainless steel is preferred. A reactor lined with glass or resin is also preferred. Furthermore, the reactor is preferably equipped with various facilities such as a liquid introduction pipe, a stirring device, and a reflux tower.

[0140] (Example of operation procedure) An example of the operating procedure for the alkylation step is shown below, but is not limited to this. A Lewis acid catalyst and chloroform are charged into a reactor equipped with a reflux tower through which a coolant (e.g., water) flows. If necessary, the reactor is sealed with an inert gas. 1,2-Dichloroethylene is introduced through a liquid inlet pipe, and the reaction is carried out under specified conditions. The reaction is terminated when 1,2-dichloroethylene is almost consumed, as determined by gas chromatographic analysis of the sampled reaction product.

[0141] After the reaction is completed, an acidic aqueous solution is added to the reaction product. Examples of such an acidic aqueous solution include an aqueous solution of at least one acid selected from the group consisting of hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, formic acid, acetic acid, monofluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, chlorodifluoroacetic acid, trichloroacetic acid, sulfuric acid, and nitric acid.

[0142] (purification) The resulting 240da can be purified by a common purification procedure. For example, raw materials and by-products can be easily separated from 240da by distillation, preferably vacuum distillation. The separated raw materials may be reused as raw materials for the alkylation step.

[0143] The resulting 240da may be used as a raw material for the dechlorination oxidation step without post-treatment such as separation of the Lewis acid catalyst or distillation purification, although this does not preclude post-treatment.

[0144] <Solvent composition> [1232xd] The solvent composition of the present invention contains at least 1232xd. The content of 1232xd is not particularly limited, but in one embodiment, 1232xd is contained in an amount of 20% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 30% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 40% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 50% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 60% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 70% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 80% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 90% by mass or more relative to the total amount of the solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 95% by mass or more of the total solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 97% by mass or more of the total solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 98% by mass or more of the total solvent composition of the present invention. In another embodiment, 1232xd is contained in an amount of 99% by mass or more of the total solvent composition of the present invention. In another embodiment, the solvent composition of the present invention consists solely of 1232xd.

[0145] In the solvent composition of the present invention, the content of 1232xd is 20% by mass or more and 99% by mass or less, 20% by mass or more and 98% by mass or less, 20% by mass or more and 97% by mass or less, 20% by mass or more and 95% by mass or less, 20% by mass or more and 90% by mass or less, 20% by mass or more and 80% by mass or less, 20% by mass or more and 70% by mass or less, 20% by mass or more and 60% by mass or less, 20% by mass or more and 50% by mass or less, 20% by mass or more and 40% by mass or less, 20% by mass or more and 30% by mass or less, 30% by mass or more and 99% by mass or less, 30% by mass or more and 98% by mass or less, 30% by mass or more and 97% by mass or less, 30% by mass or more and 95% by mass or less, 30% by mass or more and 90% by mass or less, 30% by mass or more and 80% by mass or less, 30% by mass or more and 70% by mass or less, 30% by mass or more and 60% by mass or less, 30% by mass or more and 50% by mass or less, 30% by mass or more and 40% by mass or less, 40% by mass or more and 99% by mass or less, 40% by mass or more and 98% by mass or less, 40% by mass or more and 97% by mass or less, 40% by mass or more and 95% by mass or less, 40% by mass or more and 90% by mass or less, 40% by mass or more and 80% by mass or less, 40% by mass or more and 70% by mass or less, 40% by mass or more and 60% by mass or less, 40% by mass or more and 50% by mass or less, 50% by mass or more and 99% by mass or less, 50% by mass or more and 98% by mass or less, 50% by mass or more and 97% by mass or less, 50% by mass or more and 95% by mass or less, 50% by mass or more and 90% by mass or less, 50% by mass or more and 80% by mass or less, 50% by mass or more and 70% by mass or less, 50% by mass or more and 60% by mass or less, 60% by mass or more and 99% by mass or less, 60% by mass or more and 98% by mass or less, 60% by mass or more and 97% by mass or less, 60% by mass or more and 95% by mass or less, 60% by mass or more and 90% by mass or less, 60% by mass or more and 80% by mass or less, 60% by mass or more and 70% by mass or less, 70% by mass or more and 99% by mass or less, 70% by mass or more and 98% by mass or less, 70% by mass or more and 97% by mass or less, 70% by mass or more and 95% by mass or less, 70% by mass or more and 90% by mass or less, 70% by mass or more and 80% by mass or less, 80% by mass or more and 99% by mass or less, 80% by mass or more and 98% by mass or less, 80% by mass or more and 97% by mass or less, 80% by mass or more and 95% by mass or less, 80% by mass or more and 90% by mass or less, 90% by mass or more and 99% by mass or less, 90% by mass or more and 98% by mass or less, 90% by mass or more and 97% by mass or less, 90% by mass or more and 95% by mass or less, 95% by mass or more and 99% by mass or less, 95% by mass or more and 98% by mass or less, 95% by mass or more and 97% by mass or less,It may be 97% by mass or more and 99% by mass or less, 97% by mass or more and 98% by mass or less, 98% by mass or more and 99% by mass or less, or 100% by mass.

[0146] 1232xd is an olefin with a double bond between carbon atoms, which means it has a short lifespan in the atmosphere and a low global warming potential (GWP).In addition, 1232xd has no flash point, so there is a low risk of ignition or fire in the usage environment.

[0147] In one embodiment of the present invention, 1232xd consists exclusively of the cis isomer (1232xd(Z)).

[0148] In another embodiment of the present invention, 1232xd is a mixture of the cis isomer (1232xd(Z)) and the trans isomer (1232xd(E)). The composition of the mixture of 1232xd(Z) and 1232xd(E) is not particularly limited, but may have the following molar ratio: 1232xd(Z):1232xd(E)=0.01~99.99:99.99~0.01 1232xd(Z):1232xd(E)=50.00~99.99:50.00 ~ 0.01 1232xd(Z):1232xd(E)=60.00~99.99:40.00~0.01 1232xd(Z):1232xd(E)=70.00~99.99:30.00~0.01 1232xd(Z):1232xd(E)=80.00~99.99:20.00~0.01 1232xd(Z):1232xd(E)=90.00~99.99:10.00~0.01

[0149] In yet another embodiment of the present invention, 1232xd consists solely of the trans isomer (1232xd(E)).

[0150] [1231xd] The solvent composition of the present invention may contain 1231xd in addition to 1232xd. In one embodiment, a solvent composition containing 1232xd and 1231xd has excellent cleaning performance. When the solvent composition of the present invention contains 1231xd, the lower limit of its content, relative to the total amount of the solvent composition of the present invention, is 0.001% by mass or more in one embodiment, 0.01% by mass or more in another embodiment, 0.1% by mass or more in another embodiment, 1% by mass or more in another embodiment, 3% by mass or more in another embodiment, 5% by mass or more in another embodiment, and 10% by mass or more in another embodiment. Furthermore, the upper limit of the content of 1231xd, relative to the total amount of the solvent composition of the present invention, is 40% by mass or less in one embodiment, 25% by mass or less in another embodiment, and 15% by mass or less in another embodiment.

