JP2017222731A - Inflammable solvent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inflammable solvent composition or the like that is highly safe and easy to handle, and has excellent characteristics such as washability.SOLUTION: An inflammable solvent composition contains 1,1-dichloro-2,3,3,3-tetrafluoropropene, and acetone, with a mass ratio of 1,1-dichloro-2,3,3,3-tetrafluoropropene to acetone of 85/15-89.7/10.3.SELECTED DRAWING: None

Description

  The present invention relates to a non-flammable solvent composition.

  When manufacturing parts such as IC, electronic parts, precision machine parts, optical parts, etc., when performing each process such as manufacturing process, assembly process, final finishing process, etc., dirt such as flux, processing oil, wax, mold release agent, dust, etc. For example, cleaning is performed using a solvent composition as a cleaning agent.

  As a solvent composition used in such a case, a fluorine-based solvent is known. Examples of the fluorine-based solvent include chlorofluorocarbons such as 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as “CFCs” as appropriate), 2,2-dichloro-1 , 1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1, It contains hydrochlorofluorocarbons such as 2,2,3-pentafluoropropane (hereinafter referred to as “HCFCs”). As the CFCs and HCFCs, those that are nonflammable, have low toxicity and excellent stability, and are excellent in chemical and thermal stability without damaging a base material such as metal, plastic, and elastomer are preferably used.

  However, since CFCs are chemically very stable, they have a long lifetime in the troposphere and diffuse to reach the stratosphere. CFCs that have reached the stratosphere are decomposed by ultraviolet rays and generate chlorine radicals, which may destroy the ozone layer. For this reason, production of CFCs is regulated worldwide, and production has already been abolished in developed countries.

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

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

  As a solvent replacing HFCs, HFEs, and PFCs, a halogenated olefin having a double bond between carbon atoms has been proposed. For example, chlorofluoroolefins (hereinafter referred to as “CFOs”), hydrochlorofluoroolefins (hereinafter referred to as “HCFOs”), hydrofluoroolefins (hereinafter referred to as “HFOs”). Etc. have been proposed. Since these halogenated olefins are easily decomposed, their lifetime in the atmosphere is short. For this reason, the ozone depletion coefficient (ODP) and the global warming potential (GWP) are small, and the influence on the global environment is small. However, since these halogenated olefins are easily decomposed and have poor stability, when used during washing or dilution, metals that coexist with the solvent (for example, storage containers) due to acid generated by acidification or decomposition, etc. , Piping, equipment, etc.) may corrode.

  As the above CFOs, 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter referred to as “CFO-1214ya” as appropriate) is known (for example, see Patent Document 1). .

  Since CFO-1214ya has a short life in the atmosphere, the ozone depletion coefficient is close to zero and the global warming coefficient is one digit. CFO-1214ya has a boiling point of about 46 ° C. (normal pressure) and has excellent drying properties. CFO-1214ya has a low temperature of about 46 [deg.] C. even when steam is generated by boiling, and therefore, CFO-1214ya is less likely to adversely affect heat-sensitive components (e.g., resin components). Furthermore, CFO-1214ya does not have a flash point and has low surface tension and viscosity. In addition, CFO-1214ya has degreasing properties. Thus, CFO-1214ya has excellent characteristics.

  However, CFO-1214ya has poor cleaning properties compared to HCFC-225, which is determined to be completely abolished in 2020, so that it may not be easy to perform sufficient cleaning. In order to improve detergency, it has been proposed to use a solvent composition in which CFO-1214ya is mixed with other solvents such as hydrocarbons, alcohols and ketones as a degreasing agent (for example, Patent Document 2).

International Publication No. 2014/073372 JP2013-224383A

  However, since solvents such as hydrocarbons are flammable, it may be difficult to ensure the safety of solvent compositions containing solvents such as hydrocarbons. Further, when a solvent composition is used as a cleaning agent, evaporation and condensation are repeated, so that the composition ratio of the solvent composition may fluctuate greatly and the cleaning properties may change. For this reason, handling at the time of use is not easy. As a result, it may be difficult to sufficiently improve the cleanability.

  In addition to the above, the solvent composition is used as a draining agent in order to remove moisture adhering to the surface of the component when the component is washed with water such as pure water. Even in the case, there is a problem similar to the above.

  Accordingly, an object of the present invention is to provide a non-flammable solvent composition that is safe and easy to handle and has excellent properties such as cleanability.

