JP2020041090A - Solvent composition, cleaning method, coating film forming composition, and coating film manufacturing method - Google Patents

Abstract

To provide a solvent composition capable of reducing damages to resins, a cleaning method, a composition for coating film formation and a manufacturing method of a coating film.SOLUTION: The solvent composition of the present invention includes 1,3-dichloro-2,3,3-trifluoropropene and at least one kind selected from the group consisting of saturated hydrocarbons having a carbon number 6 or more and chemical compounds represented by CHFON(x is an integer of 3 or more, y is an integer of 0 or more, z is an integer of 1 or more, and v and w are each an integer of 0 or more. y≤z and 2x-2≤y+z≤2x+3 are satisfied. In the molecule, a group represented by N-H bond, C=N bond, C≡N bond, O-H bond, C=O bond, -CHF, and a ring structure are not included).SELECTED DRAWING: None

Description

  The present invention relates to a solvent composition, a cleaning method, a composition for forming a coating film, and a method for producing a coating film.

In the manufacture of ICs, electronic parts, precision machine parts, optical parts, etc., in the manufacturing process, the assembly process, the final finishing process, etc., the components are washed with a cleaning solvent, and the flux, processing oil, wax, Removal of the release agent, dust and the like is performed.
In addition, as a method for manufacturing an article having a coating film containing a nonvolatile organic compound such as a lubricant, a solution in which the nonvolatile organic compound is dissolved in a diluting coating solvent is prepared, and the solution is applied on the article and then diluted. A method of forming a coating film by evaporating a solvent is known. The dilution coating solvent is required to have excellent solubility of the nonvolatile organic compound.

  Solvents used in such applications are non-flammable, have low toxicity, are excellent in stability, do not attack substrates such as metals, plastics and elastomers, and are excellent in chemical and thermal stability. Chlorofluorocarbons such as 2,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as "CFCs"), 2,2-dichloro-1,1,1-trifluoroethane, 1,1 -Hydro such as dichloro-1-fluoroethane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane Fluorinated solvents containing chlorofluorocarbons (hereinafter referred to as "HCFCs") and the like have been used.

  However, since CFCs and HCFCs are extremely stable chemically, they have a long lifetime in the troposphere after vaporization and diffuse to reach the stratosphere. Therefore, there is a problem that the CFCs and HCFCs that have reached the stratosphere are decomposed by ultraviolet rays, generating chlorine radicals and destroying the ozone layer.

  On the other hand, perfluorocarbons (hereinafter, referred to as “PFCs”) are known as solvents having no chlorine atom and having no adverse effect on the ozone layer. Hydrofluorocarbons (hereinafter, referred to as "HFCs"), hydrofluoroethers (hereinafter, referred to as "HFEs"), and the like have been developed as alternative solvents to CFCs and HCFCs. However, HFCs and PFCs are regulated substances under the Kyoto Protocol because of their high global warming potential.

In such a situation, a fluoroolefin having a double bond between carbon atoms has been proposed as a new solvent replacing HFCs, HFEs, and PFCs. These fluoroolefins have excellent properties that they are easily decomposed, have a short life in the atmosphere, and have a small ozone depletion potential and a small global warming potential.
For example, Patent Document 1 discloses that 1,3-dichloro-2,3,3-trifluoropropene (CHCl = CF—CF ₂ Cl; HCFO-1223yd; hereinafter also referred to as 1223yd) is used as a degreasing cleaning solution. Is disclosed.

JP-A-02-221388

  The present inventors have found that when the 1223yd described in Patent Document 1 is used for various treatments of an article, the resin constituting the article may be damaged (for example, dissolution of the resin).

  In view of the above problems, an object of the present invention is to provide a solvent composition, a cleaning method, a composition for forming a coating film, and a method for producing a coating film, which can reduce damage to a resin.

As a result of intensive studies on the above problem, the present inventor has found that a desired effect can be obtained by using a solvent composition containing 1223yd and a saturated hydrocarbon having 6 or more carbon atoms described later or a compound represented by the formula (1). It was found that they were obtained and led to the present invention.
That is, the present inventor has found that the above-described problem can be solved by the following configuration.