[0151] In the solvent composition of the present invention, the content of 1231xd is, relative to the total amount of the solvent composition of the present invention, 0.001% by mass or more and 40% by mass or less, 0.001% by mass or more and 25% by mass or less, 0.001% by mass or more and 15% by mass or less, 0.001% by mass or more and 10% by mass or less, 0.001% by mass or more and 5% by mass or less, 0.001% by mass or more and 3% by mass or less, 0.001% by mass or more and 1% by mass or less, 0.001% by mass or more and 0.1% by mass or less, 0.00 1 mass% or more and 0.01 mass% or less, 0.01 mass% or more and 40 mass% or less, 0.01 mass% or more and 25 mass% or less, 0.01 mass% or more and 15 mass% or less, 0.01 mass% or more and 10 mass% or less, 0.01 mass% or more5 Mass% or less, 0.01 mass% or more and 3 mass% or less, 0.01 mass% or more and 1 mass% or less, 0.01 mass% or more and 0.1 mass% or less, 0.1 mass% or more and 40 mass% or less, 0.1 mass% or more and 25 mass% or less, 0.1 mass% or less 15% by mass or less, 0.1% by mass or more and 10% by mass or less, 0.1% by mass or more and 5% by mass, 0.1% by mass or more and 3% by mass, 0.1% by mass or more and 1% by mass or less, 1% by mass or more and 40% by mass or less, 1% by mass or more and 25% by mass % or less, 1 mass% or more and 15 mass% or less, 1 mass% or more and 5 mass% or less, 1 mass% or more and 3 mass% or less, 3 mass% or more and 40 mass% or less, 3 mass% or more and 25 mass% or less, 3 mass% or more and 15 mass% or less Mass% or less, 3 mass% or more and 10 mass% or less, 3 mass% or more and 5 mass% or less, 5 mass% or more and 40 mass% or less, 5 mass% or more and 25 mass% or less, 5 mass% or more and 15 mass% or less, 5 mass% or more and 10 mass% or less, 10 mass% It may be greater than or equal to 40% by mass, less than or equal to 25% by mass, greater than or equal to 10% by mass and less than or equal to 15% by mass, greater than or equal to 15% by mass and less than or equal to 40% by mass, greater than or equal to 15% by mass and less than or equal to 25% by mass, or greater than or equal to 25% by mass and less than or equal to 40% by mass.

[0152] 1231xd is an olefin with a double bond between carbon atoms, which means it has a short lifespan in the atmosphere and a low global warming potential (GWP).In addition, 1231xd has no flash point, so there is a low risk of ignition or fire in the usage environment.

[0153] [Organic compound (A)] The solvent composition of the present invention may contain another organic compound (A) together with 1232xd, or together with 1232xd and 1231xd.

[0154] When the solvent composition of the present invention contains organic compound (A), the lower limit of the content thereof is 0.01% by mass or more in one embodiment, 0.1% by mass or more in another embodiment, 1% by mass or more in another embodiment, 3% by mass or more in another embodiment, 5% by mass or more in another embodiment, and 10% by mass or more in another embodiment, relative to the total amount of the solvent composition of the present invention. The upper limit of the content of organic compound (A) is 80% by mass or less in one embodiment, 70% by mass or less in another embodiment, 60% by mass or less in another embodiment, 50% by mass or less in another embodiment, 40% by mass or less in another embodiment, 30% by mass or less in another embodiment, and 20% by mass or less in another embodiment, relative to the total amount of the solvent composition of the present invention.

[0155] In the solvent composition of the present invention, the content of the organic compound (A) is 0.01% by mass or more and 80% by mass or less, 0.01% by mass or more and 70% by mass or less, 0.01% by mass or more and 60% by mass or less, 0.01% by mass or more and 50% by mass or less, 0.01% by mass or more and 40% by mass or less, 0.01% by mass or more and 30% by mass or less, 0.01% by mass or more and 20% by mass or less, 0.01% by mass or more and 10% by mass or less, 0.01% by mass or more and 5% by mass or less, 0.01% by mass or more and 3% by mass or less, 0.01% by mass or more and 1% by mass or less, 0.01% by mass or more and 0.1% by mass or less, 0.1% by mass or more and 80% by mass or less, 0.1% by mass or more and 70% by mass or less, 0.1% by mass or more and 60% by mass or less, 0.1% by mass or more and 50% by mass or less, 0.1% by mass or more and 40% by mass or less, 0.1% by mass or more and 30% by mass or less, 0.1% by mass or more and 20% by mass or less, 0.1% by mass or more and 10% by mass or less, 0.1% by mass or more and 5% by mass or less, 0.1% by mass or more and 3% by mass or less, 0.It may be 1% by mass or more and 1% by mass or less, 1% by mass or more and 80% by mass or less, 1% by mass or more and 70% by mass or less, 1% by mass or more and 60% by mass or less, 1% by mass or more and 50% by mass or less, 1% by mass or more and 40% by mass or less, 1% by mass or more and 30% by mass or less, 1% by mass or more and 20% by mass or less, 1% by mass or more and 10% by mass or less, 1% by mass or more and 5% by mass or less, 1% by mass or more and 3% by mass or less, 3% by mass or more and 80% by mass or less, 3% by mass or more and 70% by mass or less, 3% by mass or more and 60% by mass or less, 3% by mass or more and 50% by mass or less, 3% by mass or more and 40% by mass or less, 3% by mass or more and 30% by mass or less, 3% by mass or more and 20% by mass or less, 3% by mass or more and 10% by mass or less, 3% by mass or more and 5% by mass or less, 5% by mass or more and 80% by mass or less, 5% by mass or more and 70% by mass or less, 5% by mass or more and 60% by mass or less, 5% by mass or more and 50% by mass or less, 5% by mass or more and 40% by mass or less, 5% by mass or more and 30% by mass or less, 5% by mass or more and 20% by mass or less, 5% by mass or more and 10% by mass or less, 10% by mass or more and 80% by mass or less, 10% by mass or more and 70% by mass or less, 10% by mass or more and 60% by mass or less, 10% by mass or more and 50% by mass or less, 10% by mass or more and 40% by mass or less, 10% by mass or more and 30% by mass or less, 10% by mass or more and 20% by mass or less, 20% by mass or more and 80% by mass or less, 20% by mass or more and 70% by mass or less, 20% by mass or more and 60% by mass or less, 20% by mass or more and 50% by mass or less, 20% by mass or more and 40% by mass or less, 20% by mass or more and 30% by mass or less, 30% by mass or more and 80% by mass or less, 30% by mass or more and 70% by mass or less, 30% by mass or more and 60% by mass or less, 30% by mass or more and 50% by mass or less, 30% by mass or more and 40% by mass or less, 40% by mass or more and 80% by mass or less, 40% by mass or more and 70% by mass or less, 40% by mass or more and 60% by mass or less, 40% by mass or more and 50% by mass or less, 50% by mass or more and 80% by mass or less, 50% by mass or more and 70% by mass or less, 50% by mass or more and 60% by mass or less, 60% by mass or more and 80% by mass or less, 60% by mass or more and 70% by mass or less, or 70% by mass or more and 80% by mass or less.

[0156] Examples of the organic compound (A) include hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, HFCs, HFEs, etc., and these may be one type or two or more types.

[0157] The hydrocarbons used as the organic compound (A) are preferably hydrocarbons having 5 or more carbon atoms. The hydrocarbons may be chain or cyclic, and may be saturated or unsaturated. Specific examples of the hydrocarbons include 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-dimethylpentane, and the like. Examples include 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, tetralin, amylnaphthalene, etc. Among these, n-pentane, cyclopentane, n-hexane, cyclohexane, and n-heptane are preferred.