The present invention is the following non-flammable solvent composition. In the following, the term “to” means “... or more,...
[1] 1,1-dichloro-2,3,3,3-tetrafluoropropene and acetone are contained, and the mass ratio of 1,1-dichloro-2,3,3,3-tetrafluoropropene to acetone is 85. /15-89.7/10.3, a non-flammable solvent composition.
[2] The non-flammable solvent composition according to [1], wherein the mass ratio is 87.5 / 12.5.
[3] The non-flammable solvent composition according to [1] or [2], further comprising a stabilizer.
[4] The non-flammable solvent composition according to [3], wherein the stabilizer is at least one compound selected from the group consisting of phenols, ethers, epoxides, and amines.
[5] The stabilizer is a phenol, and the phenol is phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methyl. The non-flammable solvent composition according to [4], which is at least one selected from the group consisting of phenol and 2-methoxyphenol.
[6] The stabilizer is an ether, and the ether is 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, tetrahydrofuran, ethyl phenyl ether, The non-flammable solvent composition according to [4] or [5], which is at least one selected from the group consisting of diethylene glycol monoethyl ether.
[7] The stabilizer is an epoxide, and the epoxide is 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, and diethylene glycol diester. The non-flammable solvent composition according to any one of [4] to [6], which is at least one selected from the group consisting of glycidyl ethers.
[8] The stabilizer is an amine, and the amine is pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine, diisopropylamine, N-methylmorpholine, 2-methyl-2-oxazoline, The non-flammable solvent composition according to any one of [4] to [7], which is at least one selected from the group consisting of isoxazole and N-ethylmorpholine.

  According to the present invention, it is possible to provide a non-flammable solvent composition that is safe and easy to handle and has excellent properties such as cleanability.

FIG. 1 is a diagram showing the relationship between liquid phase concentration C1 (mass%) and gas phase concentration C2 (mass%) for acetone.

  Hereinafter, embodiments of the present invention will be described.

  CFO-1214ya is, for example, the presence of a phase transfer catalyst in an alkaline aqueous solution using 1,1-dichloro-2,2,3,3,3-pentafluoropropane (hereinafter referred to as “HCFC-225ca”) as a raw material. It is manufactured by the method of dehydrofluorination under. CFO-1214ya is produced by a method of dehydrofluorination in the gas phase in the presence of a catalyst such as chromium, iron, copper, activated carbon or the like using HCFC-225ca as a raw material (for example, see Japanese Patent No. 3778298). reference). In addition, in each of the above methods, an isomer mixture of HCFC-225ca and 1,3-dichloro-1,2,2,3,3-pentafluoropropane (hereinafter referred to as “HCFC-225cb”). And HCFC-225ca can be produced by a dehydrofluorination method (see, for example, International Publication No. 2010/074254). The purity of the produced CFO-1214ya can be increased by distillation or the like.

[A] Non-flammable solvent composition In the present embodiment, the non-flammable solvent composition is described as 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter, “CFO-1214ya”). ) And acetone, and both are uniformly dissolved in each other. In the non-flammable solvent composition of this embodiment, as described above, CFO-1214ya has a small ozone destruction coefficient and a global warming coefficient, and is excellent in characteristics such as drying properties. In addition, since the non-flammable solvent composition of the present embodiment is a mixed solvent in which acetone is mixed with CFO-1214ya, the detergency is improved and it can be suitably used as a draining agent.

