JP2017043742A - Solvent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solvent composition having no harmful effect on global environment, having less effect on resin material, having sufficient dryability, and having excellent solubility in oils and fats, a method for cleaning an article and a method of dry-cleaning using the solvent composition, a method for producing a lubricant solution using the solvent composition, and a method for producing an article with a lubricant coating.SOLUTION: A solvent composition comprises Z-isomer of 1-chloro-3,3,3-trifluoropropene and at least one solvent (A) selected from the group consisting of 1,1-dichloro-2,3,3,3-tetrafluoropropene, perfluorobutoxy-methane and perfluorobutoxy-ethane. The Z-isomer of 1-chloro-3,3,3-trifluoropropene is in an amount of 0.1-75 wt.% and the solvent (A) is in an amount of 25-99.9 mass%, relative to 100 mass% of the solvent composition.SELECTED DRAWING: None

Description

  The present invention relates to a solvent composition, a method for cleaning an article using the solvent composition, a dry cleaning method, a method for producing a lubricant solution, and an article with a lubricant coating.

Conventionally, as a diluting solvent such as oil and fat cleaning, flux cleaning, dust cleaning, moisture removal solvent, dry cleaning solvent, reaction solvent, lubricant, etc., non-flammable, low toxic, and excellent hydrofluorochlorocarbon (hereinafter referred to as HCFCs) Have been used. However, since HCFCs have an adverse effect on the ozone layer, production is scheduled to be abolished in developed countries in 2020.
Examples of solvents that do not adversely affect the ozone layer include perfluorocarbons (hereinafter referred to as PFCs), hydrofluorocarbons (hereinafter referred to as HFCs), and hydrofluoroethers (hereinafter referred to as HFEs). Etc. are known.
However, HFCs and PFCs are regulated substances under the Kyoto Protocol because of their large global warming potential. In addition, HFCs, HFEs, and PFCs are less soluble in fats and oils than HCFCs, and have a narrow application range as solvent applications.

As a solvent that does not adversely affect the global environment and has the same solubility as HCFCs, 1-chloro-3,3,3-trifluoro-1-propene (hereinafter also referred to as HCFO-1233zd) is proposed. (Patent Document 1).
HCFO-1233zd is known to have a structural isomer, and is usually an E form of HCFO-1233zd (hereinafter also referred to as HCFO-1233zd (E)) and a Z form of HCFO-1233zd (hereinafter, HCFO-1233zd). -1233zd (Z))). Of these structural isomers, HCFO-1233zd (Z) is suitable as a solvent because the boiling point is 40 ° C.
However, when HCFO-1233zd (Z) alone is in contact with a resin material such as an acrylic resin, it may affect the resin material such as whitening or cracking of the resin material or dissolution of the acrylic resin. It could not be used for cleaning parts and diluting applications such as lubricants.

JP 2011-510119 A

  The present invention provides a solvent composition that does not adversely affect the global environment, has a small effect on resin materials, has sufficient drying properties, and is excellent in solubility in oils and fats, etc., and an article using the solvent composition It is an object of the present invention to provide a cleaning method and a dry cleaning method, a method for producing a lubricant solution using the solvent composition, and a method for producing an article with a lubricant coating.

The present invention provides a solvent composition having the following constitution, a cleaning method using the solvent composition, a dry cleaning method, a method for producing a lubricant solution, and an article with a lubricant coating.
[1] From the Z isomer of 1-chloro-3,3,3-trifluoropropene and 1,1-dichloro-2,3,3,3-tetrafluoropropene, perfluorobutoxymethane and perfluorobutoxyethane A solvent composition comprising at least one solvent (A) selected from the group consisting of: 1-chloro-3,3,3-trifluoropropene, based on 100% by mass of the solvent composition. A solvent composition wherein the Z isomer is 0.1 to 75% by weight and the solvent (A) is 25 to 99.9% by weight.
[2] The Z isomer of 1-chloro-3,3,3-trifluoropropene is 30 to 75% by weight with respect to 100% by mass of the solvent composition, and the solvent (A) is 25 to 70%. The solvent composition according to [1], which is mass%.
[3] The solvent composition according to [1] or [2], wherein the solvent (A) is one kind of 1,1-dichloro-2,3,3,3-tetrafluoropropene.
[4] A method for washing an article, wherein the dirt attached to the article is removed by bringing the solvent composition according to any one of [1] to [3] into contact with the surface of the article.
[5] The method for cleaning an article according to [4], wherein the dirt is fats and oils and dust.
[6] The method for cleaning an article according to [4] or [5], wherein the material of the article is polyethylene, polystyrene, ABS resin, acrylic resin, or polycarbonate.
[7] A method for dry cleaning an article by bringing the article into contact with the solvent composition according to any one of [1] to [3] and a surfactant.
[8] The method for dry cleaning an article according to [7], wherein the article is a textile product.
[9] A method for producing a lubricant solution, wherein a lubricant solution is obtained by diluting the lubricant with the solvent composition according to any one of [1] to [3].
[10] Lubrication in which the lubricant solution according to [9] is applied to the surface of an article, and then the solvent composition is evaporated from the article to form a coating film containing the lubricant on the surface of the article. A method for producing an article with an agent.