[0158] The alcohols used as the organic compound (A) are preferably alcohols having 1 to 16 carbon atoms. The alcohols may be chain or cyclic, and may be saturated or unsaturated alcohols. Specific examples of the 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, and 2-heptanol. Examples of alcohols include alcohol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol, 2,6-dimethyl-4-heptanol, nonyl alcohol, and tetradecyl alcohol. Among these, methanol, ethanol, n-propyl alcohol, and isopropyl alcohol are preferred.

[0159] The ketones used as the organic compound (A) are preferably ketones having 3 to 9 carbon atoms. The ketones may be chain or cyclic, and may be saturated or unsaturated ketones. 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, and acetophenone. Among these, acetone and methyl ethyl ketone are preferred.

[0160] The ethers used as the organic compound (A) are preferably ethers having 2 to 8 carbon atoms. The ethers may be linear or cyclic, and may be saturated or unsaturated ethers. Specific examples of the ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, methyl anisole, furan, methyl furan, and tetrahydrofuran. Of these, diethyl ether, diisopropyl ether, and tetrahydrofuran are preferred.

[0161] The esters used as the organic compound (A) are preferably esters having 2 to 19 carbon atoms. The esters may be linear or cyclic, and may be saturated or unsaturated esters. Specific examples of the 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, pentyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, and butyl acetate. butyl acetate, isobutyl isobutyrate, 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, etc. Among these, methyl acetate and ethyl acetate are preferred.

[0162] The chlorocarbons used as the organic compound (A) are preferably chlorocarbons having 1 to 3 carbon atoms. The chlorocarbons may be chain or cyclic, and may be saturated or unsaturated. Specific examples of chlorocarbons include methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, and 1,2-dichloropropane. Among these, methylene chloride, trans-1,2-dichloroethylene, and trichloroethylene are more preferred.

[0163] The HFCs used as the organic compound (A) are preferably linear or cyclic HFCs having 4 to 8 carbon atoms, and more preferably HFCs in which the number of fluorine atoms per molecule is equal to or greater than the number of hydrogen atoms. Specific examples of HFCs include 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, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane. Among these, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane are preferred.

[0164] Preferred HFEs used as the organic compound (A) include C4F9OCH3, C3F7OCH3, 1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro)ethane (HFE-347pc-f), and the like.

[0165] In one embodiment, the organic compound (A) is preferably a compound having no flash point. Examples of compounds having no flash point include HFCs such as 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, and 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, and HFEs such as 1,1,2,2-tetrafluoroethoxy-1-(2,2,2-trifluoro)ethane. When a compound having a flash point is used as the organic compound (A), it is preferably used in a range in which the solvent composition of the present invention does not have a flash point.

[0166] [Additive (B)] The solvent composition of the present invention may contain additive (B) to the extent that the effects of the present invention are not impaired. In one embodiment, the additive (B) is contained in an amount of 0.0001% by mass or more, in another embodiment 0.001% by mass or more, in another embodiment 0.01% by mass or more, in another embodiment 0.1% by mass or more, in another embodiment 1% by mass or more, and in another embodiment 3% by mass or more, relative to the total amount of the solvent composition of the present invention. In another embodiment, the additive (B) is contained in an amount of 10% by mass or less, in another embodiment 5% by mass or less, in another embodiment 3% by mass or less, in another embodiment 1% by mass or less, in another embodiment 0.1% by mass or less, in another embodiment 0.01% by mass or less, and in another embodiment 0.001% by mass or less, relative to the total amount of the solvent composition of the present invention.

[0167] In the solvent composition of the present invention, the content of the additive (B) is, relative to the total amount of the solvent composition of the present invention, 0.0001% by mass or more and 10% by mass or less, 0.0001% by mass or more and 5% by mass or less, 0.0001% by mass or more and 3% by mass or less, 0.0001% by mass or more and 1% by mass or less, 0.0001% by mass or more and 0.1% by mass or more, 0.0001% by mass or more and 0.01% by mass or more, 0.0001% by mass or more and 0.001% by mass or more and 10% by mass or less, 0.001% by mass or more and 5% by mass or less, 0.001% by mass or more and 3% by mass or less, 0.001% by mass or more and 1% by mass or less, 0.001% by mass or more and 0.1% by mass or more Mass% or less, 0.001 mass% or more and 0.01 mass% or less, 0.01 mass% or more and 10 mass% or less, 0.01 mass% or more and 5 mass% or less, 0.01 mass% or more and 3 mass% or less, 0.01 mass% or more and 1 mass% or less, 0.01 mass% or more and 0.1 mass% or less, 0.1 mass% or more and 10 mass% or less, 0.1 mass% % to 5 mass%, 0.1 mass% to 3 mass%, 0.1 mass% to 1 mass%, 1 mass% to 10 mass%, 1 mass% to 5 mass%, 1 mass% to 3 mass%, 3 mass% to 10 mass%, 3 mass% to 5 mass%, or 5 mass% to 10 mass%.

[0168] Examples of the additive (B) include a stabilizer, a surfactant, a flame retardant, a metal passivator, a corrosion inhibitor, etc. It is preferable that these additives (B) are appropriately selected depending on the various uses of the solvent composition of the present invention.

[0169] (stabilizer) In one embodiment, the solvent composition of the present invention contains a stabilizer, which can suppress decomposition of the composition even under severe conditions such as heating conditions. Examples of such stabilizers include nitro compounds, epoxy compounds, phenols, imidazoles, amines, phosphorus compounds, sulfur compounds, nitrogen-containing alcohol compounds, diene compounds, aromatic unsaturated hydrocarbons, isoprenes, propadienes, and terpenes, and these may be used alone or in combination.

[0170] Specific examples of nitro compounds used as stabilizers include aliphatic nitro compounds such as nitromethane, nitroethane, 1-nitropropane, and 2-nitropropane; and aromatic nitro compounds such as nitrobenzene, o-, m-, or p-dinitrobenzene, trinitrobenzene, o-, m-, or p-nitrotoluene, o-, m-, or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, or 3,5-dimethylnitrobenzene, o-, m-, or p-nitroacetophenone, o-, m-, or p-nitrophenol, and o-, m-, or p-nitroanisole.

[0171] Specific examples of epoxy compounds used as stabilizers include monoepoxy compounds such as ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, and 2-ethylhexyl glycidyl ether; and polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, and trimethylolpropane triglycidyl ether.

[0172] Phenols used as stabilizers may have, in addition to a hydroxyl group, a substituent such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, or a halogen atom. Specific examples of phenols include monohydric phenols such as 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, eugenol, isoeugenol, butylhydroxyanisole, phenol, and xylenol, and dihydric phenols such as t-butylcatechol, hydroquinone, methylhydroquinone, t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,5-di-t-butylhydroquinone, 2,2'-methylene-bis(4-methyl-6-t-butylphenol), and 2,2'-methylene-bis(4-ethyl-6-t-butylphenol).

[0173] The imidazoles used as stabilizers are preferably imidazoles having a hydrocarbon group having 1 to 18 carbon atoms as a substituent at the N-position. This hydrocarbon group may be linear or cyclic, and may be a saturated or unsaturated hydrocarbon group. Specific examples of the imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1-(β-oxyethyl)imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2-methylimidazole, and 2-mercaptobenzimidazole.