[1] 1,3-Dichloro-2,3,3-trifluoropropene and at least one selected from the group consisting of a saturated hydrocarbon having 6 or more carbon atoms and a compound represented by the formula (1) A solvent composition comprising:
_{C x H y F z O v} N w (1)
In the formula (1), x is an integer of 3 or more, y is an integer of 0 or more, z is an integer of 1 or more, and v and w each represent an integer of 0 or more. However, y ≦ z and 2x−2 ≦ y + z ≦ 2x + 3 are satisfied, and in the molecule, an N—H bond, a C ＝ N bond, a C≡N bond, an O—H bond, a C ＝ O bond, and —CHF ₂ It does not include the represented groups and ring structures.
[2] The content of the saturated hydrocarbon at 25 ° C. and 1 atm is 15 to 45% by volume based on the total volume of the saturated hydrocarbon and 1,3-dichloro-2,3,3-trifluoropropene. The solvent composition according to [1].
[3] The solvent composition according to [1] or [2], which contains two or more kinds of the above-mentioned saturated hydrocarbons.
[4] The solvent composition according to any one of [1] to [3], wherein the boiling point of the saturated hydrocarbon is 50 to 130 ° C.
[5] The solvent composition according to any one of [1] to [4], wherein the saturated hydrocarbon has 6 to 8 carbon atoms.
[6] The solvent composition is an azeotropic composition or an azeotropic composition, and the saturated hydrocarbon is normal hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 3-dimethylbutane, cyclohexane, methylcyclopentane, normal heptane, 2-methylhexane, 3-methylhexane, 4-methylhexane, normal octane, and at least one compound selected from the group consisting of isooctane, The solvent composition according to any one of [1] to [5].
[7] The content of the compound represented by the above formula (1) at 25 ° C. and 1 atm is the content of the compound represented by the above formula (1) and 1,3-dichloro-2,3,3-trifluoropropene. The solvent composition according to [1], which is 15 to 55% by volume based on the total mass.
[8] The solvent composition according to [1] or [7], comprising two or more compounds represented by the above formula (1).
[9] The solvent composition according to any one of [1], [7] and [8], wherein the compound represented by the formula (1) has a boiling point of 50 to 130 ° C.
[10] The solvent composition according to any one of [1] and [7] to [9], wherein the compound represented by the formula (1) satisfies 4 ≦ x + v + w ≦ 9, 1 ≦ y, and 5 ≦ z. object.
[11] The solvent composition according to [10], wherein the compound represented by the formula (1) satisfies 0 ≦ v ≦ 1.
[12] The solvent composition is an azeotropic composition or an azeotropic composition, and the compound represented by the formula (1) is nonafluorobutyl methyl ether, 1,1,1,2,2, 3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, perfluoro The solvent composition according to any one of [1] and [7] to [9], which is at least one compound selected from the group consisting of hexane, perfluorotributylamine, and perfluorotripropylamine.
[13] A cleaning method characterized by contacting the surface of an article with the solvent composition according to any of [1] to [12] to remove dirt attached to the surface of the article.
[14] The cleaning method according to [13], wherein the article has on its surface at least one resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin.
[15] The cleaning method according to [13] or [14], wherein the dirt is oils and fats or dust.
[16] A coating film forming composition comprising a nonvolatile organic compound and the solvent composition according to any one of [1] to [12].
[17] After applying the composition for forming a coating film according to [16] to the surface of an article, the solvent composition is evaporated to obtain a coating film containing the nonvolatile organic compound. Method for producing a coating film.
[18] The method for producing a coating film according to [17], wherein the article has on its surface at least one resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin.

  ADVANTAGE OF THE INVENTION According to this invention, the solvent composition which can reduce the damage to a resin, the washing | cleaning method, the composition for coating film formation, and the manufacturing method of a coating film can be provided.

The meanings of the terms in the present invention are as follows.
The numerical range represented by using “to” means a range including the numerical values described before and after “to” as the lower limit and the upper limit.
1223yd has a geometric isomer, Z-form and E-form, depending on the position of the substituent on the double bond. In the present specification, when a compound name or an abbreviation of a compound is used unless otherwise specified, it indicates at least one selected from a Z-form and an E-form, and more specifically, a Z-form or an E-form, or It shows a mixture of Z-form and E-form at an arbitrary ratio.

The solvent composition of the present invention includes 1223yd, a saturated hydrocarbon having 6 or more carbon atoms (hereinafter, also referred to as “compound A”) and a compound represented by the formula (1) (hereinafter, also referred to as “compound B”). ), At least one selected from the group consisting of:
As will be shown in the examples below, 1223yd tends to damage resins (particularly polycarbonate resins, polystyrene resins and acrylonitrile-butadiene-styrene resins).
In order to solve this problem, the present inventors have found that the use of Compound A or Compound B together with 1223yd can reduce the damage that 1223yd gives to the resin. Although the details of this reason are not clear, it is considered that Compound A and Compound B selectively protect the resin.
The first embodiment of the solvent composition of the present invention is an embodiment containing 1223yd and compound A. Further, the second embodiment of the solvent composition of the present invention is an embodiment containing 1223yd and compound B. Further, the third embodiment of the solvent composition of the present invention is an embodiment including 1223yd, compound A and compound B. Hereinafter, components included in the solvent composition will be described for each embodiment.
In the following description, “effect of the present invention” means “can reduce damage to resin” unless otherwise specified.

[First Embodiment]
The solvent composition of the first embodiment contains 1223yd and compound A. It is preferable that the solvent composition of the first embodiment does not contain the compound B.

<1223yd>
1223yd means as described above, 1,3-dichloro-2,3,3-trifluoropropene _{(CHCl = CF-CF 2 Cl} ).
The content of 1223yd is preferably from 30 to 97% by mass, more preferably from 45 to 97% by mass, based on the total mass of the solvent composition.

<Compound A>
Compound A is a saturated hydrocarbon having 6 or more carbon atoms.
The number of carbon atoms in compound A is 6 or more, and is preferably 10 or less, more preferably 9 or less, and particularly preferably 8 or less from the viewpoint that the effects of the present invention are more exhibited.
Compound A may be linear or branched. Compound A may have a ring structure or may have a ring structure.