The solvent composition of the present invention does not adversely affect the global environment, has little influence on the resin material, has sufficient drying properties, and is excellent in solubility in oils and fats.
INDUSTRIAL APPLICABILITY The article cleaning method and dry cleaning method of the present invention do not adversely affect the global environment, have a small effect on the resin material, and can clean dirt adhering to the article.
The lubricant solution of the present invention does not adversely affect the global environment, has a small effect on articles, and is excellent in coating properties.
According to the method for manufacturing an article with a lubricant coating film of the present invention, an article with a lubricant coating film having a lubricant coating film can be manufactured which does not adversely affect the global environment and has little influence on the article.

<Solvent composition>
The solvent composition of the present invention comprises HCFO-1233zd (Z), 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene (CF ₃ CF═CCl ₂ , CFO-1214ya), and at least one solvent selected from the group consisting of fluoro-butoxy methane _{(C 4 F 9 OCH 3,} HFE-7100) and perfluoro butoxy ethane _{(C 4 F 9 OC 2 H} 5, HFE-7200). Hereinafter, at least one selected from the group consisting of CFO-1214ya, HFE-7100, and HFE-7200 is also referred to as a solvent (A).

  The solvent composition of the present invention may contain an organic solvent other than HCFO-1233zd (Z) and solvent (A) (hereinafter also referred to as organic solvent (B)), if necessary. Moreover, an additive (hereinafter also referred to as additive (C)) may be included within a range not impairing the effects of the present invention.

(HCFO-1233zd (Z))
Since HCFO-1233zd (Z) is an olefin having a double bond between carbon atoms, the lifetime in the atmosphere is short, and the ozone depletion coefficient and global warming coefficient are small.
Although HCFO-1233zd (Z) is an olefin, it is difficult to decompose even in the presence of oxygen and has high stability.
HCFO-1233zd (Z) has an excellent drying property because it has a boiling point of about 40 ° C. Moreover, since the temperature of the steam is about 40 ° C., handling is easy.
HCFO-1233zd (Z) does not have a flash point.
HCFO-1233zd (Z) has low surface tension and viscosity, and easily evaporates even at room temperature.
HCFO-1233zd (Z) is excellent in cleaning removal of processing oil, fluorine oil, silicone oil, synthetic oil, mold release agent, dust and the like, and solubility of lubricants such as fluorine oil and silicone oil.

  As described above, HCFO-1233zd (Z) has excellent solubility in various components and has sufficient performance as a diluent solvent for cleaning agents and lubricants. In addition, HCFO-1233zd (Z) has a boiling point suitable for the solvent, so it is easy to handle at the time of use, and does not volatilize when used at room temperature. Also excellent.

HCFO-1233zd (Z) can be produced by a known method.
For example, there is a method of dehydrofluorinating 3-chloro-1,1,1,3-tetrafluoropropane (R-244fa) in the presence of a catalyst (Japanese Patent Laid-Open No. 2009-263365). HCFO-1233zd (Z) can be obtained by purifying HCFO-1233zd obtained by the above method by distillation.

  HCFO-1233zd (Z) obtained by the above method contains impurities such as raw material HCFC-244fa. The content of impurities in HCFO-1233zd (Z) is preferably 1% by mass or less, and more preferably 0.5% by mass or less from the viewpoint of excellent solubility of the lubricant and reduction of the influence on the global environment. . That is, the purity of HCFO-1233zd (Z) is preferably 99% by mass or more, and more preferably 99.5% by mass or more. The purity of HCFO-1233zd (Z) can be increased by distillation purification or the like.

  The water content of HCFO-1233zd (Z) is preferably 50 mass ppm or less, and more preferably 10 mass ppm or less. If the water content of HCFO-1233zd (Z) is less than or equal to the above upper limit, it is possible to prevent HCFO-1233zd (Z) from being altered due to decomposition during storage.

  Examples of the method for removing moisture in HCFO-1233zd (Z) include a method using zeolite as a dehydrating agent. The zeolite may be a natural product or a synthetic product, and synthetic zeolite is preferred from the viewpoint of stable quality and availability.

(Solvent (A))
By including the solvent (A), the solvent composition of the present invention has a small influence on the resin material and is excellent in solubility of fats and oils.

CFO-1214ya:
Since CFO-1214ya is an olefin having a double bond between a carbon atom and a carbon atom, it has a short lifetime in the atmosphere and a small ozone depletion coefficient and global warming coefficient.
Since CFO-1214ya has a boiling point of about 46 ° C., it has excellent drying properties. Moreover, since it is about 46 degreeC even if it boiled and it becomes a vapor | steam, handling is easy.
CFO-1214ya does not have a flash point.
CFO-1214ya has a low surface tension and low viscosity and easily evaporates even at room temperature.
CFO-1214ya is less affected by the resin material and can be used for resin materials such as acrylic resin, ABS resin, polycarbonate, and polyethylene that cannot use HCFO-1233zd (Z).
CFO-1214ya is excellent in the solubility of various lubricants and can form a lubricant solution.
On the other hand, when CFO-1214ya is used as a diluent solvent for the diamine-modified silicone oil, the storage stability of the obtained lubricant solution containing the diamine-modified silicone oil is not sufficient.