[0174] Specific examples of amines used as stabilizers include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dibenzylamine, tribenzylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, diphenylamine, diethylhydroxylamine, diphenylamine, 4-aminodiphenylamine, N-phenyl-1-naphthylamine, and phenothiazine.

[0175] Specific examples of phosphorus compounds used as stabilizers include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, and tris(2,4-di-t-butylphenyl) phosphite.

[0176] Specific examples of sulfur compounds used as stabilizers include didodecyl 3,3'-thiodipropionate, ditetradecyl 3,3'-thiodipropionate, 3-(dodecylthio)propionic acid, and dioctadecyl 3,3'-thiodipropionate.

[0177] Specific examples of nitrogen-containing alcohol compounds used as stabilizers include N-stearyl-N,N',N'-tris(polyoxyethylene)-1,3-diaminopropane, ethylenediamine-N,N'-diethanol, ethylenediamine-N,N,N',N'-tetra-2-propanol, triethylenetetramine-N-2-propanol, xylenediamine-N-2-propanol, alkylolamide, oleic acid triethanolamine ester, laurylamine-N,N-diethanol, stearylamine-N,N-diethanol, oleylamine-N,N-diethanol, bis(2-hydroxyethyl)soybean amine, oleic acid dialcoholamide, stearylaminopropylaminoethanol, and 1,3-propylenediamine-N-C12-18-alkyl-N'-ethanol.

[0178] Specific examples of aromatic unsaturated hydrocarbons used as stabilizers include α-methylstyrene and p-isopropenyltoluene.

[0179] (surfactant) In one embodiment, the solvent composition of the present invention contains a surfactant, thereby further improving detergency, interfacial activity, etc. Examples of such surfactants include cationic surfactants, nonionic surfactants, anionic surfactants, and zwitterionic surfactants, and these may be used alone or in combination of two or more types.

[0180] Examples of preferred cationic surfactants include quaternary ammonium salts such as dodecyldimethylammonium chloride and trimethylammonium chloride. Examples of preferred nonionic surfactants include surfactants such as polyoxyalkylene nonylphenyl ethers, polyoxyalkylene alkyl ethers, fatty acid alkanolamides, glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, propylene glycol fatty acid esters, and esters of phosphoric acid and fatty acids. Examples of preferred anionic surfactants include alkyl sulfate ester salts such as polyoxyethylene alkyl sulfate ester salts, carboxylate salts such as fatty acid salts (soap), and sulfonates such as α-olefin sulfonates and lauryl sulfate. Examples of preferred amphoteric surfactants include betaine compounds such as alkyl betaines.

[0181] (Flame retardant) In one embodiment, the solvent composition of the present invention can improve flammability by including a flame retardant, such as phosphates, halogenated aromatic compounds, fluorinated iodocarbons, and fluorinated bromocarbons.

[0182] [Other ingredients] The solvent composition of the present invention may contain other components to the extent that the effects of the present invention are not impaired. The other components are not particularly limited as long as they are not the above-mentioned components, i.e., 1232xd, 1231xd, organic compound (A), or additive (B). For example, they may be impurities derived from the above-mentioned components. Examples of such impurities include, but are not limited to, raw materials used in the manufacturing process of the above-mentioned components.

[0183] <Cleaning agent> The solvent composition of the present invention has suitable fluidity and solubility, and is therefore suitable for removing foreign matter from articles by washing it away or dissolving it.

[0184] Examples of materials for the article include metal, resin, rubber, fiber, glass, ceramics, and composite materials thereof. Examples of composite materials include laminates of metal and resin. Specific examples of the article include, but are not limited to, precision machine parts, electronic materials (printed circuit boards, liquid crystal displays, magnetic recording components, semiconductor materials, etc.), resin-processed parts, optical lenses, textile products, medical instruments, etc.

[0185] Examples of foreign matter include, but are not limited to, oils and fats such as grease, processing oil, silicone oil, oils and fats, flux, wax, ink, mineral oil, and release agents containing silicone oil, as well as dirt such as dust, droplets, and water droplets.

[0186] Cleaning of various vehicles, conveyances and means of transport such as automobiles, motorcycles, bicycles, construction machinery, agricultural machinery, aircraft, railway vehicles and ships (particularly brake cleaners for these vehicles) requires a step of wetting and rinsing away dirt. The composition of the present invention has an appropriate boiling point and can wet and rinse away dirt, making it suitable for such cleaning.

[0187] The method for cleaning an article is not particularly limited, but the article is brought into contact with the solvent composition of the present invention or the aerosol composition described below. Examples include immersing the article to be cleaned in the solvent composition of the present invention to rinse away dirt, wiping with a rag, spray cleaning, and the like, and these methods may be used in combination. A particularly preferred embodiment involves placing the solvent composition in an ultrasonic cleaner, immersing the article to be cleaned in the solution, and performing an ultrasonic cleaning treatment. Another preferred embodiment is spray cleaning, for example, by mixing the solvent composition of the present invention with a propellant gas to form an aerosol and spraying it onto various articles to be cleaned.

[0188] <Aerosol Composition> The solvent composition of the present invention may be mixed with a propellant gas to form an aerosol composition.

[0189] The propellant gas may be a liquefied gas or a compressed gas, such as, but not limited to, LPG (liquefied petroleum gas), DME (dimethyl ether), carbon dioxide, chlorofluorocarbon gas, nitrogen gas, compressed air, or a combination of two or more of the above gases, such as a mixture of LPG and DME or a mixture of LPG and carbon dioxide.

[0190] The aerosol composition of the present invention can be produced by mixing the solvent composition of the present invention with the above-mentioned propellant gas, and can be provided by filling it into a pressure-resistant can.

[0191] <Dry cleaning applications> The solvent composition of the present invention is suitable as a detergent for textile products, i.e., a dry cleaning agent. Examples of textile products include clothing such as shirts, sweaters, jackets, skirts, trousers, jumpers, gloves, scarves, and stoles. The solvent composition of the present invention is particularly suitable for dry cleaning of textile products containing acrylic fibers.

[0192] In the method for dry cleaning a textile product using the solvent composition of the present invention, the composition is brought into contact with the surface of the textile product to remove dirt adhering to the surface of the textile product. In this case, it is preferable to use the surfactant described above as an additive in the composition of the present invention.

[0193] <Diluted solution> The solvent composition or aerosol composition of the present invention is suitable as a dilution solvent for diluting various chemical substances. As one embodiment of the dilution solution, the solvent composition of the present invention can be mixed with a lubricant to form a lubricant solution.

[0194] <Method of producing diluted solution> The various chemical substances with which the solvent composition or aerosol composition of the present invention can be diluted are not particularly limited, but examples thereof include lubricants and rust inhibitors.

[0195] As one embodiment of the method for producing a diluted solution, a method for producing a lubricant solution will be described below. A lubricant solution can be produced by diluting a lubricant with the solvent composition of the present invention. A coated article can be produced by applying the lubricant solution to the surface of an article and then volatilizing the solvent composition of the present invention from the article, thereby forming a coating film containing a lubricant on the surface of the article. The lubricant solution of the present invention can be applied without affecting articles containing resin materials.

[0196] Examples of methods for applying the lubricant solution include application with a brush, application with a spray, application by immersing an article in the lubricant solution, and application methods in which the lubricant solution is brought into contact with the inner wall of a tube or syringe needle by sucking up the lubricant solution.