Although details will be described later, the non-flammable solvent composition of the present embodiment has a mass ratio of 1,1-dichloro-2,3,3,3-tetrafluoropropene to acetone of 87.5 / 12.5. In some cases, the relative volatility α represented by the following formula (1) is 1. That is, when the content ratio R1 of acetone is 12.5 mass% and the content ratio R2 of CFO-1214ya is 87.5 mass% (R1 = 12.5 mass%, R2 = 87.5 mass%) Becomes an azeotropic mixture (azeotropic point 43.5 ° C.). When the relative volatility α is 0.9 or more and 1.1 or less, the composition changes little because it is close to the azeotropic composition (α = 1). For this reason, in the non-flammable solvent composition of the present embodiment, CFO-1214ya and acetone are mixed so that the relative volatility α is in the range of 0.9 to 1.1. Specifically, the non-flammable solvent composition of the present embodiment has a mass ratio of 1,1-dichloro-2,3,3,3-tetrafluoropropene to acetone of 85/15 to 89.7 / 10. 3. In other words, the non-flammable solvent composition of the present embodiment has a CFO-1214ya content ratio R1 in the range of 85.0 mass% to 89.7 mass%, and an acetone content ratio R2 of 10.3 mass%. It is the range of the mass% or more and 15.0 mass% or less. Therefore, since the non-flammable solvent composition of the present embodiment is close to the azeotropic composition, the composition ratio fluctuation is small, and handling is easy when used as a cleaning agent or the like. In the formula (1), RL1 is mass% of acetone in the liquid phase part, RL2 is mass% of CFO-1214ya in the liquid phase part, and RG1 is mass% of acetone in the gas phase part. Yes, RG2 is the mass% of CFO-1214ya in the gas phase.
(Formula for obtaining relative volatility α)
α = (RL2 / RL1) / (RG2 / RG1) (1)

  As described above, the non-flammable solvent composition of this embodiment is a mixed solvent obtained by mixing flammable acetone with CFO-1214ya, but does not have a flash point. Specifically, the non-flammable solvent composition of the present embodiment does not ignite in the Cleveland open test method (JIS K 2265-4). For this reason, the non-flammable solvent composition of the present embodiment can ensure high safety.

  In the present embodiment, the non-flammable solvent composition is particularly preferably an azeotropic mixture. That is, in the non-flammable solvent composition of this embodiment, the content ratio R1 of acetone is preferably 12.5% by mass, and the content ratio R2 of CFO-1214ya is preferably 87.5% by mass. When the non-flammable solvent composition is an azeotrope, since there is almost no change in composition when used as a cleaning agent or the like, handling becomes easier, and operations such as cleaning can be performed effectively.

  In this embodiment, the non-flammable solvent composition described above may further contain a stabilizer. The stabilizer prevents CFO-1214ya from being decomposed by oxygen, and makes CFO-1214ya stable. For this reason, when a stabilizer is contained, pH change is suppressed even by storage in the presence of oxygen.

  Specifically, the stabilizer is a compound whose pH change rate Rc is determined to be 20 or less by the stability test described below. The stabilizer is preferably a compound having a pH change rate of 10 or less, more preferably a compound having a pH of 5 or less. In the stability test, the test solution is adjusted (100 g) by containing a stabilizer in CFO-1214ya (purity 99% by mass or more). Here, the test solution is adjusted so that the concentration of the stabilizer is 1% by mass. And the test liquid is preserve | saved at room temperature (21-23 degreeC) for 3 days. The change rate Rc of pH is calculated based on the pH value (V0) immediately after adjustment and the pH value (V1) after storage, as shown in the following formula (2).

  Rc = (| V0−V1 | / V0) × 100 (2)

  In this embodiment, it is preferable that the content rate of a stabilizer is 1 mass ppm or more with respect to CFO-1214ya. When the content of the stabilizer is smaller than the above lower limit value, decomposition of CFO-1214ya may not be sufficiently suppressed. Further, the content of the stabilizer is preferably 10% by mass or less. When the content of the stabilizer is larger than the above upper limit value, the characteristics of CFO-1214ya (characteristics with low surface tension and viscosity, characteristics with high permeability, characteristics that easily evaporate at room temperature, etc.) may be impaired. At the same time, the stabilization of CFO-1214ya may not be further improved. The content ratio of the stabilizer is more preferably in the range of 3 mass ppm to 7 mass%, and most preferably in the range of 5 mass ppm to 5 mass%.

  In the present embodiment, the stabilizer is preferably at least one compound selected from the group consisting of phenols, ethers, epoxides, and amines. Among the above, phenols suppress the decomposition of CFO-1214ya by the action of preventing the oxidation of CFO-1214ya. Moreover, amines suppress the decomposition | disassembly of CFO-1214ya by an acidic substance by the effect | action which neutralizes the acidic substance produced by decomposition | disassembly.

  The stabilizer is preferably a plurality of compounds selected from a plurality of different compounds among the plurality of compounds described above. For example, it is preferable to select a compound of a phenol and a compound of a compound other than the phenol as a stabilizer.

  In the non-flammable solvent composition containing the stabilizer, the content ratio of CFO-1214ya is preferably 80% by mass or more, and more preferably 90% by mass or more. The stabilizer is preferably one that dissolves in a non-flammable solvent composition containing CFO-1214ya and acetone.