  As described above, CFO-1214ya is excellent in solubility in various components except for low storage stability of a lubricant solution obtained by dissolving a specific lubricant, and is a diluent for a cleaning agent or a lubricant. As a result, it has sufficient performance.

CFO-1214ya can be produced by a known method.
For example, 1,1-dichloro-2,2,3,3,3-pentafluoropropane (hereinafter referred to as HCFC-225ca) and 1,3-dichloro-1,2,2,3,3-pentafluoro A method of dehydrofluorinating HCFC-225ca in an alkaline aqueous solution in the presence of a phase transfer catalyst using an isomer mixture of propane (hereinafter referred to as HCFC-225cb) as a raw material (WO 2010/074254) is mentioned. ).

  CFO-1214ya obtained by the above method contains unreacted impurities such as HCFC-225ca and HCFC-225cb. The content of impurities in CFO-1214ya is preferably 1% by mass or less, and more preferably 0.5% by mass or less, from the viewpoint of excellent solubility of the lubricant and reducing the influence on the global environment. That is, the purity of CFO-1214ya is preferably 99% by mass or more, and more preferably 99.5% by mass or more. The purity of CFO-1214ya can be increased by distillation or the like.

  The water content of CFO-1214ya is preferably 50 mass ppm or less, and more preferably 10 mass ppm or less. If the water content of CFO-1214ya is less than or equal to the above upper limit value, it is possible to prevent the CFO-1214ya from being degraded and degraded during storage or the like.

  The method for removing moisture in CFO-1214ya is the same as the method for removing moisture in HCFO-1233zd (Z).

HFE-7100:
HFE-7100 means one or more compounds selected from the group of compounds represented by C ₄ F ₉ OCH ₃ . Preferred compounds of HFE-7100 are 1-methoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1-methoxy-1,1,2,2,3,3. One or more compounds selected from 4,4,4-nonafluorobutane, particularly preferably 1-methoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1 A mixture with methoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane.
HFE-7100 has an excellent drying property because it has a boiling point of about 61 ° C. In addition, even if it is boiled into steam, it is about 61 ° C., so even parts that are easily affected by heat, such as resin parts, are less likely to be adversely affected.
HFE-7100 does not have a flash point.
HFE-7100 has a low surface tension and viscosity and easily evaporates even at room temperature.
HFE-7100 can be used for resin materials such as acrylic resin, ABS resin, polycarbonate, and polyethylene, which are less affected by the resin material and cannot use HCFO-1233zd (Z).
On the other hand, since HFE-7100 does not have a chlorine atom in the molecule, the solubility of fats and oils such as processing oil and lubricating oil may not be sufficient.

  As described above, HFE-7100 has no flash point except that the solubility of fats and oils is not sufficient, has little influence on the resin material, and is excellent in drying properties.

HFE-7100 can be produced by a known method.
For example, as described in Japanese Patent No. 2908033, CF ₃ CF ₂ CF ₂ C (O) F, CF ₃ CF (CF ₃ ) C (O) F and C ₂ F ₅ C (O) CF ₃ and Obtain these mixtures and any suitable source source of anhydrous fluoride ions, such as anhydrous alkali metal fluorides (eg, potassium fluoride or cesium fluoride), or anhydrous silver fluoride, from Aldrich Chemical Company It can be prepared by reacting with an alkylating agent such as dimethyl sulfate in an anhydrous polar aprotic solvent in the presence of a quaternary ammonium compound such as ADOGEN 464.

HFE-7200:
HFE-7200 means one or more compounds selected from the group of compounds represented by C ₄ F ₉ OC ₂ H ₅ . Preferred compounds of HFE-7200 are 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1-ethoxy-1,1,2,2,3,3. One or more compounds selected from 4,4,4-nonafluorobutane, particularly preferably 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1 -A mixture of ethoxy-1,1,2,2,3,3,4,4,4-nonafluorobutane.
HFE-7200 has an excellent drying property because it has a boiling point of about 61 ° C. In addition, even if it is boiled into steam, it is about 61 ° C., so even parts that are easily affected by heat, such as resin parts, are less likely to be adversely affected.
HFE-7200 does not have a flash point.
HFE-7200 has low surface tension and viscosity, and easily evaporates even at room temperature.
HFE-7200 can be used for resin materials such as acrylic resin, ABS resin, polycarbonate, and polyethylene, which are less affected by the resin material and cannot use HCFO-1233zd (Z).
On the other hand, since HFE-7200 does not have a chlorine atom in its molecule, the solubility of fats and oils such as processing oil and lubricating oil may not be sufficient.

