Fluorine-containing solvent composition

Abstract

To provide a novel composition that can be used in a wide range of applications.SOLUTION: Disclosed are compositions comprising perfluoroheptene and chlorotrifluoropropene, detergents comprising the same, and methods of cleaning an article by using the same.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a fluorine-based solvent composition containing perfluoroheptene (PFH) and chlorotrifluoropropene. [Background technology]

[0002] Fluorinated solvents, including halogenated hydrocarbons such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), have been used in many industries for a wide range of applications including, but not limited to, aerosol propellants, refrigerants, solvents, cleaning agents, blowing agents for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing agents, and displacement drying agents.

[0003] However, CFCs and HCFCs are known to be ozone-depleting substances, and HCFCs, particularly HCFC-225, have been widely used due to their excellent non-flammability, polymer compatibility, and stability. However, HCFCs have an ozone-depleting potential and a high global warming potential, so they were completely phased out in 2019. On the other hand, although HFCs do not pose a risk of depleting the ozone layer, they do contribute to global warming as greenhouse gases, and therefore there is a demand for alternatives that have a lower environmental impact, i.e., an ozone depletion potential of zero and a very low global warming potential.

[0004] As such substitutes, hydrochlorofluoroolefins (HCFOs), hydrofluoroolefins (HFOs), and perfluoroolefins (PFOs) have been developed, and among PFOs, perfluoroheptene (PFH), in which all hydrogen has been replaced with fluorine, has zero ozone depletion potential and low global warming potential, and various uses have been proposed (Patent Document 1, Patent Document 2). Also, chlorotrifluoropropene is known as an HCFO, and is considered to be useful as a cleaning agent, solvent, etc. (Patent Document 6). However, in cleaning applications, HCFOs have a high ability to dissolve polymers (strong polymer attack (solubility)), so they cannot be used in products containing polymers, and HFOs and PFHs have low oil solubility, so it has been difficult to obtain a cleaning effect.

[0005] It is also known that azeotropic compositions that do not fractionate during use or distillation during recovery, that is, that have constant boiling point properties and do not fractionate during boiling or evaporation, are useful (e.g., Patent Document 3, Patent Document 4, and Patent Document 5). However, as described in Patent Document 1, it is impossible to theoretically predict whether or not an azeotropic composition will be formed, and the search for new azeotropic compositions with excellent properties is ongoing for various combinations. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2017-110035 A [Patent Document 2] International Publication No. 2019 / 213193 [Patent Document 3] Special Publication No. 6-501949 [Patent Document 4] Special Publication No. 2013-514444 [Patent Document 5] Special Publication No. 2012-528922 [Patent Document 6] International Publication No. 2018 / 092780 Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a novel azeotrope-like composition which solves the above problems and can be used in a wide range of industrial applications. [Means for solving the problem]

[0008] The present inventors have discovered that a composition containing perfluoroheptene (PFH), which has an ozone depletion potential of zero and a low global warming potential, and chlorotrifluoropropene, which has excellent oil solubility, is a composition that is highly safe and environmentally friendly, has excellent polymer compatibility (polymer attack (solubility) is suppressed), and forms an azeotrope-like composition that behaves similarly to a single compound, thereby completing the present invention.

[0009] That is, the present invention is characterized in the following points. 1. A composition containing perfluoroheptene and chlorotrifluoropropene. 2. An azeotropic or azeotrope-like composition consisting of perfluoroheptene and chlorotrifluoropropene. 3. The composition according to 1. or 2., wherein the perfluoroheptene is at least one selected from 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene, and isomers thereof. 4. The composition according to 1. or 2., wherein the chlorotrifluoropropene is at least one member selected from the group consisting of 1-chloro-2,3,3-trifluoropropene, 1-chloro-3,3,3-trifluoro-1-propene, and isomers thereof. 5. The composition according to any one of 1. to 4., which consists of 10.0 to 75.0 mass % of perfluoroheptene and 25.0 to 90.0 mass % of 1-chloro-2,3,3-trifluoro-1-propene. 6. The composition according to any one of 1. to 5., which comprises 20.0 to 75.0 mass % of perfluoroheptene and 25.0 to 80.0 mass % of 1-chloro-2,3,3-trifluoro-1-propene. 7. The composition according to any one of 1. to 6., which comprises 45.0 to 55.0 mass % of perfluoroheptene and 45.0 to 55.0 mass % of 1-chloro-2,3,3-trifluoro-1-propene. 8. The composition according to any one of 1. to 4., which comprises 5.0 to 30.0 mass % of perfluoroheptene and 70.0 to 95.0 mass % of 1-chloro-3,3,3-trifluoro-1-propene. 9. The composition according to any one of 1. to 4. or 8., which comprises 10.0 to 20.0 mass % of perfluoroheptene and 80.0 to 90.0 mass % of 1-chloro-3,3,3-trifluoro-1-propene. A cleaning agent comprising the composition according to any one of 10.1 to 9. A method for cleaning articles using a cleaning agent as described in paragraph 11.10. Effect of the Invention