  In the present embodiment, the non-flammable solvent composition may contain other compounds as required in addition to the stabilizer.

[B] Stabilizer The details of each compound that functions as a stabilizer will be sequentially described below.

[B-1] Phenols Phenols are aromatic hydroxy compounds in which one or more hydroxy groups are substituted on the aromatic hydrocarbon nucleus. In the present embodiment, the phenols contained as a stabilizer preferably have an aromatic hydrocarbon nucleus as a benzene nucleus (benzene ring).

  Phenols include compounds in which a substituent such as a hydrocarbon group, an alkoxy group, an acyl group, a carbonyl group, or a halogen is replaced with a hydrogen atom in an aromatic hydrocarbon nucleus. Here, examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkoxy group, an acyl group, an aromatic hydrocarbon group, and an aralkyl group. In the phenols contained as a stabilizer in the present embodiment, the number of carbon atoms of each substituent of the alkyl group, alkenyl group, alkoxy group, acyl group, and carbonyl group is preferably 6 or less. And it is preferable that carbon number of each substituent of an aromatic hydrocarbon group and an aralkyl group is 10 or less. Of the hydrocarbon groups, an alkyl group or an alkenyl group is preferably a substituent, and an alkyl group is particularly preferable.

  In addition to this, in the phenols contained as a stabilizer in the present embodiment, it is preferable that an alkyl group or an alkoxy group is substituted at the ortho position with respect to the hydroxy group substituted on the aromatic hydrocarbon nucleus. . The alkyl group substituted at the ortho position is preferably a branched alkyl group such as a tertiary butyl group. In this case, both of the two ortho positions may be substituted with an alkyl group.

  For example, phenols contained as stabilizers are phenol, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, 1,3,5-benzenetriol, 2,6-ditertiary butyl. -4-methylphenol, 2,4,6-tritertiary butylphenol, 2-tertiary butylphenol, 3-tertiary butylphenol, 4-tertiary butylphenol, 2,4-ditertiary butylphenol, 2,6-ditertiary butylphenol 4,6-ditertiary butylphenol, 1-cresol, 2-cresol, 3-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 2 , 3,6-trimethyl Phenol, 2,4,6-trimethylphenol, 2,5,6-trimethylphenol, 3-isopropylphenol, 2-isopropyl-5-methylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2 -Ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-propoxyphenol, 3-propoxyphenol, 4-propoxyphenol, and tertiary butylcatechol.

  Among the above-mentioned phenols, phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol, and 2-methoxyphenol are Particularly preferred as a stabilizer.

  The proportion of phenol as a stabilizer is preferably in the range of 1 ppm by mass to 10% by mass, more preferably in the range of 5 ppm by mass to 5% by mass, with respect to CFO-1214ya. A range of 10 mass ppm or more and 1 mass% or less is more preferable. When the content ratio is smaller than the lower limit, CFO-1214ya may not be sufficiently stabilized. In addition, when the content ratio is larger than the above lower limit value, characteristics of CFO-1214ya (characteristics with low surface tension and viscosity, characteristics with high permeability, characteristics that easily evaporate at room temperature, etc.) may be impaired. The stabilization of CFO-1214ya may not be further improved.

[B-2] Ethers Ethers are organic compounds having an ether bond, and include chain ethers and cyclic ethers (excluding epoxy rings that are 3-membered cyclic ethers). Ethers include compounds having a plurality of ether bonds. The ethers contained as a stabilizer in the present embodiment preferably have 12 or less carbon atoms. Moreover, the hydrocarbon group which comprises an ether bond in ethers may be substituted by substituents, such as a halogen atom and a hydroxy group. Here, the compound having an epoxy group is classified not as an ether but as an epoxide.

  For example, ethers contained as stabilizers include dimethyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether, diallyl ether, ethyl methyl ether, ethyl propyl ether, ethyl isopropyl ether, ethyl Isobutyl ether, ethyl isopentyl ether, ethyl vinyl ether, allyl ethyl ether, ethyl phenyl ether, ethyl naphthyl ether, ethyl propargyl ether, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, ethylene glycol monomethyl Ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether , Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, anisole, anethole, trimethoxyethane, triethoxyethane, furan, 2-methylfuran and tetraph It is Drofuran.