  As described above, HFE-7200 does not have a flash point except that the solubility of fats and oils is not sufficient, has little influence on the resin material, and is excellent in drying properties.

HFE-7200 can be produced by a known method.
For example, as described in Japanese Patent No. 3068199, CF ₃ CF ₂ CF ₂ C (O) F, CF ₃ CF (CF ₃ ) C (O) F, and C ₂ F ₅ C (O) CF ₃ As well as any suitable source of anhydrous fluoride ions, such as anhydrous alkali metal fluorides (eg, potassium fluoride or cesium fluoride) or anhydrous silver fluoride, and ADOGEN 464 available from Aldrich Chemical Company Can be prepared by reacting with an alkylating agent such as diethyl sulfate in an anhydrous polar aprotic solvent in the presence of a quaternary ammonium compound.

  Although the solvent (A) may be one type or two or more types, the solvent (A) is preferably CFO-1214ya1 type from the viewpoint of excellent solubility in fats and oils.

(Organic solvent (B))
The organic solvent (B) is an organic solvent that is soluble in HCFO-1233zd (Z) and the solvent (A). The organic solvent (B) is appropriately selected according to various purposes such as increasing the solubility and adjusting the volatilization rate.
Examples of the organic solvent (B) include HCFO-1233zd (Z), hydrocarbons, alcohols, ketones, ethers (excluding compounds listed as HFEs) soluble in the solvent (A). Examples include esters, chlorocarbons, HFCs, HFEs and the like.

As the hydrocarbons, hydrocarbons having 5 or more carbon atoms are preferable. The hydrocarbons may be chain-like, cyclic, saturated hydrocarbons, or unsaturated hydrocarbons.
As hydrocarbons, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 2- Methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2-methylheptane, 2, 2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, 2-methyl-2-butane 1-pentene, 2-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, Examples include dipentene, decalin, tetralin, and amylnaphthalene, and n-pentane, cyclopentane, n-hexane, cyclohexane, and n-heptane are preferable.

As alcohol, C1-C16 alcohol is preferable. The alcohol may be a chain, may be cyclic, may be a saturated alcohol, or may be an unsaturated alcohol.
Examples of alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, and 1-ethyl-1. -Propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4-methyl-2- Pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3,5,5-trimethyl -1-hexanol, 1-decanol, -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, tetradecyl alcohol, etc. are mentioned, Methanol, ethanol, and isopropyl alcohol are preferable.

As ketones, C3-C9 ketones are preferable. The ketones may be linear, cyclic, saturated ketones, 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, holon, 2-octanone, Examples include cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanedione, 2,5-hexanedione, diacetone alcohol, acetophenone and the like, and acetone and methyl ethyl ketone are preferred.

As ethers, C2-C8 ethers are preferable. The ethers may be chain-like, cyclic, saturated ethers, or unsaturated ethers.
Examples of ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, methyl anisole, furan, methyl furan, tetrahydrofuran, and the like. preferable.

As the esters, esters having 2 to 19 carbon atoms are preferable. Esters may be linear, cyclic, saturated esters, and unsaturated esters.
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, acetic acid Methoxybutyl, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl isobutyrate, 2 -Ethyl hydroxy-2-methylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, gamma-butyrolactone, diethyl oxalate, dibutyl oxalate, dipentyl oxalate, malo Diethyl, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, and the like, methyl acetate, ethyl acetate is preferred.

As chlorocarbons, C1-C3 chlorocarbons are preferable. The chlorocarbons may be chain-like, cyclic, saturated chlorocarbons, or unsaturated chlorocarbons.
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, 1,2-dichloropropane, etc., methylene chloride, trans-1,2- Dichloroethylene and trichlorethylene are more preferable.

As the HFCs, linear or cyclic HFCs having 4 to 8 carbon atoms are preferable, and HFCs in which the number of fluorine atoms in one molecule is equal to or more than the number of hydrogen atoms are more preferable.
As HFCs, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,2,2 , 3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3,3,4, 4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, etc. 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1, 1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is preferred.
As HFEs, 1,1,2,2-tetrafluoroethoxy-1- (2,2,2-trifluoro) ethane and the like are preferable.

  1 type may be sufficient as an organic solvent (B), and 2 or more types may be sufficient as it. Further, when two or more kinds of organic solvents (B) are included, the combination thereof may be a combination of solvents of the same category or a combination of solvents of different categories. For example, it may be a combination of two kinds selected from hydrocarbons, or a combination of one kind selected from hydrocarbons and one kind selected from alcohols.

  The organic solvent (B) is more preferably a solvent having no flash point. Examples of organic solvents having no flash point include 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4, HFCs such as 4-nonafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,2,2- And HFEs such as tetrafluoroethoxy-1- (2,2,2-trifluoro) ethane. When a solvent having a flash point is used as the organic solvent (B), the solvent composition is preferably used in a range having no flash point.