[0010] According to the present invention, it is possible to provide a composition that has an ozone depletion potential of zero and a very low global warming potential. The composition of the present invention contains perfluoroheptene (PFH) and chlorotrifluoropropene, which has excellent oil solubility, and is a composition that is highly safe and environmentally friendly, and has excellent polymer compatibility (polymer attack (solubility) is suppressed). The present invention also has the advantage that it is an azeotrope-like composition that behaves similarly to a single compound and is not flammable. [Brief description of the drawings]

[0011] [Figure 1] 1 shows a vapor-liquid equilibrium curve of Example 1. [Diagram 2] 2 shows a vapor-liquid equilibrium curve of Example 2. [Diagram 3] The results of the resin compatibility test for Example 3 (right) and Comparative Example 2 (left) are shown. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in detail below. The composition of the present invention consists essentially of perfluoroheptene (PFH) and chlorotrifluoropropene, and it is preferred that both components together account for 50% or more of the composition, desirably 55% or more, and more desirably 60% or more.

[0013] In the present invention, PFH is not particularly limited to its structural isomer or stereoisomer, and may be a single isomer or a mixture of isomers. Preferably, PFH is at least one selected from 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene (perfluoro-3-heptene), 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene (perfluoro-2-heptene), and isomers thereof. More preferably, cis-perfluoro-3-heptene, trans-perfluoro-3-heptene, or a mixture containing them. In particular, trans-perfluoro-3-heptene or a mixture containing it is preferred.

[0014] Chlorotrifluoropropene (HCFO-1233) has various isomers, but the HCFO-1233 used in the present invention is preferably 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), 1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd), or a mixture thereof. HCFO-1233yd is preferably cis-HCFO-1233yd or a mixture containing cis-HCFO-1233yd.

[0015] As recognized in the art, an azeotropic composition is a mixture of two or more distinct components which, when in liquid form at a given pressure, boils at a substantially constant temperature, which is either above or below the boiling temperatures of the individual components, and which provides a vapor composition that is essentially the same as the overall liquid composition during boiling (see, e.g., M. F. Doherty and (See MFMalone, Conceptual Design of Distillation Systems, McGraw-Hill, New York, 2001, pp. 185-186, 351-359).

[0016] In this case, when the composition of the liquid is changed in various ways within a range close to the composition of the azeotropic mixture and the vapor-liquid equilibrium relationship at constant pressure is measured, it is known that the boiling point of the azeotropic composition becomes extremely maximum or minimum.

[0017] Thus, the essential characteristics of an azeotropic composition are that at a given pressure, the boiling point of the liquid composition is fixed, and that the composition of the vapor above the boiling composition is essentially that of the entire liquid composition during boiling (i.e., no fractionation of the components of the liquid composition occurs). It is also recognized in the art that when an azeotropic composition is subjected to boiling at different pressures, both the boiling point and the mass percentage of each component of the azeotropic composition may change. Thus, an azeotropic composition may be defined in terms of a unique relationship that exists between the components, or in terms of a compositional range of the components, or in terms of the exact mass percentage of each component of a composition characterized by a fixed boiling point at a specified pressure.

[0018] The compositions of the present invention refer to compositions that behave like azeotropic compositions (i.e., have constant boiling point properties or a tendency not to fractionate upon boiling or evaporation). Thus, during boiling or evaporation, the vapor-liquid compositions change only to a minimal or negligible extent, if at all. This is in contrast to non-azeotrope-like compositions, in which the vapor-liquid compositions change to a significant extent during boiling or evaporation.