Specific examples of compound A include normal hexane, methylcyclopentane, cyclohexane, normal heptane, normal octane, isooctane, normal decane, 2,3-dimethylbutane, 2,2-dimethylbutane, 2,2,3,3- Tetramethylbutane, 2,2,3-trimethylbutane, 2,3,4,6-tetramethylheptane, 3,3,5,5-tetramethylheptane, 2,2,5,5-tetramethylheptane, , 2,6,6-tetramethylheptane, 2,6,6-trimethyloctane, 2,2,4-trimethyloctane, 2,2,3-trimethyloctane, 2,2,6-trimethyloctane, 2,2 , 4,4,5-pentamethylhexane, 3-isopropyl-2-methylhexane, 3,3,4,4-tetramethylhexane, 4-E 3,3-dimethylhexane, 4-ethyl-2,4-ethyldimethylhexane, 4-ethyl-2,3-ethyldimethylhexane, 4-ethyl-2,2-ethyldimethylhexane, 3-ethyl-3 , 4-ethyldimethylhexane, 3-ethyl-2,5-ethyldimethylhexane, 3-ethyl-2,4-ethyldimethylhexane, 3-ethyl-2,3-ethyldimethylhexane, 3-ethyl-2,2 -Ethyldimethylhexane, 2,3,4,5-tetramethylhexane, 2,3,4,4-tetramethylhexane, 2,3,3,5-tetramethylhexane, 2,3,3,4-tetra Methylhexane, 2,2,4,5-tetramethylhexane, 2,2,4,4-tetramethylhexane, 2,2,3,5-tetramethylhexane, 2,2,3,4- Tramethylhexane, 2,2,5,5-tetramethylhexane, 2,2,3,3-tetramethylhexane, 3-ethyl-4-methylhexane, 3-ethyl-3-methylhexane, 4-ethyl- 2-methylhexane, 3-ethyl-2-methylhexane, 3,3,4-trimethylhexane, 2,4,4-trimethylhexane, 2,3,5-trimethylhexane, 2,3,4-trimethylhexane, 2,3,3-trimethylhexane, 2,2,5-trimethylhexane, 2,2,4-trimethylhexane, 2,2,3-trimethylhexane, 3,4-dimethylhexane, 3,3-dimethylhexane, 2,5-dimethylhexane, 2,4-dimethylhexane, 2,3-dimethylhexane, 2,2-dimethylhexane, 4-methylhexane, 3-methyl Hexane, 2-methylhexane, 3-methylpentane, 2-methylpentane, 3-ethylpentane, 3,3-dimethylpentane, 2,4-dimethylpentane, 2,3-dimethylpentane, 2,2-dimethylpentane, 2,2,4-trimethylpentane, 2,3,3,4-tetramethylpentane, 2,2,4,4-tetramethylpentane, 2,2,3,4-tetramethylpentane, 2,2,3 3,3-tetramethylpentane, 3,3-diethylpentane, 3-methyl-3-ethylpentane, 3-ethyl-2-methylpentane, 2,3,4-trimethylpentane, 2,3,3-trimethylpentane, 2,2,3-trimethylpentane, 2,4-dimethyl-3-ethylpentane, 2,3-dimethyl-3-ethylpentane, 2,2-dimethyl-3-ethyl Pentane, 3,3-dimethyl-2-ethylpentane, 3-ethyl-2,2,3-trimethylpentane, 3-ethyl-2,3,4-trimethylpentane, 3-ethyl-2,2,4-trimethyl Pentane, 2,4-dimethyl-3-isopropylpentane, 2,2,3,4,4-pentamethylpentane, 2,2,3,3,4-pentamethylpentane, 2-methylheptane, 4-ethyl- 2-methylheptane, 4,4-dimethylheptane, 2,6-dimethylheptane, 2,5-dimethylheptane, 2,4-dimethylheptane, 2,2-dimethylheptane, 3,4,4-trimethylheptane, 2 2,5,5-trimethylheptane, 2,4,6-trimethylheptane, 2,4,5-trimethylheptane, 2,4,4-trimethylheptane, 2,3,6-to Methylheptane, 2,3,3-trimethylheptane, 2,2,6-trimethylheptane, 2,2,5-trimethylheptane, 2,2,4-trimethylheptane, 2,2,3-trimethylheptane, 3, Examples include 3,5-trimethylheptane, 4,4-dimethyloctane, 2,7-dimethyloctane, 2,2-dimethyloctane, 2,2,4,4,6,8,8-heptamethylnonane.
Among these, compound A is preferably at least one compound selected from the group consisting of normal decane, normal hexane, cyclohexane, and normal octane, from the viewpoint that the effects of the present invention are more exhibited, From the viewpoint of excellent volatility when used as a coating solvent, at least one compound selected from the group consisting of normal hexane, cyclohexane, and normal octane is particularly preferable.

  As the compound A, normal hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethyl can be formed from an azeotropic composition or an azeotropic composition with 1223yd. Butane, cyclohexane, methylcyclopentane, normal heptane, 2-methylhexane, 3-methylhexane, 4-methylhexane, normal octane, and at least one compound selected from the group consisting of isooctane is preferable, and normal hexane, Cyclohexane, normal heptane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, and 2,3-dimethylbutane are particularly preferred.