  Among the above ethers, cyclic ethers that are 4- to 6-membered rings are preferred as stabilizers. In particular, 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, tetrahydrofuran, ethyl phenyl ether, and diethylene glycol monoethyl ether are preferable as the stabilizer.

  The proportion of ethers as a stabilizer is preferably in the range of 1 ppm by mass to 10% by mass, more preferably in the range of 10 ppm by mass to 7% by mass, relative to CFO-1214ya. A range of 0.01% by mass or more and 5% by mass or less is more preferable. When the content ratio is smaller than the lower limit, CFO-1214ya may not be sufficiently stabilized. In addition, when the content ratio is larger than the above lower limit value, characteristics of CFO-1214ya (characteristics with low surface tension and viscosity, characteristics with high permeability, characteristics that easily evaporate at room temperature, etc.) may be impaired. The stabilization of CFO-1214ya may not be further improved.

[B-3] Epoxides Epoxides are organic compounds having an epoxy group that is a 3-membered ether. Epoxides include compounds having a plurality of epoxy groups. Epoxides include compounds having a substituent such as a halogen atom, an etheric oxygen atom, or a hydroxy group. Epoxides contained as a stabilizer in the present embodiment preferably have 12 or less carbon atoms.

  For example, epoxides contained as stabilizers are 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl. Ether, vinyl glycidyl ether, allyl glycidyl ether, diethylene glycol diglycidyl ether, epichlorohydrin, d-limonene oxide, and l-limonene oxide.

  Of the above epoxides, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, and diethylene glycol diglycidyl ether are particularly preferred as stabilizers.

  The ratio of containing epoxides as a stabilizer is preferably in the range of 1 ppm by mass to 10% by mass, more preferably in the range of 10 ppm by mass to 7% by mass, with respect to CFO-1214ya. A range of 0.01% by mass or more and 5% by mass or less is more preferable. When the content ratio is smaller than the lower limit, CFO-1214ya may not be sufficiently stabilized. In addition, when the content ratio is larger than the above lower limit value, characteristics of CFO-1214ya (characteristics with low surface tension and viscosity, characteristics with high permeability, characteristics that easily evaporate at room temperature, etc.) may be impaired. The stabilization of CFO-1214ya may not be further improved.

[B-4] Amines Amines are organic compounds having primary to tertiary amino groups. Amines include both acyclic and cyclic (cyclic compounds in which the nitrogen atom of an amino acid is an atom constituting the ring). Acyclic amines are, for example, aliphatic amines and aromatic amines. Cyclic amines are 4-6 membered ring compounds whose number of nitrogen atoms which constitutes a ring is 1-3, for example. The amines contained as a stabilizer preferably have 16 or less carbon atoms, particularly preferably 10 or less. In addition, the group bonded to the nitrogen atom of the secondary amino group and the tertiary amino group is preferably an alkyl group or a hydroxyalkyl group having 6 or less carbon atoms.

  For example, amines contained as stabilizers are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine. , Isobutylamine, diisobutylamine, secondary-butylamine, tertiary-butylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, 2-ethylhexylamine, allylamine, diallylamine, triallylamine, aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, pyridine, picoline, morpholine, N-methylmorpholine, benzylamine, diben Ruamine, α-methylbenzylamine, propylenediamine, diethylhydroxyamine, pyrrole, N-methylpyrrole, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, ethanolamine, diethanolamine, triethanolamine, propanolamine, di Propanolamine, isopropanolamine, diisopropanolamine, N-methylethanolamine, N, N-dimethylethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, diphenylamine, 2-methyl-2-oxazoline, isoxazole, and Ethylenediamine.

  Of the above amines, alkylamines and cyclic amines are preferred as stabilizers. In particular, pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine, diisopropylamine, N-methylmorpholine, 2-methyl-2-oxazoline, isoxazole, and N-ethylmorpholine are preferred as stabilizers. .

  The proportion of amines as a stabilizer is preferably in the range of 1 ppm by mass to 10% by mass, more preferably in the range of 5 ppm by mass to 5% by mass, relative to CFO-1214ya. A range of 10 mass ppm or more and 1 mass% or less is more preferable. When the content ratio is smaller than the lower limit, CFO-1214ya may not be sufficiently stabilized. In addition, when the content ratio is larger than the above lower limit value, characteristics of CFO-1214ya (characteristics with low surface tension and viscosity, characteristics with high permeability, characteristics that easily evaporate at room temperature, etc.) may be impaired. The stabilization of CFO-1214ya may not be further improved.