[0019] The compositions of the present invention also exhibit liquidus and vapor phases with substantially no temperature difference, i.e., the difference between the liquidus and vapor temperatures at a given pressure will be small. In the present invention, compositions with a liquidus temperature difference of 2° C. or less (based on the minimum azeotropic point) are considered to be azeotrope-like compositions.

[0020] Furthermore, it is well known in the art that a system is defined as forming an azeotrope or azeotrope-like composition when its relative volatility approaches 1.0. Relative volatility is the ratio of the volatility of component 1 to the volatility of component 2. The ratio of the mole fraction of a component in the vapor to that in the liquid is the volatility of that component.

[0021] The azeotrope-like composition of the present invention containing PFH and chlorotrifluoropropene desirably has a boiling point in the range of 30 to 100°C, preferably 40 to 80°C, under atmospheric pressure.

[0022] In the present invention, when the chlorotrifluoropropene is 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), the composition of the present invention preferably has a boiling point of 49 to 51°C, more preferably 49 to 50°C, under atmospheric pressure. The blending ratio is preferably PFH:HCFO-1233yd=10-75% by mass:90-25% by mass, more preferably 20-75% by mass:80-25% by mass, and even more preferably 45-55% by mass:55-45% by mass. When PFH is less than 10% by mass (i.e., when the amount of HCFO is too large compared to PFH), polymer attack (solubility) may increase, and conversely, when PFH exceeds 75% by mass (i.e., when the amount of HCFO is too small compared to PFH), the oil removal rate may decrease.

[0023] In the present invention, when the chlorotrifluoropropene is 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), the composition of the present invention preferably has a boiling point of 36 to 41°C, more preferably 38.5 to 40.5°C, under atmospheric pressure. The blending ratio is preferably PFH:HCFO-1233zd=5-30% by mass:95-70% by mass, and more preferably 10-20% by mass:90-80% by mass. When PFH is less than 5% by mass (i.e., when the amount of HCFO is too large compared to PFH), polymer attack (solubility) may increase, and conversely, when PFH is more than 30% by mass (i.e., when the amount of HCFO is too small compared to PFH), the oil removal rate may decrease.

[0024] The composition of the present invention preferably further contains an alcohol, preferably at least one selected from alcohols having 1 to 3 carbon atoms, more preferably ethanol.

[0025] The composition of the present invention may contain one or more stabilizers, such as nitroalkanes, epoxides, furans, benzotriazoles, phenols, amines or phosphates, as necessary, and the amount of the stabilizer is 0.01 to 5 mass %, preferably 0.05 to 0.5 mass %, based on the composition.

[0026] The composition of the present invention may also contain other components, such as alcohols (other than alcohols having 1 to 3 carbon atoms), ketones, ethers, esters, hydrocarbons, amines, glycol ethers, and siloxanes, as necessary, to the extent that the features of the present invention are not impaired.

[0027] The composition of the present invention has an ozone depletion potential (ODP) of zero and a global warming potential (GWP ) is about 100 or less, preferably 50 or less, and more preferably 10 or less. Here, the ODP and GWP in the present invention are based on the World Meteorological Organization report "Scientific This is defined in the "Assessment of Ozone Depletion, 2002".

[0028] The compositions of the present invention can be used in a wide variety of applications where halogenated hydrocarbons have traditionally been used, such as aerosol propellants, refrigerants, solvents, cleaning agents, particulate removal fluids, blowing agents (foam expansion agents) for thermoplastic and thermoset foams, heat transfer media, gaseous dielectrics, fire extinguishing and suppression agents, power cycle working fluids, polymerization media, carrier fluids, buffing agents, and displacement drying agents.

[0029] When the present invention is used as a cleaning agent, the objects to be cleaned with the composition of the present invention are not particularly limited, but the composition can be suitably used for objects that are continuously produced and cleaned, such as electronic, electrical and mechanical parts, or small automotive parts. In particular, the composition of the present invention is particularly useful for cleaning solid surfaces having organic (oil) or inorganic dirt on the surface thereof, such as semiconductor surfaces, electronic substrate surfaces, electronic circuits, CMOS (Complementary Metal Oxide Semiconductor), MEMS (Microelectronics), etc. The present invention can be suitably used as a cleaning agent for cleaning surfaces having fine structures, such as surfaces of hard disks, electro-mechanical systems, and other surfaces having fine structures.