[0197] Lubricants are used to reduce friction at the contact surfaces and prevent heat generation and wear damage when two components move in contact with each other. Lubricants may be in any form, such as liquid (oil), semi-solid (grease), or solid. Mineral oil-based lubricants, synthetic oil-based lubricants, fluorine-based lubricants, and silicone-based lubricants are preferred because of their excellent solubility in the composition of the present invention. The term "fluorine-based lubricant" refers to a lubricant having a fluorine atom in its molecule. The term "silicone-based lubricant" refers to a lubricant containing silicone. The lubricant solution may contain one type of lubricant or two or more types. The fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination.

[0198] Examples of fluorine-based lubricants include fluorine-based solid lubricants such as fluorine oil, fluorine grease, and polytetrafluoroethylene resin powder. Preferred fluorine-based oils include perfluoropolyethers and oligomers of chlorotrifluoroethylene. Examples include products under the product names "Krytox (registered trademark) GPL102" (manufactured by DuPont Co., Ltd.), "Daifloil #1," "Daifloil #3," "Daifloil #10," "Daifloil #20," "Daifloil #50," "Daifloil #100," and "Demnum S-65" (manufactured by Daikin Industries, Ltd.). Preferred fluorine-based greases are those that use fluorine oils such as perfluoropolyethers and oligomers of chlorotrifluoroethylene as a base oil, blended with polytetrafluoroethylene powder and other thickeners. For example, examples of such products include "Krytox (registered trademark) Grease 240AC" (manufactured by DuPont Co., Ltd.), "Daifloil Grease DG-203", "Demnum L65", "Demnum L100", and "Demnum L200" (all manufactured by Daikin Corporation), "Sumitec F936" (manufactured by Sumitomo Lubricants Co., Ltd.), "Molycoat (registered trademark) HP-300", "Molycoat (registered trademark) HP-500", "Molycoat (registered trademark) HP-870", and "Molycoat (registered trademark) 6169".

[0199] Examples of silicone-based lubricants include silicone oils and silicone greases. Preferred silicone oils include dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, and modified silicone oils with organic groups introduced into the side chains or terminals. Examples include products under the names "Shin-Etsu Silicone KF-96," "Shin-Etsu Silicone KF-965," "Shin-Etsu Silicone KF-968," "Shin-Etsu Silicone KF-868," "Shin-Etsu Silicone KF-99," "Shin-Etsu Silicone KF-50," "Shin-Etsu Silicone KF-54," "Shin-Etsu Silicone HIVACF-4," "Shin-Etsu Silicone HIVACF-5," "Shin-Etsu Silicone KF-56A," and "Shin-Etsu Silicone KF-995" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "SH200," and "MDX4-4159" (all manufactured by Dow Corning Toray Co., Ltd.). Preferred silicone greases are those containing the above-listed silicone oils as a base oil, thickeners such as metal soaps, and various additives. Examples of such silicones include those with the product names "Shin-Etsu Silicone G-30 Series," "Shin-Etsu Silicone G-40 Series," "Shin-Etsu Silicone FG-720 Series," "Shin-Etsu Silicone G-411," "Shin-Etsu Silicone G-501," "Shin-Etsu Silicone G-6500," "Shin-Etsu Silicone G-330," "Shin-Etsu Silicone G-340," "Shin-Etsu Silicone G-350," and "Shin-Etsu Silicone G-630" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "Molycoat (registered trademark) SH33L," "Molycoat (registered trademark) 41," "Molycoat (registered trademark) 44," "Molycoat (registered trademark) 822M," "Molycoat (registered trademark) 111," "Molycoat (registered trademark) High Vacuum Grease," and "Molycoat (registered trademark) Thermal Diffusion Compound" (all manufactured by Dow Corning Toray Co., Ltd.).

[0200] The content of the lubricant in the lubricant solution of the present invention is preferably 0.01% by mass or more and 50% by mass or less, more preferably 0.05% by mass or more and 30% by mass or less, and even more preferably 0.1% by mass or more and 20% by mass or less, based on the total amount of the lubricant solution. If the content of the lubricant is within the above range, the thickness of the coating film when the lubricant solution is applied and the thickness of the lubricant coating film after drying will be within an appropriate range. Easy to adjust to the desired range.

[0201] <For draining agents> In one embodiment, the solvent or aerosol composition of the present invention can be used as a draining agent.

[0202] <Foaming agent applications> The solvent composition or aerosol composition of the present invention can be used as a blowing agent for producing rigid polyurethane foam or polyisocyanurate foam. Solvent or aerosol composition A rigid polyurethane foam or polyisocyanurate foam can be produced by reacting a mixture (premix) of a blowing agent consisting of the above, one or more polyols, a catalyst, a foam stabilizer, etc. with an isocyanate.

[0203] Isocyanates include aromatic, alicyclic, and aliphatic isocyanates, and bifunctional isocyanates are generally used. Examples of such isocyanates include polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, tolylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and dicyclohexylmethane isocyanate, as well as prepolymer-type modified products, nurate-modified products, and urea-modified products thereof. These are used alone or in mixtures.

[0204] The polyol contained in the premix may be a polyether polyol, a polyester polyol, a polyhydric alcohol, a hydroxyl group-containing diethylene polymer, etc., but a polyether polyol is generally used. In addition, the polyester polyol or the polyether polyol may be the main component, or other polyols may be used.

[0205] Examples of polyester polyols include compounds derived from phthalic anhydride, waste polyester, and castor oil, as well as condensation polyester polyols, lactone polyester polyols, and polycarbonate polyols.

[0206] From the viewpoints of compatibility with blowing agents, foamability, foam properties, etc., it is preferable that the hydroxyl value (OH value) of the polyester polyol is 100 mgKOH / g or more and 400 mgKOH / g or less, and that the viscosity is 200 mPa·s / 25°C or more and 4000 mPa·s / 25°C or less.

[0207] Preferred examples of polyether polyols include polypropylene glycol, polytetramethylene glycol, and modified products thereof, as well as those obtained by adding a cyclic ether such as propylene oxide, ethylene oxide, epichlorohydrin, or butylene oxide to an initiator that contains active hydrogen, such as a sugar, a polyhydric alcohol, or an alkanolamine.

[0208] The polyether polyol used usually has a hydroxyl value of 400 mgKOH / g or more and 1000 mgKOH / g or less.

[0209] The catalyst contained in the premix includes an organometallic catalyst and an organic amine catalyst. As the organometallic catalyst, an organotin compound is preferably used, such as stannous octoate, stannous laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, and dioctyltin diacetate. As the organic amine catalyst, a tertiary amine such as triethylenediamine, N-ethylmorpholine, bis(2-dimethylaminoethyl)ether, and N,N',N'-triethylethanolamine is preferably used.

[0210] The foam stabilizer contained in the premix is ​​usually an organic silicon compound surfactant, such as SH-193, SH-195, SH-200, or SRX-253 manufactured by Toray Silicone Co., Ltd., F-230, F-305, F-341, or F-348 manufactured by Shin-Etsu Silicone Co., Ltd., or L-544, L-5310, L-5320, L-5420, or L-5720 manufactured by Nippon Unicar Co., Ltd. , and Examples include TFA-4200 and TFA-4202 manufactured by Toshiba Silicone Co., Ltd.

[0211] Flame retardants contained in the premix are phosphate esters used in rigid polyurethane foams or polyisocyanurate foams, such as tris(2-chloroethyl) phosphate, tris(2-chloropropyl) phosphate, tris(butoxyethyl) phosphate, trismethyl phosphate, trisethyl phosphate, triphenyl phosphate, and tris(isopropylphenyl) phosphate.