(Additive (C))
The additive (C) is a component other than the HCFO-1233zd (Z), the solvent (A) and the organic solvent (B) of the present invention. A stabilizer is mentioned as an additive (C).
Examples of stabilizers include nitromethane, nitroethane, nitropropane, nitrobenzene, diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, tert-butylamine, α-picoline, N-methylbenzylamine, diallylamine, N-methyl. Morpholine, N-methylpyrrole, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4′-dihydroxy Phenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-t-butyl-p-cresol, 2- (2′-hydroxy-5) '-Methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N , N-bis-2-ethylhexyl) aminomethyl] benzotriazole, 1,2-propylene oxide, 1,2-butylene oxide, 1,4-dioxane, butyl glycidyl ether, phenyl glycidyl ether and the like.

  When the solvent composition of the present invention contains a stabilizer, the solvent composition can be used without being decomposed even under severe conditions such as heating conditions. Examples of preferable stabilizers include N-methylmorpholine, N-methylpyrrole, p-tert-butylphenol, 2,6-di-t, because olefins such as 1214ya which are easily decomposed in the presence of oxygen can be stabilized. -Butyl-p-cresol.

(Ratio of each component)
In the solvent composition of the present invention, HCFO-1233zd (Z) is 0.1 to 75% by weight and solvent (A) is 25 to 99.9% by weight with respect to 100% by weight of the solvent composition. In the solvent composition of the present invention, HCFO-1233zd (Z) is preferably 10 to 70% by weight and solvent (A) is preferably 30 to 90% by weight with respect to 100% by weight of the solvent composition. Thereby, the influence on the resin material can be further suppressed.

The solvent composition of the present invention is more preferably 30 to 75% by weight of HCFO-1233zd (Z) and 25 to 70% by weight of solvent (A) with respect to 100% by weight of the solvent composition. Most preferably, −1233zd (Z) is 30 to 50% by weight and the solvent (A) is 50 to 70% by weight. By setting it as the said range, the influence on resin is small and the storage stability of a solvent can be improved.
30 mass% or less is preferable among 100 mass% of a solvent composition, and, as for the ratio of an organic solvent (B), 10 mass% or less is more preferable.
5 mass% or less is preferable among 100 mass% of a solvent composition, and, as for the ratio of an additive (C), 1 mass% or less is more preferable.
When HCFO-1233zd (Z) and the solvent (A) form an azeotropic composition, the use of the azeotropic composition does not change the composition during use, and the solvent composition can be easily reused. From this point, it is preferable.

  When the solvent composition of the present invention contains a stabilizer as the additive (C), the ratio of HCFO-1233zd (Z) is preferably 29.9999 to 75% by mass in 100% by mass of the solvent composition, 29.99-50 mass% is more preferable. The ratio of the solvent (A) is preferably 24.9999 to 70% by mass, and more preferably 49.99 to 70% by mass. The proportion of the stabilizer is preferably 0.0001 to 5% by mass and more preferably 0.01 to 1% by mass in 100% by mass of the solvent composition. If it is the said range, stability of a solvent composition will improve further.

The solvent composition of the present invention does not adversely affect the global environment, has little influence on the resin material, has sufficient drying properties, and is excellent in solubility in oils and fats.
Since the solvent composition of this invention is excellent in the performance as a solvent, it can be used conveniently for various uses. Specific applications include grease, processing oil, silicone oil, flux, wax, ink, mineral oil, release agents including silicone oil, and other oils, dust, droplets, water droplets, and other contaminants. A cleaning solvent, a diluting solvent for diluting various chemical substances, a water removing agent for removing water adhering to the solid surface, an extraction solvent, a paint solvent, a dry cleaning solvent and the like can be mentioned.

Examples of materials for articles to which the solvent composition of the present invention can be applied include metals, resins, rubbers, fibers, glasses, ceramics, and composite materials thereof. Examples of the composite material include a laminate of a metal and a resin.
In particular, the solvent composition of the present invention can be used for resin materials such as acrylic resin, ABS resin, polycarbonate, polyethylene, and polystyrene, for which HCFO-1233zd (Z) could not be used.
Specific examples of the article include textile products, medical instruments, electrical equipment, precision machines, optical articles, and parts thereof. Specific examples of electrical devices, precision machines, optical articles, and parts thereof include ICs, capacitors, printed boards, micromotors, relays, bearings, optical lenses, glass substrates, and the like.

(How to clean articles)
In the method for cleaning an article of the present invention, the dirt adhering to the article is removed by bringing the solvent composition of the present invention into contact with the surface of the article.
The specific cleaning method is not particularly limited as long as the solvent composition of the present invention is brought into contact with the surface of the article. For example, hand wiping, dipping, spraying, shaking, ultrasonic, steam cleaning, or A combined method or the like may be employed. A well-known thing can also be suitably selected also about a washing | cleaning apparatus, washing | cleaning conditions, etc.