When the solvent composition forms an azeotropic composition or an azeotrope-like composition, the composition fluctuation of the solvent composition during use is small.
In the azeotropic composition, the composition of the gas phase generated by vaporization of the liquid phase is the same as the composition of the liquid phase, or the composition of the liquid phase generated by the liquefaction of the gas phase is the same as the composition of the gas phase Is defined as The azeotropic composition can be repeatedly used as a solvent composition because the composition does not change due to evaporation and condensation. Note that the composition of the azeotropic composition changes depending on the pressure conditions.
An azeotropic composition exhibits a behavior similar to that of an azeotropic composition. That is, in the azeotropic-like composition, the composition of the gas phase generated by vaporization of the liquid phase is substantially the same as the composition of the liquid phase, or the composition of the liquid phase generated by the liquefaction of the gas phase is the composition of the gas phase. Is almost the same as Since the composition of the azeotropic composition hardly changes due to evaporation and condensation, it can be repeatedly used as a solvent composition, like the azeotropic composition.

The boiling point of compound A is preferably from 50 to 130 ° C, more preferably from 50 to 100 ° C, since the vapor pressure at room temperature is not too high when used as a detergent or a solvent for coating, and volatility is required. Is more preferable, and 50 to 80C is particularly preferable.
In addition, the boiling point in the present invention means a boiling point under one atmosphere unless otherwise specified.

The content of the compound A at 25 ° C. and 1 atm is preferably 10 to 50% by volume, more preferably 15 to 45% by volume, particularly preferably 15 to 35% by volume, based on the total volume of the compound A and 1223yd. Here, the content (% by volume) of the compound A is a value calculated based on the volumes of the compound A and 1223yd at 25 ° C.
When the content of Compound A is 45% by volume or less, a solvent composition that is difficult to ignite is obtained. When the content of the compound A is 10% by volume or more, the effect of the present invention is more exhibited.
Compound A may be used alone or in combination of two or more. When two or more compounds A are contained, the total content of the compounds A is preferably within the above range.

<Other components>
The solvent composition of the first embodiment may include components other than 1223yd and compound A.
A specific example of such a component includes a surfactant (soap). When the solvent composition contains a surfactant, the washability of the article can be improved, and it is particularly suitable for dry cleaning.
Specific examples of the surfactant include a cationic surfactant, a nonionic surfactant, an anionic surfactant, and a zwitterionic surfactant.
Specific examples of the cationic surfactant include quaternary ammonium salts such as dodecyldodecyldimethylammonium chloride and trimethylammonium chloride.
Specific examples of the nonionic surfactant include polyoxyalkylene nonyl phenyl ether, polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, phosphoric acid and fatty acid And a surfactant such as an ester.
Specific examples of the anionic surfactant include alkyl sulfates such as polyoxyethylene alkyl sulfate, carboxylate such as fatty acid salt (soap), sulfonate such as α-olefin sulfonate and lauryl sulfate. Is mentioned.
Specific examples of the amphoteric surfactant include betaine compounds such as alkyl betaine.

  The content of the surfactant is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and particularly preferably from 0.2 to 2% by mass, based on the total mass of the solvent composition.

<Application>
The solvent composition of the first embodiment can be suitably used for cleaning articles. Specifically, the surface of the article is brought into contact with the solvent composition of the first embodiment to remove dirt attached to the surface of the article.
Examples of the stain adhering to the article include a stain that is used in manufacturing the article or a component constituting the article and must be finally removed or a stain that adheres when the article is used. Examples of substances that form stains include grease, processing oil, silicone oil, flux, wax, ink, mineral oil, oils and fats such as release agents including silicone oil, dust, and the like.
In particular, it can be suitably used for cleaning and removing processing oil and a release agent attached to the surface of an article.
Specific examples of the processing oil include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press working oil, punching oil, drawing oil, assembly oil, and drawing oil.
As a specific means for removing the dirt, for example, hand wiping, dipping, spraying, rocking, ultrasonic cleaning, steam cleaning, or a combination thereof can be employed.

The solvent composition of the first embodiment can be suitably used as a diluting coating solvent for forming a coating film containing a nonvolatile organic compound.
In the present invention, the non-volatile organic compound means an organic compound having a boiling point higher than that of the solvent composition and remaining on the surface even after the solvent composition evaporates. Specific examples of the non-volatile organic compound include a lubricant for imparting lubricity to an article such as silicone oil, a rust inhibitor for imparting a rust-preventing effect to a metal part, and a water-repellent property for imparting an article with water repellency. Examples of the coating agent include a moisture-proof coating agent and an antifouling coating agent such as a fingerprint removal adhesion preventing agent for imparting antifouling performance to articles.
Specific examples of the non-volatile organic compound as a lubricant, a rust inhibitor, a moisture-proof coating agent, and an anti-fouling coating agent include the compounds described in WO2017 / 018010.

  The solvent composition of the first embodiment is not limited to the use described above, and can be suitably used for other uses such as dry cleaning.

Specific examples of articles to which the solvent composition of the first embodiment can be applied include electronic devices (for example, capacitors, diodes, printed circuit boards), optical devices (for example, lenses, polarizing plates), and precision devices (for example, micromotors, Bearings), transportation equipment, medical equipment, and textile products.
Materials to which the solvent composition of the first embodiment can be applied include metals, resins, elastomers, glass, ceramics, fabrics, and composite materials thereof.
Here, when 1223yd is used alone, the resin tends to be easily damaged, and particularly, the polycarbonate resin, the polystyrene resin, and the acrylonitrile-butadiene-styrene resin are easily damaged.
However, according to the solvent composition of the first embodiment, since the compound A is contained, the damage caused by 1223yd to the resin can be reduced. Therefore, the solvent composition of the first embodiment is used for an article having a resin (in particular, at least one resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin) on the surface. Can also be suitably used.