[0212] In one embodiment, the premix may contain an ultraviolet inhibitor, a scorch inhibitor, a premix storage stabilizer, etc. This can improve various physical properties of the rigid polyurethane foam or polyisocyanurate foam.

[0213] <Heat transfer medium applications> In one embodiment, the solvent composition of the present invention is suitable as a heat transfer medium for refrigeration cycle systems, high-temperature heat pump systems, organic Rankine cycle systems, etc. In some embodiments, the solvent composition of the present invention is suitable as a cleaning agent for cleaning these cycle systems.

[0214] In this specification, the term "refrigeration cycle system" refers to a vapor compression refrigeration cycle system including at least the following elemental devices: an evaporator, a compressor, a condenser, and an expansion valve, and is primarily intended for cooling. The expansion valve is a device for throttling and expanding a heat transfer medium, and may be a capillary tube. In addition to the above elemental devices, the refrigeration cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery unit, and a non-condensable gas separator. The refrigeration cycle system may be used as a refrigerator, an air conditioning system, or a cooling device.

[0215] In this specification, the term "high-temperature heat pump cycle system" refers to a vapor compression heat pump cycle system including at least the following elemental devices: an evaporator, a compressor, a condenser, and an expansion valve, and is intended primarily for heating. The expansion valve is a device for throttling and expanding a heat transfer medium, and may be a capillary tube. In addition to the above-mentioned elemental devices, the high-temperature heat pump cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery unit, and a non-condensable gas separator. The high-temperature heat pump cycle system may be used as a hot water supply system, a steam generation system, or a heating device. The high-temperature heat pump cycle system may also utilize solar thermal energy, factory waste heat, or the like as a heat source.

[0216] In this specification, the term "organic Rankine cycle system" refers to a Rankine cycle system including at least the component devices of an evaporator, an expander, a condenser, and a booster pump, and is intended primarily to convert thermal energy into electrical energy. In addition to the component devices, the organic Rankine cycle system may also include an internal heat exchanger, a dryer, a liquid separator, an oil recovery unit, and a non-condensable gas separator. The organic Rankine cycle system may also be used as a power generation device that recovers medium- to low-temperature heat. The organic Rankine cycle system may also utilize solar thermal energy, factory waste heat, or the like as a heat source.

[0217] <Fire extinguishing composition> The fire extinguishant composition of the present invention contains at least 1232xd and a non-flammable gas other than 1232xd. 1232xd may be 1232xd(Z), 1232xd(E), or a mixture of 1232xd(Z) and 1232xd(E).

[0218] Examples of the non-flammable gas contained in the fire extinguisher composition include carbon dioxide, nitrogen, helium, argon, krypton, xenon, radon, trifluoromethane, iodinated trifluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, 1-chloro-1,2,2,2-trifluoroethane, pentafluoroethane, 1,1,1,2,2,3,3-hexafluoropropane, 1,1,1,2,3,3,3-hexafluoropropane, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, (E)1,3,3,3-tetrafluoroethane, The fluorocarbon polymer may contain at least one selected from the group consisting of 2-bromo-3,3,3-trifluoropropene, (E) 1-chloro-3,3,3-trifluoropropene, (Z) 1-chloro-3,3,3-trifluoropropene, 2-bromo-3,3,3-trifluoropropene, 1-bromo-3,3,3-trifluoropropene, (Z) 1,1,1,4,4,4-hexafluoro-2-butene, (E) 1,1,1,4,4,4-hexafluoro-2-butene, dodecafluoro-2-methylpentan-3-one, tetradecafluoro-2,4-dimethylpentan-3-one, and tetradecafluoro-2-methylhexan-3-one.

[0219] The non-flammable gas preferably has a boiling point lower than that of 1232xd.

[0220] The proportion of 1232xd relative to the total amount of 1232xd and the non-flammable gas in the fire extinguishant composition can be, for example, 10 mol % or more and 99 mol % or less.

[0221] In one embodiment of the fire extinguishant composition of the present invention, the non-flammable gas may contain carbon dioxide, and the proportion of 1232xd to the total amount of 1232xd and the non-flammable gas may be 20 mol % or more and 99 mol % or less.

[0222] In one embodiment of the fire extinguishant composition of the present invention, the non-flammable gas may contain nitrogen, and the proportion of 1232xd to the total amount of 1232xd and the non-flammable gas may be 20 mol % or more and 99 mol % or less. [Example]

[0223] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

[0224] In the following description, FID% refers to the area % when analyzed by a gas chromatograph with an FID detector.

[0225] <Fluorination of 1230xd> Liquid phase fluorination of 1.1230xd [Example 1-A1] A 200 mL stainless steel autoclave equipped with a condenser and a pressure gauge, through which a 20 °C cooling solution was circulated, was charged with 30 g (0.16 mol) of 1,2,3,3-tetrachloro-1-propene (1230xd) with a purity of 97% FID and 40.0 g (2.00 mol, 1230xd / hydrogen fluoride molar ratio = approximately 1 / 12). The autoclave was then heated to 120 °C. When the pressure exceeded approximately 4 MPaG, the reaction product gas was withdrawn through the needle valve at the condenser outlet to maintain a pressure of 4.0 MPaG to 4.5 MPaG. The withdrawn gas was passed through a fluororesin gas washing bottle containing ice water cooled in an ice-water bath to absorb the acid, and the reaction product organic matter was collected in a glass trap in a dry ice acetone bath. Three hours after the start of the temperature increase, it was confirmed that the pressure no longer increased. The reactor was then purged, and the extracted gas was collected in a fluororesin gas washing bottle containing ice water cooled in an ice-water bath and a glass trap in a dry ice acetone bath. After cooling the reactor, the reaction mixture in the autoclave and the material collected in the glass trap in the dry ice acetone bath were all mixed in a fluororesin gas washing bottle containing ice water, and the combined solution was separated and collected from the aqueous phase using a fluororesin separatory funnel. The amount of organic matter collected was 22.1 g, and the 1232xd geometric isomer ratio in the organic matter was cis:trans = 93:7.

[0226] [Example 1-A2] The reaction was carried out in the same manner as in Example 1-A1, except that the reaction temperature was 140° C. The amount of the recovered organic substance was 21.8 g.

[0227] [Example 1-A3] The reaction temperature was 160°C, and 80.0 g of hydrogen fluoride (4.00 mol, 1230xd / hydrogen fluoride molar ratio = approximately 1 / 24) was added. will be introduced The reaction was carried out in the same manner as in Example 1-A1 except that the amount of the recovered organic matter was 19.6 g.

[0228] [Example 1-A4] The reaction was carried out in the same manner as in Example 1-A2, except that 3 g of tin chloride (SnCl4) was added. The amount of the recovered organic matter was 21.8 g.

[0229] [Example 1-A5] A reaction was carried out in the same manner as in Example 1-A1, except that 454 g (2.53 mol) of 1,2,3,3-tetrachloro-1-propene (1230xd) with a purity of 97 FID% and 1000.0 g (55.0 mol, 1230xd / hydrogen fluoride molar ratio = approximately 1 / 22) were introduced into a 2 L stainless steel autoclave equipped with a condenser and a pressure gauge through which a cooling liquid at 20°C was circulated, and then the autoclave was heated to 160°C. The amount of organic matter recovered was 350 g.