For example, a cleaning apparatus and a cleaning method disclosed in International Publication No. 2008/149907 are listed.
When the solvent composition of the present invention is used for cleaning with the cleaning apparatus disclosed in International Publication No. 2008/149907, the temperature of the solvent composition of the present invention in the first immersion tank is 25 ° C. or higher. It is preferable to be less than the boiling point. If it is in the said range, degreasing cleaning of processing oil etc. can be performed easily and the cleaning effect by an ultrasonic wave is high. Moreover, it is preferable that the temperature of the solvent composition of this invention in a 2nd immersion tank shall be 10-35 degreeC. If it is in the said range, the rinse cleaning effect is high. Moreover, it is preferable that the temperature of the solvent composition of this invention in a 1st immersion tank is higher than the temperature of the solvent composition of a 2nd immersion tank from the point of detergency.

(Dry cleaning method for goods)
The solvent composition of the present invention is suitable as a textile cleaning solvent, that is, a dry cleaning solvent.
Textile products include clothing such as shirts, sweaters, jackets, skirts, trousers, jumpers, gloves, mufflers, and stalls. The solvent composition of the present invention is particularly suitable as a solvent for dry cleaning of textiles containing acrylic fibers.

  In the dry cleaning method of the present invention, the solvent composition and the surfactant of the present invention are brought into contact with the surface of the fiber product to remove stains attached to the surface of the fiber product.

Examples of the surfactant include a cationic surfactant, a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.
Examples of preferred cationic surfactants include quaternary ammonium salts such as dodecyldimethylammonium chloride and trimethylammonium chloride.
Examples of preferred nonionic surfactants include polyoxyalkylene nonylphenyl ether, polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, phosphoric acid and fatty acid And surfactants such as esters.
Examples of preferred anionic surfactants include alkyl sulfates such as polyoxyethylene alkyl sulfates, carboxylates such as fatty acid salts (soap), sulfonates such as α-olefin sulfonates and lauryl sulfates. Is mentioned.
Examples of preferable amphoteric surfactants include betaine compounds such as alkylbetaines.

  The mass ratio of the solvent composition and the surfactant used in the dry cleaning method of the present invention (solvent composition / surfactant) is preferably 20/1 to 1000/1, preferably 100/1 to 1000/1. It is more preferable that If it is the said range, not only the fats and oils stain | pollution | contamination adhering to the textiles but the soil of inorganic salts, such as sweat, can be wash | cleaned simultaneously.

(Method for producing diluted solution)
Various chemical substances that can be diluted by the solvent composition of the present invention are not particularly limited, and examples thereof include lubricants and rust preventives.

As an embodiment of the diluted solution manufacturing method, a lubricant solution manufacturing method will be described below.
A lubricant solution can be produced by diluting the lubricant with the solvent composition of the present invention. By applying the lubricant solution to the surface of the article and then evaporating the solvent composition from the article, a coated article having a coating film containing the lubricant formed on the article surface can be produced. The lubricant solution of the present invention can be applied without affecting the article containing the resin material.

  Lubricant solution application methods include, for example, application by brush, application by spraying, application by immersing an article in the lubricant solution, and bringing the lubricant solution into contact with the inner wall of the tube or needle by sucking up the lubricant solution. The application method etc. to make are mentioned.

  The lubricant is used to reduce friction on the contact surface and prevent heat generation and wear damage when the two members move with the surfaces in contact with each other. The lubricant may be in any form of liquid (oil), semi-solid (grease), and solid. As the lubricant, a mineral oil-based lubricant, a synthetic oil-based lubricant, a fluorine-based lubricant, or a silicone-based lubricant is preferable because of its excellent solubility in the solvent composition of the present invention. In addition, a fluorine-type lubricant means the lubricant which has a fluorine atom in a molecule | numerator. Further, the silicone-based lubricant means a lubricant containing silicone. The lubricant contained in the lubricant solution may be one type or two or more types. Each of the fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination.

  Examples of the fluorine-based lubricant include fluorine-based solid lubricants such as fluorine oil, fluorine grease, and polytetrafluoroethylene resin powder. As the fluorine oil, perfluoropolyether or a low polymer of chlorotrifluoroethylene is preferable. For example, the product name “Crytox (registered trademark) GPL102” (manufactured by DuPont), “Daifloil # 1”, “Daiflooil # 3”, “Daiflooil # 10”, “Daiflooil # 20”, “Daiflooil # 50”, “Daifloil # 100”, “DEMNUM S-65” (manufactured by Daikin Industries, Ltd.), and the like. The fluorine grease is preferably a blend of polytetrafluoroethylene powder or other thickener with a fluorine oil such as perfluoropolyether or a low polymer of chlorotrifluoroethylene as a base oil. For example, the product names “Crytox (registered trademark) Grease 240AC” (manufactured by DuPont), “Daiflooil Grease DG-203”, “Demnam L65”, “Demnam L100”, “Demnam L200” (above, Daikin Corporation) Company-made), "Sumitec F936" (manufactured by Sumiko Lubricant Co., Ltd.), "Molicoat (registered trademark) HP-300", "Molicoat (registered trademark) HP-500", "Moricoat (registered trademark) HP-870" , “Moricoat (registered trademark) 6169”, and the like.