[Second embodiment]
The solvent composition of the first embodiment contains 1223yd and compound B. Since 1223yd is as described in the first embodiment, the description is omitted. It is preferable that the solvent composition of the second embodiment does not contain the compound A.

<Compound B>
Compound B is a compound represented by the following formula (1).
_{C x H y F z O v} N w (1)
In the formula (1), x is an integer of 3 or more, y is an integer of 0 or more, z is an integer of 1 or more, and v and w each represent an integer of 0 or more.
However, y ≦ z and 2x−2 ≦ y + z ≦ 2x + 3 are satisfied, and the molecule is represented by N—H bond, C ＝ N bond, C≡N bond, O—H bond, C ＝ O bond, and —CHF ₂ . And the ring structure is not included.

x is an integer of 3 or more, and is preferably 4 or more, more preferably 9 or less, more preferably 8 or less, and particularly preferably 7 or less, from the viewpoint that the effects of the present invention are more exhibited.
y is an integer of 0 or more, and is preferably 1 or more from the viewpoint of GWP (Global Warming Potential). However, y ≦ z is satisfied.
z is an integer of 1 or more, and is preferably 5 or more from the viewpoint that the effects of the present invention are more exhibited. Further, x ≦ z is preferable.
v is an integer of 0 or more, and preferably 0 to 1 from the viewpoint that the effects of the present invention are more exhibited.
w is an integer of 0 or more, preferably 0 to 1, and particularly preferably 0 from the viewpoint of more exerting the effects of the present invention.
x + v + w is an integer of 3 or more, and preferably 4 to 9 from the viewpoint that the effects of the present invention are more excellent.
y + z satisfies 2x−2 ≦ y + z ≦ 2x + 3, and preferably satisfies 2x−2 ≦ y + z ≦ 2x + 2 from the viewpoint that the effects of the present invention are more excellent.

Compound B has an N—H bond (a structure in which a nitrogen atom and a hydrogen atom are bonded), a C ＝ N bond (a structure in which a carbon atom and a nitrogen atom are double-bonded), a C≡N bond (in a molecule). A structure in which a carbon atom and a nitrogen atom are triple-bonded), an OH bond (a structure in which an oxygen atom is bonded to a hydrogen atom; for example, a hydroxyl group), and a C ＝ O bond (a carbon atom and an oxygen atom are doubled) (Eg, a carbonyl group).
That is, when compound B contains a nitrogen atom, compound B contains a tertiary amine structure, and when compound B contains an oxygen atom, compound B contains an ether bond.
Moreover, Compound B does not include a group represented by the -CHF _2. That is, when the compound B containing a fluorine _{atom, -CH 2 F, -CF 3,} -CF 2 -, - groups may include such CHF-.
The compound B is a non-cyclic compound containing no ring structure (for example, an aliphatic hydrocarbon ring such as cycloalkane or cycloalkene, an aromatic hydrocarbon ring such as benzene or naphthalene, or a heterocyclic ring such as tetrahydrofuran or piperidine). Compound.

Preferred embodiments of the compound B include compounds satisfying 4 ≦ x + v + w ≦ 9, 1 ≦ y and 5 ≦ z.
More preferable embodiments of the compound B include compounds satisfying 4 ≦ x + v + w ≦ 9, 1 ≦ y, 5 ≦ z, and 0 ≦ v ≦ 1.

  Specific examples of compound B include perfluorooctane, perfluorooctene, perfluorononane, perfluorodecane, perfluoro-n-hexadecane, perfluorodecalin, perfluorododecane, perfluoro-2,7-dimethyloctane, and 1H , 1H, 2H-perfluoro-1-octene, perfluoroisobutane, 1H, 1H, 2H-perfluoro-1-decene, perfluoro-2,3-dimethylbutane, perfluoro-2-methylpentane, perfluoro- 3-methylpentane, octafluoropropane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1′-oxybis (1,1,2,2,3,3,3 3-heptafluoro) propane, 1,1,1,2,2,3,3,4,4-nonafluoro-4- (penta Fluoroethoxy) butane, 3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, 1,1,1,3,4,4,5,5,5-nonafluoro-2- (Trifluoromethyl) -2-pentene, 1,1,2,3,3,4,4,4-octafluoro-1-butene, 1,1,2,2,3,3,3-heptafluoropropyl -2,2,3,3,3-pentafluoropropyl ether, 1,1,1,2,2,3,3-heptafluoropentane, 1,1,1,3,3,3-hexafluoro-2 -(Trifluoromethyl) propane, perfluorohexane, perfluoropentane, perfluorobutane, perfluoroheptane, hexafluoro-1,3-butadiene, (Z) -1,1,1,4,4,4-hexa Fluoro-2-butene, 1,1,1 2,3,4,4,5,5,5-decafluoro-2-pentene, heptafluoropropyl methyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro- 3-methoxy-4- (trifluoromethyl) pentane, nonafluorobutyl methyl ether, nonafluorobutyl ethyl ether, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentane Fluorobutane, 2,2,3,3-tetrafluoropropyl-1,1,2,2-tetrafluoroethyl ether, 1,3,3,3-tetrafluoropropene, 1,1,1,2,2 3,3,4,4,5,5,6,6-tridecafluorooctane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane, octafluorobutane, ethyltris (Trifluoro Methyl) methyl ether, perfluorotributylamine, perfluorotripropylamine, tris (pentafluoroethyl) amine, methoxytridecafluoroheptene and the like.