[0230] Table 1 shows the results of gas chromatography analysis for Examples 1-A1 to 1-A5. [Table 1]

[0231] In Table 1, "converted yield" indicates the simple purity converted yield of 1232xd calculated according to the following formula. Simple purity conversion yield of 1232xd = 100 x (amount of recovered organic matter x 1232xd FID% / 1232xd molecular weight) / (1230xd feed amount x 1230xd purity / 1230xd molecular weight)

[0232] In Table 1, "-" indicates that it was not detected.

[0233] 2. Vapor-phase fluorination of 1230xd [Preparation Example 1] Preparation of fluorinated activated alumina 300 g of activated alumina (Sumitomo Chemical KHS-46: particle size 4-6 mm, specific surface area 155 m / g) was weighed out and the powder adhering to the surface was washed with water. 1150 g of 10 wt% hydrofluoric acid was slowly added to the washed alumina, stirred, and allowed to stand for approximately 4 hours. After rinsing with water, it was filtered and dried overnight at room temperature, and then dried in an electric furnace at 200 °C for 2 hours. 150 mL of this dried activated alumina was placed in a 1-inch inner diameter, 40 cm long stainless steel (SUS316) reactor tube. The tube was heated to 200 °C in an electric furnace while flowing nitrogen at a flow rate of 150 cc / min. Hydrogen fluoride was then flowed in together with the nitrogen at a flow rate of 0.1 g / min. The temperature rose as this hydrogen fluoride treatment proceeded, but the flow rates of the nitrogen and hydrogen fluoride were adjusted so that the internal temperature did not exceed 400 °C. Once the heat generation subsided, the nitrogen flow rate was reduced to 30 cc / min, and the set temperature of the electric furnace was increased by 50°C every 30 minutes, finally reaching 400°C, and this state was maintained for 2 hours. In this way, a fluorinated activated alumina (hereinafter also referred to as catalyst 1) was prepared.

[0234] [Preparation Example 2] Preparation of fluorinated chromium-supported alumina catalyst A 20% by mass aqueous solution of chromium chloride was placed in an Erlenmeyer flask, and 100 mL of the fluorinated activated alumina prepared in Preparation Example 1 was immersed therein and held for 3 hours. The alumina was filtered and dried at 70°C under reduced pressure using a rotary evaporator. 100 mL of this chromium-supported alumina was placed in a vacuum oven equipped with an electric furnace. Inner diameter The mixture was packed into a 1-inch, 40 cm long, cylindrical stainless steel (SUS316) reactor tube and heated to 200 °C while flowing nitrogen gas. When water no longer flowed, nitrogen gas was simultaneously supplied at a flow rate of 150 cc / min and hydrogen fluoride at a flow rate of 0.1 g / min. The flow rates of nitrogen and hydrogen fluoride were adjusted so that the internal temperature did not exceed 400 °C. When the hot spot caused by fluorination of the packed chromium-supported alumina reached the outlet end of the reactor tube, the nitrogen flow rate was reduced to 30 cc / min, and the set temperature of the electric furnace was increased by 50 °C every 30 minutes, finally reaching 400 °C and maintained at that temperature for 2 hours. In this way, fluorinated chromium-supported alumina (hereinafter also referred to as Catalyst 2) was prepared.

[0235] [Preparation Example 3] Preparation of fluorinated chromium-loaded activated carbon A 20% by mass aqueous solution of chromium chloride was added to an Erlenmeyer flask, and 100 mL of activated carbon was immersed and left for 3 hours. The activated carbon was filtered and dried at 70°C under reduced pressure using a rotary evaporator. 100 mL of the chromium-loaded activated carbon thus obtained was then heated in a furnace equipped with an electric furnace. Inner diameter The mixture was packed into a 1-inch, 40 cm long, cylindrical stainless steel (SUS316) reactor tube and heated to 200 °C while flowing nitrogen gas. When water no longer flowed, nitrogen gas was simultaneously fed at a flow rate of 150 cc / min and hydrogen fluoride at a flow rate of 0.1 g / min. The flow rates of nitrogen and hydrogen fluoride were adjusted so that the internal temperature did not exceed 400 °C. When the hot spot caused by fluorination of the packed chromium-loaded activated carbon reached the outlet end of the reactor tube, the nitrogen flow rate was reduced to 30 cc / min, and the set temperature of the electric furnace was increased by 50 °C every 30 minutes, finally reaching 400 °C and maintained at that temperature for 2 hours. In this way, a fluorinated chromium-loaded activated carbon (hereinafter also referred to as Catalyst 3) was prepared.

[0236] [Example 1-B1] 50 ml of the catalyst prepared in Preparation Example 2 was loaded into a 1-inch x 40 cm stainless steel (SUS316) reactor equipped with an electric furnace, and the temperature inside the reactor was raised to 250°C while nitrogen gas was flowing at a flow rate of approximately 30 cc / min. The nitrogen feed was stopped, and the vaporized raw materials 1,2,3,3-tetrachloro-1-propene (1230xd) were introduced at a flow rate of 0.20 g / min and hydrogen fluoride at a flow rate of 0.20 g / min. The pressure was atmospheric, and the contact time with the catalyst was 12 seconds. Once the flow rate stabilized, a 100 ml ice-water trap cooled with ice water was installed at the outlet of the reactor, and the organic matter was recovered and the by-product acid was absorbed for approximately 30 minutes, and the weight recovery rate was calculated. The organic components from which the acid had been removed were analyzed by gas chromatography. The composition of the recovered components and the conversion rate of the raw materials were calculated and the results are shown in the table below. 2 The calculation methods for the weight recovery rate and raw material conversion rate are as follows: Weight recovery rate: 100 x (increase in ice water trap) [g] ) / (raw materials [g] +Hydrogen Fluoride [g] ) Raw material conversion rate: 100 x (1 - FID% of raw material composition in recovered organic matter / FID% of raw material composition)

[0237] [Example 1-B2] The same procedure as in Example 1-B1 was carried out except that the temperature inside the reaction tube was set to 200°C.

[0238] [Example 1-B3] The same procedure as in Example 1-B1 was carried out except that the temperature inside the reaction tube was set to 300°C.

[0239] [Example 1-B4] The same procedure as in Example 1-B1 was carried out except that the temperature inside the reaction tube was set to 350°C.

[0240] The results of Examples 1-B1 to 1-B4 are shown in Table 2. [Table 2]

[0241] Referring to Table 2, it can be seen that 1232xd can be synthesized by fluorinating 1230xd in the temperature range of 200°C or higher and 350°C or lower.

[0242] [Example 1-B5] The same procedure as in Example 1-B1 was carried out except that catalyst 3 was packed in place of catalyst 2.

[0243] [Example 1-B6] The same procedure as in Example 1-B1 was carried out except that catalyst 1 was packed in place of catalyst 2.

[0244] [Example 1-B7] The same operation as in Example 1-B1 was carried out, except that 50 ml of activated carbon (Shirasagi G2X4 / 6-1) was packed as a packing material instead of Catalyst 2.