  Examples of the silicone lubricant include silicone oil and silicone grease. As the silicone oil, dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, and modified silicone oil in which an organic group is introduced into a side chain or a terminal are preferable. For example, the product 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 HIVAC F-4", "Shin-Etsu Silicone HIV AC F-5", "Shin-Etsu Silicone KF-56A", "Shin-Etsu Silicone KF-995" Company-made), “SH200”, “MDX4-4159” (manufactured by Toray Dow Corning Co., Ltd.) and the like. The silicone grease is preferably a product in which the various silicone oils listed above are used as a base oil and a thickener such as metal soap and various additives are blended. For example, 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”, “Shin-Etsu Silicone G-630” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Moricoat ( (Registered trademark) SH33L "," Molicoat (registered trademark) 41 "," Moricoat (registered trademark) 44 "," Moricoat (registered trademark) 822M "," Moricoat (registered trademark) 111 "," Molicoat (registered trademark) high vacuum " Grease ”,“ Molicoat (registered trademark) thermal diffusion compound ”(above, Toray Dow Corning ), And the like.

  0.01-50 mass% is preferable, as for content of the lubricant in the said lubricant solution (100 mass%), 0.05-30 mass% is more preferable, and 0.1-20 mass% is further more preferable. When the content of the lubricant is within the above range, it is easy to adjust the thickness of the coating film when the lubricant solution is applied and the thickness of the lubricant coating after drying to an appropriate range.

(Production Example 1) Production of HCFO-1233zd (Z) HCFO-1233zd (Z) was produced according to the method of JP2013-87066. That is, HCFC-244fa was dehydrochlorinated in the presence of sodium hydroxide to obtain crude HCFO-1233zd (Z) containing HCFC-244fa. The obtained crude HCFO-1233zd (Z) was charged into an autoclave, heated in an oil bath at 150 ° C., and stirred for 3 hours. After completion of the reaction, the reaction solution was collected and filtered, and then the filtrate was distilled and purified to obtain HCFO-1233zd (Z) having a purity of 99.5 mol%.
(Manufacture example 2) Manufacture of CFO-1214ya CFO-1214ya was manufactured by the method as described in international publication WO2010 / 074254 pamphlet. That is, it is obtained by reacting asahydrin AK225 with 1,3-dichloro-1,2,2,3,3-pentafluoropropane (HCFC-225cb) using tetrabutylammonium bromide (TBAB) as a phase transfer catalyst. The organic phase of the crude reaction liquid was distilled and purified to obtain CFO-1214ya having a purity of 99.5 mol%.

(Evaluation of effects on resin materials)
(Examples 1 to 23)
HCFO-1233zd (Z) and solvent (A) were prepared in 100 ml screw-heat-resistant heat-resistant bottles in the amounts shown in Tables 1 to 3, respectively, so that the total solvent composition would be 100 g, and acrylic resin (PMMA) and acrylonitrile -Test pieces (25 mm x 25 mm x thickness 3 mm) of butadiene-styrene copolymer (ABS resin), polycarbonate (PC), and polyethylene (PE) were put one by one. After the screw mouth heat-resistant bottle was allowed to stand at room temperature for 30 minutes, the test piece was taken out and the appearance was evaluated according to the following criteria.
A: No change in appearance is observed on the test piece.
○: The test piece has a slight crack or a slight loss of transparency, but there is no practical problem.
Δ: Clear cracks are observed on the surface of the test piece, or the transparency is lost.
X: A test piece melt | dissolves or a test piece cracks.

  In addition, Novec7100 (made by 3M) was used as HFE-7100, and Novec7200 (made by 3M) was used as HFE-7200.

  It turns out that the solvent composition of Examples 1-4 of Tables 1-3, Examples 7-10, and Examples 13-16 has little influence on each resin material. On the other hand, as can be seen from Examples 6, 12, and 18 in Tables 1 to 3, when HCFO-1233zd (Z) is 80% by mass or more of the solvent composition, it is understood that the resin material is affected.

(Lubricant solubility test)
(Examples 19 to 25)
HCFO-1233zd (Z) and CFO-1214ya were each prepared in the amounts shown in Table 4 so that the total amount of the solvent composition in the heat-resistant glass bottle was 100 g, and lubricating oil (silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. 5 g of name KF-868) was added. The state (solubility) of the solution immediately after adding the lubricating oil was evaluated. Thereafter, the state of the solution (storage stability) after storage at 40 ° C. for 3 days was evaluated.
The state of the solution was observed and evaluated according to the following criteria.
○ (excellent): No cloudiness is seen.
Δ (good): Although light cloudiness is observed, there is no practical problem.
X (defect): The cloudiness is clearly seen or the test object does not dissolve in the solvent.

  As can be seen from Examples 21 to 24 in Table 4, the solvent composition of the present invention is excellent in the solubility of the lubricating oil. Moreover, as can be seen from Examples 21 to 24, when HCFO-1233zd (Z) is 30% by mass or more, the storage stability of a solution in which lubricating oil is dissolved is also excellent.