Among these, compound B is 1,1,1,3,3-pentafluorobutane (Solcan 365 mfc, manufactured by Solvay Japan), 1,1,1,2 from the viewpoint that the effects of the present invention are more exhibited. , 3,4,4,5,5,5-Decafluoropentane (Bertrel XF, manufactured by DuPont Fluorochemicals, Mitsui), Methoxytridecafluoroheptene (Bertrel Suprion, manufactured by Mitsui-Kemers Fluoro Products) , (Z) -1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz, manufactured by Chemers), 1,1,1,2,2,3,3,4,4 , 5,5,6,6-tridecafluorooctane (ASAHICLIN AC-6000, manufactured by AGC), heptafluoropropyl methyl ether (Novec 7000, manufactured by 3M), nonafluorob Methyl ether (Novec 7100, 3M), nonafluorobutyl ethyl ether (Novec 7200, 3M), 1,1,1,2,2,3,4,5,5,5-decafluoro-3 -Methoxy-4- (trifluoromethyl) pentane (Novec 7300, manufactured by 3M), perfluorohexane (Fluorinert FC-72, manufactured by 3M), perfluoroheptane (Fluorinert FC-84, manufactured by 3M), perfluoro Tripropylamine (Fluorinert FC-3283, manufactured by 3M), 1,1,1,2,2,3,3,4,4-nonafluorohexane, 2,2,3,3-tetrafluoropropyl-1, 1,2,2-tetrafluoroethyl ether, perfluorotributylamine (Fluorinert FC-43, manufactured by 3M), 1,1,1,3,3 Pentafluoropropane (HCF-245fa), and, 1,3,3,3 least one compound selected from the group consisting of tetrafluoropropene (HFO-1234ze) are preferred.
More preferable examples of the compound B include 1,1,1,3,3-pentafluorobutane (Solcan 365 mfc, manufactured by Solvay Japan), 1,1,1,2,3,4,4,5,5,5 5-decafluoropentane (Bertrel XF, manufactured by Du Pont-Mitsui Fluorochemicals), 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane (Asahi Clean AC-6000, manufactured by AGC, perfluorohexane (Fluorinert FC-72, manufactured by 3M), nonafluorobutyl methyl ether (Novec 7100, manufactured by 3M), 1,1,1,2,2,3, 4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane (Novec 7300, manufactured by 3M) and methoxytridecafluoroheptene (Bertrel) And at least one selected from the group consisting of Suplion and Mitsui-Kemers Fluoro Products).

  Compound B can form an azeotropic composition or an azeotrope-like composition with 1223yd, so that nonafluorobutyl methyl ether (Novec 7100, manufactured by 3M), 1,1,1,2,2,3,4 , 5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane (Novec 7300, 3M), perfluorohexane (Fluorinert FC-72, 3M), perfluorotripropylamine (Fluorinert FC-3283, 3M), 1,1,1,2,2,3,3,4,4-nonafluorohexane, and perfluorotributylamine (Fluorinert FC-43, 3M) At least one compound selected from the group is preferred.

The content of the compound B at 25 ° C. and 1 atm is preferably 15 to 55% by volume, more preferably 15 to 45% by volume, still more preferably 20 to 45% by volume, based on the total mass of the compound B and 1223yd. -40% by volume is particularly preferred.
When the content of the compound B is 45% by volume or less, the solubility of the solvent composition in liquid paraffin is excellent. When the content of the compound B is 15% by volume or more, the effect of the present invention is more exhibited.
Compound B may be used alone or in combination of two or more. When two or more compounds B are contained, the total content of the compounds B is preferably within the above range.

  The boiling point of the compound B is preferably 50 to 130 ° C, more preferably 50 to 100 ° C, since the vapor pressure at room temperature is not too high when used as a detergent or a coating solvent, and volatility is required. Is more preferable, and 50 to 80C is particularly preferable.

The solvent composition of the second embodiment may contain components other than those described above. Specific examples of the other components are the same as those of the solvent composition of the first embodiment, and a description thereof will not be repeated.
The use of the solvent composition of the second embodiment and applicable articles are the same as those of the solvent composition of the first embodiment, and a description thereof will be omitted.

[Third embodiment]
The solvent composition of the third embodiment includes 1223yd, compound A, and compound B. Since 1223yd and compound A are as described in the first embodiment, and compound B is as described in the second embodiment, description thereof will be omitted.
In the solvent composition of the third embodiment, the total content of Compound A and Compound B at 25 ° C. and 1 atm is preferably 15 to 80% by volume based on the total volume of Compound A, Compound B and 1223yd. -55 volume% is more preferable, 20-45 volume% is still more preferable, and 20-40 volume% is especially preferable.
The content of Compound A at 25 ° C. and 1 atm is preferably 20 to 80% by volume, particularly preferably 40 to 60% by volume, based on the total volume of Compound A and Compound B.

The solvent composition of the third embodiment may contain components other than those described above. Specific examples of the other components are the same as those of the solvent composition of the first embodiment, and a description thereof will not be repeated.
The use of the solvent composition of the third embodiment and applicable articles are the same as those of the solvent composition of the first embodiment, and therefore, description thereof will be omitted.