  In addition, when the non-flammable solvent composition containing the stabilizer comes into contact with copper or a copper alloy at the time of use, it may further contain a triazole in order to prevent corrosion of the copper or the copper alloy. . The triazoles contained in this embodiment are, for example, 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3′-tertiary-butyl-5′-methyl) Selected from phenyl) -5-chloro-benzotriazole, 1,2,3-benzotriazole, 1-[(N, N-bis-2-ethylhexyl) aminomethyl] benzotriazole. In particular, it is preferable to contain 1,2,3-benzotriazole. The content ratio of the above triazoles is preferably 10 mass ppm or more and 1 mass% or less with respect to the whole non-flammable solvent composition.

[C] Application The non-flammable solvent composition of the present embodiment can be used in various applications.

  Specifically, the non-flammable solvent composition of the present embodiment can be suitably used as a cleaning agent. The non-flammable solvent composition of the present embodiment, for example, when producing parts such as IC, electronic parts, precision machine parts, optical parts, etc., dirt (flux, processing oil, wax, It can be suitably used when removing mold release agents, dust, etc.). For example, in various cleaning methods such as hand cleaning, immersion cleaning, spray cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, and steam cleaning, it is possible to perform cleaning under any cleaning conditions (temperature, amount, number of times, etc.) is there.

  In addition to the above, the non-flammable solvent composition of the present embodiment effectively removes water adhering to the surface of the parts, etc., when the parts, etc. are washed using water such as pure water. And can be suitably used as a draining agent. For example, metal (iron, stainless steel, magnesium, aluminum, zinc, silver, copper, copper alloy, tin, alumite sulfate, etc.), plastic (vinyl chloride resin, polyethylene resin, polypropylene, polystyrene, polycarbonate, polyacetal, polyphenylene oxide, phenol resin) , ABS resin, nylon 6, nylon 66, PTFE resin, PCTFE resin, PEEK resin, epoxy resin, etc.) or water adhering to the surface formed of glass is effectively removed. Draining is performed by bringing the non-flammable solvent composition of the present embodiment into contact with the surface of the component or the like to which water has adhered. For example, draining can be performed under any draining conditions (temperature, amount, number of times, etc.) in methods such as immersion, spraying, immersion rocking, immersion ultrasonic wave, and steam exposure.

  In addition, the non-flammable solvent composition used as a cleaning agent or the like as described above and remaining on the surface of a part or the like is removed by drying. Drying can be performed under any drying conditions (temperature, time, etc.) in various drying methods such as heat drying, vacuum drying, and natural drying. In the case of the non-flammable solvent composition of the present embodiment, it rapidly evaporates at room temperature, so that it can be removed from the surface by natural drying. Further, as described above, the non-flammable solvent composition used as a cleaning agent or the like may be recovered and regenerated.

  Examples and the like will be specifically described below. In addition, the following Examples do not limit the scope of the present invention.

1. Specific volatility α
In order to measure the specific volatility α, a vapor-liquid equilibrium state under atmospheric pressure (1.011 × 10 ⁵ Pa) was measured for a mixture of CFO-1214ya and acetone. Specifically, first, a mixed solvent (300 g) obtained by mixing CFO-1214ya and acetone in various mass ratios was used using an Osmer-type vapor-liquid equilibrium distillation apparatus (Osmer equilibrium distillation apparatus B type set manufactured by Shibata Kagaku Co., Ltd.). (Pressure condition: 9.96 × 10 ^{4 to} 1.02 × 10 ⁵ Pa). And when the mixed solvent became a gas-liquid equilibrium state in the distillation, samples were taken from each of the gas phase and the liquid phase. And the composition of each sample was analyzed using gas chromatography. Thereafter, the relative volatility α was determined based on the analysis result.

  FIG. 1 shows the relationship between liquid phase concentration C1 (mass%) and gas phase concentration C2 (mass%) for acetone. Table 1 shows the relationship between the content ratio R1 of CFO-1214ya and the content ratio R2 of acetone and the relative volatility α.