(Evaluation of cleaning performance of fats and oils)
(Examples 26 to 32)
A cleaning test was performed using the solvent compositions prepared by adding HCFO-1233zd (Z) and the solvent (A) in amounts shown in Table 5 so that the total amount of the solvent composition was 100 g.
A test piece (25 mm × 30 mm × 2 mm) of SUS-304 was immersed in the cutting oil shown in Table 5, and then immersed in 50 mL of the solvent composition for 1 minute, and the degree to which the cutting oil was removed was observed by pulling up. . Detergency was evaluated according to the following criteria.
A (excellent): Cutting oil is completely removed.
○ (good): Cutting oil is almost removed.
Δ (slightly poor): A small amount of cutting oil remains.
X (defect): A considerable amount of cutting oil remains.
In addition, the cutting oil in a table | surface shows the following product, respectively.
HT-10: Daphne Marg Plus HT-10, manufactured by Idemitsu Kosan Co., Ltd.
AM20: Daphne Marg Plus AM20, manufactured by Idemitsu Kosan Co., Ltd.
HM25: Daphne Marg Plus HM25, manufactured by Idemitsu Kosan Co., Ltd.
G-6318FK: G-6318FK, manufactured by Nippon Tool Oil Co., Ltd.

As shown in Example 26 to Example 32 of Table 5, it can be seen that the solvent composition of the present invention is excellent in the detergency of fats and oils as when HCFO-1233zd (Z) or CFO-1214ya is used alone. .
(Example 33) Application test of lubricant solution:
A solvent composition in which the compositions of HCFO-1233zd (Z) and CFO-1214ya were 30% by mass and 70% by mass, respectively, was prepared. To this solvent composition, a commercially available silicone oil (manufactured by Toray Dow Silicone Co., MDX4-4159) was added so that the concentration in the solution would be 10% by mass to prepare a lubricant solution.
Lubricant solution is applied with an average thickness of about 0.4 mm on the surface of an aluminum vapor deposition plate obtained by vapor-depositing aluminum on an iron plate, and air-dried under conditions of 19 to 21 ° C. A lubricant coating was formed.
No white turbidity was observed in the lubricant solution, the solvent was quickly evaporated from the lubricant solution after application, and the state of the lubricant coating was good.
(Example 34) Application test of lubricant solution:
A solvent composition in which the compositions of HCFO-1233zd (Z) and CFO-1214ya were 70% by mass and 30% by mass, respectively, was prepared. As in Example 33, MDX4-4159 was added as a commercially available silicone oil so as to be 10% by mass to prepare a lubricant solution. A lubricant application test was performed in the same manner as in Example 33. No white turbidity was observed in the lubricant solution, the solvent was quickly evaporated from the lubricant solution after application, and the state of the lubricant coating was good.

  Since the solvent composition of the present invention is excellent in performance as a solvent, it is useful as a cleaning solvent, a diluting solvent, and a dry cleaning solvent for removing dirt such as fats and oils and dust. In particular, it is useful for removing dirt, oils and fats adhering to articles made of a resin material, and for dry cleaning.

Claims (10)

The Z isomer of 1-chloro-3,3,3-trifluoropropene;
1,1-dichloro-2,3,3,3-tetrafluoropropene, at least one solvent (A) selected from the group consisting of perfluorobutoxymethane and perfluorobutoxyethane. And
The Z isomer of 1-chloro-3,3,3-trifluoropropene is 0.1 to 75% by weight with respect to 100% by mass of the solvent composition, and the solvent (A) is 25 to 99%. Solvent composition which is 9 mass%.   The Z isomer of 1-chloro-3,3,3-trifluoropropene is 30 to 75% by weight and the solvent (A) is 25 to 70% by weight with respect to 100% by weight of the solvent composition. The solvent composition according to claim 1.   The solvent composition according to claim 1 or 2, wherein the solvent (A) is 1,1-dichloro-2,3,3,3-tetrafluoropropene.   The washing | cleaning method of articles | goods which removes the stain | pollution | contamination adhering to articles | goods by making the solvent composition as described in any one of Claims 1-3 contact the surface of articles | goods.   The method for cleaning an article according to claim 4, wherein the dirt is fats and oils and dust.   The method for cleaning an article according to claim 4 or 5, wherein the article is made of polyethylene, polystyrene, ABS resin, acrylic resin or polycarbonate.   A method of dry cleaning an article by bringing the article into contact with the solvent composition according to any one of claims 1 to 3 and a surfactant.   The method for dry cleaning an article according to claim 7, wherein the article is a textile product.   The manufacturing method of a lubricant solution which obtains a lubricant solution by diluting a lubricant with the solvent composition according to any one of claims 1 to 3.   An article with a lubricant, wherein the lubricant solution according to claim 9 is applied to the surface of the article, and then the solvent composition is evaporated from the article to form a coating film containing the lubricant on the surface of the article. Manufacturing method.