[0245] Table 3 shows the results of Example 1-B1 and Example 1-B5 to Example 1-B7. [Table 3]

[0246] <Synthesis of 240da>

[0247] [Example 2-1] A 2 L three-neck flask equipped with a thermometer, an inlet tube for introducing the liquid, and a Dimroth condenser was charged with 35 g (10 mol%) of powdered aluminum chloride and 1,275 g (10.7 mol) of chloroform, and then sealed with nitrogen. The flask was then heated to an internal temperature of approximately 60 °C in an oil bath, and 256 g (2.64 mol) of 1,2-dichloroethylene was introduced through the inlet tube over 2 hours. The mixture was stirred at 60 °C for 30 minutes, completing the reaction. The reaction solution was cooled to room temperature, washed with 500 mL of 5 wt% hydrogen chloride water, and the organic phase was dried over molecular sieves. The excess chloroform was then separated using an evaporator. This resulted in the recovery of 505 g of 240 da crude product with a purity of 98 FID% (86.5% yield calculated based on purity based on 1,2-dichloroethylene).

[0248] [Example 2-2] The same procedure as in Example 2-1 was carried out, except that the materials used were 7.3 g (20 mol%) of aluminum chloride, 31 g (0.26 mol) of chloroform, and 100 g (1.0 mol) of 1,2-dichloroethylene. As a result, 50 g of crude 240da with a purity of 92 FID% (80.1% yield calculated as purity based on chloroform) was recovered. The only component in the crude 240da other than 240da was heptachloropentane.

[0249] [Example 2-3] The same procedure as in Example 2-1 was carried out, except that the starting materials were 7.3 g (20 mol%) of aluminum chloride, 31 g (0.26 mol) of chloroform, and 25 g (0.26 mol) of 1,2-dichloroethylene. As a result, 44 g of crude 240da with a purity of 96 FID% (75.2% yield calculated based on purity based on 1,2-dichloroethylene) was recovered. The only component in the crude 240da other than 240da was heptachloropentane.

[0250] <1230xd synthesis>

[0251] [Example 3] A 2 L three-neck flask equipped with a thermometer, a dropping funnel, and a Dimroth condenser through which water could flow was charged with 500 g (2.26 mol) of the 240da crude product synthesized in Example 2-1 and 3.0 g of tetrabutylammonium bromide, and cooled to approximately 10°C in an ice-water bath. 550 g (3.4 mol, 1.5 equivalents) of 25 wt% aqueous sodium hydroxide solution was added dropwise via the dropping funnel over 2 hours, and the mixture was stirred at room temperature (approximately 20°C) for 18 hours. The reaction solution was washed with 500 mL of 10 wt% aqueous hydrogen chloride, then washed with water and saturated aqueous bicarbonate, and dried over molecular sieves. This yielded 410 g of crude 1230xd with a purity of 97% FID.

[0252] < Cleaning Sexuality Test>

[0253] [Example 4] A test piece made of SUS-316L (2.8 mm x 10 mm x 30 mm) was immersed in the oil shown in Table 4 to allow the oil to adhere to it. This was then immersed in 10 mL of the solvent shown in Table 4 for 30 seconds, and then air-dried at room temperature (23°C) for 2 minutes. The dried test piece was visually observed, and the cleanability was evaluated according to the following criteria. ◎: Very good. Oil is completely removed. Good: Oil scale is observed in some places, but it has been largely removed. ×: Poor. A lot of oil remains.

[0254] The results are shown in Table 4. [Table 4]

[0255] In Table 4, the types of oil are as follows: Press oil A: Japan Engineering Sakuyu Co., Ltd. PG-3246 Press oil B: Japan Engineering Sakuyu Co., Ltd. PG-3740 Work oil A: Japan Engineering Sakuyu Co., Ltd. CF-879 Work oil B: Japan Engineering Sakuyu Co., Ltd. C-4115 Anti-rust oil: Japan Engineering Sakuyu Co., Ltd. P-5960 Mineral oil: Compressor oil manufactured by Sumiko Lubricants Co., Ltd. Silicone oil: Shin-Etsu Chemical Co., Ltd. KF-96-100CS

[0256] <Solubility test>

[0257] [Example 5] 10 g of the solvent shown in Table 5 and 1 g of the oil shown in Table 5 were added to a 50 mL glass sample bottle and shaken to mix. This was left to stand in a laboratory controlled at room temperature (23°C). After 30 minutes, the state of the solution was visually observed, and the solubility was evaluated according to the following criteria. A: Very good. The oil is completely dissolved and uniform. B: Partially good. Some of the oil is dissolved, but two-phase separation is observed. C: Poor. The oil did not dissolve and two-phase separation was observed.

[0258] The results are shown in Table 5. [Table 5]

[0259] In Table 5, the types of oil are as follows: Press oil A: Japan Engineering Sakuyu Co., Ltd. PG-3246 Press oil B: Japan Engineering Sakuyu Co., Ltd. PG-3740 Work oil A: Japan Engineering Sakuyu Co., Ltd. CF-879 Work oil B: Japan Engineering Sakuyu Co., Ltd. C-4115 Anti-rust oil: Japan Engineering Sakuyu Co., Ltd. P-5960 Mineral oil: Compressor oil manufactured by Sumiko Lubricants Co., Ltd. Silicone oil: Shin-Etsu Chemical Co., Ltd. KF-96-100CS

[0260] [Example 6] All the solvent and oil mixtures used in Example 5 were combined and recovered. From the recovered mixture, simple distillation was performed to obtain 1232xd with a purity of 99GC%.

Claims

1. A solvent composition comprising 1,2-dichloro-3,3-difluoro-1-propene, The 1,2-dichloro-3,3-difluoro-1-propene includes both cis-1,2-dichloro-3,3-difluoro-1-propene and trans-1,2-dichloro-3,3-difluoro-1-propene, A solvent composition, wherein the molar ratio of the cis-1,2-dichloro-3,3-difluoro-1-propene to the trans-1,2-dichloro-3,3-difluoro-1-propene is 93:7 to 99.99:0.

01.

2. 2. The solvent composition according to claim 1, further comprising at least one organic compound selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, HFCs, and HFEs.

3. 3. The solvent composition according to claim 1, further comprising at least one additive selected from the group consisting of stabilizers, surfactants, flame retardants, metal passivators, and corrosion inhibitors.

4. An aerosol composition comprising the solvent composition according to any one of claims 1 to 3 and a propellant gas.

5. A method for cleaning an article, comprising a step of contacting the article with the solvent composition according to any one of claims 1 to 3 or the aerosol composition according to claim 4.

6. A method for producing a lubricant solution, comprising diluting a lubricant with the solvent composition according to any one of claims 1 to 3 or the aerosol composition according to claim 4.

7. A method for producing a lubricated article, comprising applying the lubricant solution according to claim 6 to a surface of an article, and then volatilizing the solvent composition or aerosol composition from the article, thereby forming a coating film containing the lubricant on the surface of the article.

8. A cleaning agent comprising the solvent composition according to any one of claims 1 to 3 or the aerosol composition according to claim 4.

9. A draining agent comprising the solvent composition according to any one of claims 1 to 3 or the aerosol composition according to claim 4.

10. A blowing agent comprising the solvent composition according to any one of claims 1 to 3 or the aerosol composition according to claim 4.

11. A heat transfer medium comprising the solvent composition according to any one of claims 1 to 3.

12. An organic Rankine cycle system using the heat transfer medium according to claim 11.

13. A high-temperature heat pump cycle system using the heat transfer medium according to claim 11.

14. A refrigeration cycle system using the heat transfer medium according to claim 11.

15. A fire extinguisher composition comprising the solvent composition according to any one of claims 1 to 3 and at least a non-flammable gas other than 1,2-dichloro-3,3-difluoro-1-propene.

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