  As shown in FIG. 1, for acetone, when the liquid phase concentration C1 is 12.5% by mass, the gas phase concentration C2 is 12.5% by mass, and the liquid phase and the gas phase are mutually in a gas-liquid equilibrium state. It is the same composition. For this reason, as shown in Table 1, when the content ratio of acetone is 12.5 mass% and the content ratio of CFO-1214ya is 87.5 mass%, the relative volatility α is 1. And an azeotropic mixture (azeotropic point 43.5 ° C.). Since the azeotrope has almost no change in composition, it is easy to handle when used as a cleaning agent or the like, and can effectively perform operations such as cleaning.

  As shown in Table 1, the content ratio R1 of CFO-1214ya is in the range of 85.0 mass% or more and 89.7 mass% or less, and the content ratio R2 of acetone is 10.3 mass% or more, 15.0 mass%. % In the range, the relative volatility α is in the range from 0.9 to 1.1. When the relative volatility α is in the above range (0.9 ≦ α ≦ 1.1), the change in the composition is small because it is close to the azeotropic point (α = 1). For this reason, in this case, as in the case of the azeotrope, the composition ratio does not fluctuate greatly when used as a cleaning agent or the like, so that handling is easy.

2. Flammability Table 2 shows the results of measuring the flash point of the mixed solvents of each example by the Cleveland open test method (JIS K 2265-4).

  As shown in Table 2, Examples 1 to 3 have no flash point. On the other hand, Example 4 and Example 5 have a flash point. As can be seen from this, it is composed of both CFO-1214ya and acetone, the content ratio of CFO-1214ya is in the range of 85.0 mass% to 89.7 mass%, and the content ratio of acetone is 10.3 mass%. When it is in the range of mass% or more and 15.0 mass% or less, it is non-flammable and can ensure high safety.

3. Solubility Table 3 shows the results of measuring the solubility of the solvents in each example. Oil A (trade name Suncut 50S, manufactured by Nippon Grease Co., Ltd.), Oil B (trade name: Daphnimag Plus HM25, manufactured by Idemitsu Kosan Co., Ltd.), and Oil C (trade name: C-4005 working oil, Nippon working oil The result of the solubility with respect to each of oil D (brand name Reliacut DS10, JX Nippon Mining & Energy Co., Ltd. product) is shown. In addition, Example 8 shows the measurement result of the solubility with respect to HCFC-225 (trade name AK-225 (manufactured by Asahi Glass Co., Ltd.)).

  First, 10 g of each of oils A to D was prepared in a 20 ml container. Next, 0.1 g of the solvent was added dropwise to the container and mixed. Next, about the oil which mixed the solvent, the presence or absence of white turbidity and the presence or absence of isolation | separation were confirmed visually. And when white turbidity or two-layer separation arose, it was judged that it was not melt | dissolving. This operation was repeated until a total of 10 g of solvent was added dropwise. The results are shown in Table 3. Here, “less than 1%” means that white turbidity or two-layer separation occurred when an amount of 1% by mass of oil was added dropwise to the total amount of oil and solvent. Also, “50%” means that when the total amount of solvent dropped reaches 10 g, that is, when oil is added in an amount of 50% by mass with respect to the total mass of oil and solvent, white turbidity or two-layer separation occurs. Indicates not.

  As shown in Table 3, Examples 1 to 3 have high solubility in each of the plurality of oils A to D. On the other hand, in Examples 6 to 8, the solvent does not dissolve in the oil for some of the plurality of oils A to D, and the solubility is low. As can be seen from this, it is composed of both CFO-1214ya and acetone, the content ratio of CFO-1214ya is in the range of 85.0 mass% to 89.7 mass%, and the content ratio of acetone is 10.3 mass%. When the content is in the range of not less than 1% by mass and not more than 15.0% by mass, the oil can be effectively washed because of its high solubility in oil.

4). Flux detergency Table 4 shows the results of evaluating the flux detergency for the solvents of each example. The result of the flux cleaning property with respect to each of Flux A (trade name: JS-15CAT, manufactured by Hiroki Co., Ltd.) and Flux B (trade name: ES-1061SP-2, manufactured by Senju Metal Industry Co., Ltd.) is shown. In Example 9, a mixed solvent of HCFC-225, ethanol, and a stabilizer (HCFC-225: ethanol: stabilizer = 95.1: 4.5: 0.4) (trade name AK-225AES (Asahi Glass Co., Ltd.) The evaluation of the flux detergency with respect to the production)) is shown.