[0030] In particular, the composition of the present invention is highly safe and environmentally friendly, has excellent polymer compatibility (polymer attack (solubility) is suppressed), has high oil solubility and excellent cleaning properties, and forms an azeotrope-like composition that behaves similarly to a single compound, making it suitable for cleaning resin products.

[0031] The composition of the present invention can also be suitably used as a refrigerant for cooling. In particular, since the composition of the present invention exhibits azeotropy, it is also suitable as a refrigerant for use in a cooling method (boiling cooling) that includes a step of condensing the composition of the present invention and a step of evaporating the composition near an object to be cooled.

[0032] Furthermore, the compositions of the present invention can be suitably used as blowing agents (foam expansion agents) for producing thermoplastic or thermoset foams. The present invention will be described in detail below with reference to examples. EXAMPLES

[0033] The boiling point, surface tension, density, viscosity, and flash point of a mixture of PFH and chlorotrifluoropropene were measured and calculated, and the oil solubility and resin compatibility tests were performed using the following methods.

[0034] [Boiling point (equilibrium reflux boiling point)] The boiling point (equilibrium reflux boiling point) was measured in accordance with JIS K 2233, except that the cooling water temperature was set to 5°C and heating was performed directly without any interposition between the hot plate and the flask.

[0035] Density: Amager's Law V m =Σx j V j V: Density x: mole fraction The density of PFH is 1.63 g / ml (calculated using NIST REFPROP Ver. 10 at 25°C), the density of HCFO-1233yd is 1.39 g / ml (quoted from AGC Research Report 69 (2019) Development of Environmentally Friendly Fluorinated Solvent AMOLEA (registered trademark) AS-300), and the density of HCFO-1233zd is 1.31g / ml (quoted from Central Glass Co., Ltd., 1233Z, Excellent environmental performance, high cleaning power, next generation fluorine-based solvent, October 2015) was used.

[0036] The viscosity of the composition was calculated according to the following formula. Viscosity: McAllister's method lnη m =Σx i f(η i ) η: Viscosity x: mole fraction f(η): logarithm of viscosity The viscosity of PFH is 0.77 mPa·s (calculated using NIST REFPROP Ver.10, set at 25°C), the viscosity of HCFO-1233yd is 0.57 mPa·s (quoted from AGC Research Report 69 (2019) Development of Environmentally Friendly Fluorinated Solvent AMOLEA (registered trademark) AS-300), and the viscosity of HCFO-1233zd is 0.41 mPa·s (Central Glass Co., Ltd., 1233Z Excellent environmental performance, high cleaning power Next Generation Fluorine Solvents (cited from October 2015) were used.

[0037] [surface tension] The surface tension of the composition was calculated according to the following formula. Surface tension: Macleod-Sugden correlation σ 1 / 4 =[P](ρ L -ρ V ) / MW σ; surface tension P: Parachor coefficient ρ L :Liquid specific gravity ρ v :Vapor density, MW: molecular weight The surface tension value of PFH was 13.8 mN / m (calculated using NIST REFPROP Ver.10, set at 25°C), the surface tension of HCFO-1233yd was 21.7 mN / m (quoted from AGC Research Report 69 (2019) Development of Environmentally Friendly Fluorinated Solvent AMOLEA (registered trademark) AS-300), and the surface tension of HCFO-1233zd was 18.6 mN / m (quoted from Central Glass Co., Ltd., 1233Z Excellent Environmental Performance, High Cleaning Power Next Generation Fluorinated Solvent, October 2015).

[0038] [flash point] The flash point was measured by the tag closed cup and Cleveland open cup flash point tests according to JIS K 2265-1980.

[0039] [Oil dissolution rate] Into a 50 ml glass screw bottle, 20 g of any of the compositions of Examples 1 to 7 shown in Table 1 was added, and the amount of oil shown in the "Amount of oil mixed" in Table 2 or Table 3 (expressed as mass % relative to 20 g of composition) was added. The bottle was shaken by hand at room temperature for 30 seconds and then allowed to stand, and the appearance of the solution was visually observed. ○: Homogeneous solution (no cloudiness or separation into two layers) ×: Cloudy or separated into two layers

[0040] [Oil removal rate] The oil removal rate is used as an index of cleaning performance and is calculated using the following formula:

number

[0041] [Washing conditions] As the cleaning agent, the composition shown in Table 1 is used. As the equipment, a tabletop ultrasonic cleaner (three-frequency ultrasonic cleaner VS-100III type) is used, and cleaning is performed at an ultrasonic frequency of 28 kHz, an output of 100 W, a cleaning time of 3 minutes, and at room temperature.