[Washing method]
The cleaning method of the present invention provides the above-described solvent composition (that is, the solvent composition of the first embodiment, the solvent composition of the second embodiment, or the solvent composition of the third embodiment) on the surface of an article. (Composition) to remove dirt adhering to the surface of the article.
Since the solvent composition, the article, and the stain are as described above, description thereof will be omitted.
When the solvent composition contains the above-mentioned surfactant, the cleaning method of the present invention is suitable for dry cleaning, and more specifically, is suitable for removing dirt attached to textiles.

Specific examples of the cleaning method of the present invention include hand wiping cleaning, immersion cleaning, spray cleaning, immersion rocking cleaning, immersion ultrasonic cleaning, steam cleaning, and a combination thereof.
In these cleaning methods, the cleaning conditions such as the contact time and the number of times, and the temperature of the solvent composition at that time may be appropriately selected according to the cleaning method. In addition, a known apparatus can be appropriately selected according to each cleaning method. When the solvent composition of the present invention is used in these cleaning methods, the components contained in the solvent composition hardly decompose, and can be repeatedly used for a long time while maintaining the cleaning property.
The cleaning method of the present invention can be carried out, for example, using the method described in WO 2017/018010 and a cleaning apparatus.

[Production method of coating film]
The method for producing a coating film of the present invention includes the solvent composition described above (that is, the solvent composition according to the first embodiment, the solvent composition according to the second embodiment, or the solvent composition according to the third embodiment). ) And a non-volatile organic compound are applied to the surface of an article, and then the solvent composition is evaporated to obtain a coating containing the non-volatile organic compound.
The solvent composition according to the first embodiment, the solvent composition according to the second embodiment, the solvent composition according to the third embodiment, the non-volatile organic compound, and the article are as described above, and thus description thereof will be omitted.

The coating film forming composition is usually prepared as a solution composition in which a nonvolatile organic compound is dissolved in a solvent composition. The method for preparing the composition for forming a coating film is not particularly limited as long as the nonvolatile organic compound can be uniformly dissolved in the solvent composition at a predetermined ratio. The composition for forming a coating film basically comprises only a nonvolatile organic compound and a solvent composition.
The content of the nonvolatile organic compound is preferably from 0.01 to 50% by mass, more preferably from 0.05 to 30% by mass, and preferably from 0.1 to 20% by mass, based on the total mass of the composition for forming a coating film. Is particularly preferred. When the content of the nonvolatile organic compound is within the above range, it is easy to adjust the thickness of the coating film when the composition for forming a coating film is applied and the thickness of the coating film after drying to an appropriate range.
The balance of the composition for forming a coating film excluding the nonvolatile organic compound is the content of the solvent composition.

Specific examples of the method of applying the composition for forming a coating film include coating with a brush, spray coating, coating by dipping the article in the composition for forming a coating, and tube or injection by sucking up the composition for forming a coating. Coating in which the coating-forming composition is brought into contact with the inner wall of the needle is exemplified.
As a method for evaporating the solvent composition from the coating film forming composition, a known drying method can be mentioned, and specifically, air drying and heating can be mentioned. The drying temperature is preferably from 20 to 100C.
When the solvent composition of the present invention is used as the solvent contained in the coating film forming composition, the components of the solvent composition hardly decompose during storage or use of the coating film forming composition.

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these examples.

[Synthesis of 1223yd]
1223yd was synthesized according to the method described in British Patent No. 709887.

[Examples 1 to 44, Comparative Examples 1 to 21]
The obtained 1223yd and the compounds described in Tables 1 to 3 were mixed so that the volume mixing ratio (% by volume) at 25 ° C. became a value shown in Tables 1 to 3, and each of Examples and Comparative Examples was mixed. A solvent composition was obtained. However, Comparative Example 21 includes only 1223yd.

Here, of the components described in Tables 1 to 3, an outline of the components described by trade names is shown below.
Bertrel XF: 1,1,1,2,3,4,4,5,5,5-decafluoropentane manufactured by Mitsui Chemers Fluoro Products Co., Ltd. AC-6000: manufactured by AGC Co., 1,1,1 , 2,2,3,3,4,4,5,5,6,6-tridecafluorooctane solcane 365mfc: 1,1,1,3,3-pentafluorobutane Novec 7100 manufactured by Solvay Japan : Nonafluorobutyl methyl ether (mixture of isomers) manufactured by 3M
-Novec 7300: 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane / Bertrel-Suplion manufactured by 3M: Mitsui・ Methoxytridecafluoroheptene (mixture of isomers) manufactured by Chemers Fluoro Products
-Fluorinert FC-72: manufactured by 3M, an isomer mixture containing perfluorohexane as a main component-Zeorola H: manufactured by Zeon, 1,1,2,2,3,3,4-heptafluorocyclopentane-AE -3000: 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, manufactured by AGC

[Evaluation test]
The following evaluation tests were performed using each of the solvent compositions obtained as described above.

<Material compatibility test>
100 g of the solvent composition was put into a 100 ml screw-neck heat-resistant bottle, and one test piece (25 mm × 25 mm × thickness 3 mm) of various materials (polycarbonate (PC)) was put. Then, after leaving still at 25 ° C. for 5 minutes, the test piece was taken out and the appearance change was evaluated according to the following evaluation criteria. In Comparative Example 21, a solvent containing only 1223yd was used instead of the solvent composition.
〇: No change in appearance was observed on the test piece.
C: Swelling and devitrification are slightly observed in the test piece, but there is no practical problem.
X: Dissolution or cracking of the test piece.