  First, solder was attached to a JIS-II type substrate coated with the fluxes A and B. Next, the flux was washed using the solvent of each example. First, immersion cleaning (35 ° C., ultrasonic wave: 200 W, 35 kHz), cold bath cleaning, and steam cleaning were sequentially performed for 90 seconds. Thereafter, flux cleaning properties were evaluated. Here, the flux cleaning property was evaluated by visual observation. Along with this, flux cleaning performance was evaluated by measuring ionic residues. The ionic residue was measured using an omega meter (trade name Model 600SMD, manufactured by Nippon Alpha Metals Co., Ltd.) under a measurement time of 15 minutes.

Evaluation by visual observation was performed according to the following criteria.
○: No residue ×: Residue

Evaluation by ionic residue measurement was performed according to the following criteria (measured values in parentheses in the table).
○: 14 μg NaCl / sq. in. In the following cases: x: 14 μg NaCl / sq. in. When exceeding

  As shown in Table 4, Example 1 has excellent flux cleaning properties as in Example 9. On the other hand, Example 7 is inferior in flux cleaning property. As can be seen from this, when it is composed of both CFO-1214ya and acetone, the content ratio of CFO-1214ya is 87.5 mass%, and the content ratio of acetone is 12.5 mass%, the flux It can be cleaned effectively.

5. Table 5 shows the results of evaluating the drainability of the solvents of each example. In Table 5, Example 10 shows drainability against a mixed solvent of HCFC-225 and ethanol (HCFC-225: ethanol = 95.5: 4.5) (trade name is AK-225AE (Asahi Glass Co., Ltd.)). Was evaluated.

  When evaluating drainability, first immerse a glass plate with water on the surface in the solvent of each example heated to a temperature of 40 ° C. and irradiate the glass plate with ultrasonic waves. did. Next, the glass plate was pulled up from the solvent, and the surface of the glass plate was observed. And drainage was evaluated based on the presence or absence of water remaining on the surface of the glass plate.

Evaluation of drainability was performed according to the following criteria from the observation results.
○: No water remaining ×: Water remaining

  As shown in Table 5, Example 1 to Example 3 are excellent in drainability as in Example 10. On the other hand, Example 7 and Example 8 are inferior in drainage. As can be seen from this, it is composed of both CFO-1214ya and acetone, the content ratio of CFO-1214ya is in the range of 85.0 mass% to 89.7 mass%, and the content ratio of acetone is 10.3 mass%. When it is in the range of not less than 1% by mass and not more than 15.0% by mass, the drainability is excellent.

  The above-described embodiments, examples, and the like are exemplifications, and can be appropriately omitted, replaced, or changed without departing from the scope of the invention.

Claims (8)

1,1-dichloro-2,3,3,3-tetrafluoropropene and acetone,
The mass ratio of 1,1-dichloro-2,3,3,3-tetrafluoropropene to acetone is 85/15 to 89.7 / 10.3.
Non-flammable solvent composition. The mass ratio is 87.5 / 12.5,
The non-flammable solvent composition according to claim 1.   The non-flammable solvent composition according to claim 1 or 2, further comprising a stabilizer. The stabilizer is at least one compound selected from the group consisting of phenols, ethers, epoxides, and amines;
The non-flammable solvent composition according to claim 3. The stabilizer is a phenol, and the phenol is phenol, 1,2-benzenediol, 2,6-ditertiarybutyl-4-methylphenol, 3-cresol, 2-isopropyl-5-methylphenol, and , At least one selected from the group consisting of 2-methoxyphenol,
The non-flammable solvent composition according to claim 4. The stabilizer is an ether, and the ether is 1,4-dioxane, 1,3-dioxane, 1,3,5-trioxane, furan, 2-methylfuran, tetrahydrofuran, ethylphenyl ether, and diethylene glycol. Is at least one selected from the group consisting of monoethyl ether,
The non-flammable solvent composition according to claim 4 or 5. The stabilizer is an epoxide, and the epoxide is from 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, and diethylene glycol diglycidyl ether. Is at least one selected from the group consisting of
The non-flammable solvent composition according to any one of claims 4 to 6. The stabilizer is an amine, and the amine is pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine, diisopropylamine, N-methylmorpholine, 2-methyl-2-oxazoline, isoxazole, And at least one selected from the group consisting of N-ethylmorpholine,
The non-flammable solvent composition according to any one of claims 4 to 7.

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