<Liquid paraffin solubility test>
Liquid paraffin (a reagent manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added to the solvent composition so as to be 10% by mass, shaken well, and allowed to stand at 25 ° C. for 5 minutes. The solubility was evaluated according to the following evaluation criteria. In Comparative Example 21, a solvent containing only 1223yd was used instead of the solvent composition.
[Evaluation criteria]
〇: Two-layer separation of cloudiness and liquid paraffin was not observed.
Δ: Light turbidity was observed but no two-layer separation was observed, and there was no practical problem.
×: Clear turbidity or separation of liquid paraffin is clearly observed.

<Simple ignition test>
5 g of the solvent composition was placed in a glass petri dish having a diameter of 100 mm, and an ignition test was performed at 25 ° C. using an ignition rod, and the ignition state was evaluated according to the following evaluation criteria. In Comparative Example 21, a solvent containing only 1223yd was used instead of the solvent composition.
〇: Flame does not transfer to the solvent in the petri dish. Do not ignite.
Δ: The flame is transferred to the solvent, but disappears within 3 seconds.
X: The solvent flame moves and burns for 3 seconds or more.

  Tables 1 to 3 show the results of the above evaluation tests.

  As shown in Tables 1 to 3, using a solvent composition containing 1223yd and compound A (Examples 1 to 16) and a solvent composition containing 1223yd and compound B (Examples 17 to 44) , 1223yd and a compound that does not correspond to compound A and compound B (Comparative Examples 1 to 20), and the case where only 1223yd was used (Comparative Example 21). It was found that the damage could be reduced.

Claims (18)

1,3-dichloro-2,3,3-trifluoropropene and at least one selected from the group consisting of a saturated hydrocarbon having 6 or more carbon atoms and a compound represented by the formula (1). Characteristic solvent composition.
_{C x H y F z O v} N w (1)
In the formula (1), x is an integer of 3 or more, y is an integer of 0 or more, z is an integer of 1 or more, and v and w each represent an integer of 0 or more. However, y ≦ z and 2x−2 ≦ y + z ≦ 2x + 3 are satisfied, and in the molecule, an N—H bond, a C ＝ N bond, a C≡N bond, an O—H bond, a C ＝ O bond, and —CHF ₂ It does not include the represented groups and ring structures.   The content of the saturated hydrocarbon at 25 ° C. and 1 atm is 15 to 45% by volume based on the total volume of the saturated hydrocarbon and 1,3-dichloro-2,3,3-trifluoropropene. Item 7. The solvent composition according to Item 1.   The solvent composition according to claim 1, wherein the solvent composition contains two or more types of the saturated hydrocarbon.   The solvent composition according to any one of claims 1 to 3, wherein the boiling point of the saturated hydrocarbon is 50 to 130 ° C.   The solvent composition according to any one of claims 1 to 4, wherein the saturated hydrocarbon has 6 to 8 carbon atoms. The solvent composition is an azeotropic composition or an azeotropic composition,
The saturated hydrocarbon is normal hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, cyclohexane, methylcyclopentane, normal heptane, 2-methylhexane, 3-methyl The solvent composition according to any one of claims 1 to 5, which is at least one compound selected from the group consisting of hexane, 4-methylhexane, normal octane, and isooctane.   The content of the compound represented by the formula (1) at 25 ° C. and 1 atm is calculated based on the total mass of the compound represented by the formula (1) and 1,3-dichloro-2,3,3-trifluoropropene. The solvent composition according to claim 1, which is 15 to 55% by volume.   The solvent composition according to claim 1, comprising two or more compounds represented by the formula (1).   9. The solvent composition according to claim 1, wherein the compound represented by the formula (1) has a boiling point of 50 to 130 ° C. 10.   The solvent composition according to any one of claims 1 and 7 to 9, wherein the compound represented by the formula (1) satisfies 4 ≦ x + v + w ≦ 9, 1 ≦ y, and 5 ≦ z.   The solvent composition according to claim 10, wherein the compound represented by the formula (1) satisfies 0 ≦ v ≦ 1. The solvent composition is an azeotropic composition or an azeotropic composition,
When the compound represented by the formula (1) is nonafluorobutyl methyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoro Methyl) pentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, perfluorohexane, perfluorotributylamine and at least one selected from the group consisting of perfluorotripropylamine The solvent composition according to any one of claims 1 and 7 to 9, which is a compound.   A cleaning method, comprising: bringing a solvent composition according to any one of claims 1 to 12 into contact with a surface of an article to remove dirt attached to the surface of the article.   The cleaning method according to claim 13, wherein the article has at least one resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin on the surface.   The cleaning method according to claim 13, wherein the dirt is oils and fats or dust.   A composition for forming a coating film, comprising a nonvolatile organic compound and the solvent composition according to any one of claims 1 to 12.   After applying the composition for forming a coating film according to claim 16 to the surface of an article, the solvent composition is evaporated to obtain a coating film containing the nonvolatile organic compound. Production method.   The method according to claim 17, wherein the article has at least one resin selected from the group consisting of a polycarbonate resin, a polystyrene resin, and an acrylonitrile-butadiene-styrene resin on the surface.