[0042] [Resin compatibility test (ABS resin)] A test piece (2×20×100 mm) made of ABS resin was immersed in the composition shown in Table 2 at room temperature for 3 minutes, and the presence or absence of surface change was visually observed. 〇: No change ×: Softening

[0043] The PFH and chlorotrifluoropropene used in the examples and comparative examples are as follows. ·PFH 93% by weight of perfluoro-3-heptene, and 7% by mass perfluoro-2-heptene, A mixture consisting of Chlorotrifluoropropene HCFO-1233yd (AGC AMOLEA (registered trademark) AS-300) HCFO-1233zd (Central Glass Co., Ltd., Serefin (registered trademark) 1233Z) The oils and resins used in the examples and comparative examples are as follows. ·Oils Polyalkylene glycol (PAG) (Snice (registered trademark) P 56, manufactured by Japan Sun Oil Co., Ltd.) Polyvinyl ether synthetic base oil (PVE) (Daphne (registered trademark) hermetic oil FV68S, manufactured by Idemitsu Kosan Co., Ltd.) Naphthenic mineral oil (Suniso (registered trademark) 4GS, manufactured by Japan Sun Oil Co., Ltd.) Refrigeration Oil) Polyethylene glycol (PEG-200, manufactured by Sanyo Chemical Industries, Ltd.) Liquid Paraffin (Liquid Paraffin LP No.70-S, manufactured by Sanko Chemical Industry Co., Ltd.) ·Resins ABS resin (Techno UMF Co., Ltd., Psychotech T1101)

[0044] [Examples 1 to 7, Comparative Examples 1 to 3] The boiling point, surface tension, density, viscosity, and flash point of each composition of the present invention, as well as PFH, HCFO-1233yd, and HCFO-1233zd, are shown in Table 1. The oil solubilities of Examples 1 to 3 are shown in Table 2, and the oil solubilities of Examples 4 to 7 are shown in Table 3. In addition, the oil removal rates of Examples 3 and 4 and Comparative Examples 1 to 3 are shown in Table 4. Furthermore, the results of the ABS resin compatibility test are shown in Table 5, and photographs of the results of the resin compatibility test of the ABS resin of Example 3 and Comparative Example 2 are shown in Figure 3. Moreover, the vapor-liquid equilibrium curves of Examples 3 and 4 are shown in FIG. 1 and FIG. In FIG. 1, a minimum boiling point is observed when the mass ratio of PFH / HCFO-1233yd is approximately 50 / 50, and in FIG. 2, a minimum boiling point is observed when the mass ratio of PFH / HCFO-1233zd is approximately 16 / 84 mass%, confirming that PFH and chlorotrifluoropropene exhibit an azeotropic behavior. In addition, in FIG. 3, in the composition of Comparative Example 2, the ABS resin was dissolved into the composition, and thus the composition became cloudy. However, in the composition of Example 3, no such cloudiness was observed. As shown in Tables 1 to 5 and FIG. 3, the compositions of the examples exhibit an excellent oil removal rate and high detergency, while also exhibiting extremely low polymer attack (solubility).

[0045] [Table 1]

[0046] [Table 2]

[0047] [Table 3]

[0048] [Table 4]

[0049] [Table 5]

Claims

1. A cleaning composition comprising an azeotrope or azeotrope-like composition consisting of 10.0 to 75.0 mass % perfluoroheptene and 25.0 to 90.0 mass % 1-chloro-2,3,3-trifluoropropene.

2. A cleaning composition comprising an azeotrope or azeotrope-like composition consisting of 5.0 to 30.0 mass % perfluoroheptene and 70.0 to 95.0 mass % 1-chloro-3,3,3-trifluoro-1-propene.

3. 3. The cleaning composition according to claim 1, wherein the perfluoroheptene is at least one selected from the group consisting of 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-3-heptene, 1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene, and isomers thereof.

4. 2. The cleaning composition according to claim 1, which comprises an azeotrope or azeotrope-like composition consisting of 20.0 to 75.0% by weight of perfluoroheptene and 25.0 to 80.0% by weight of 1-chloro-2,3,3-trifluoro-1-propene.

5. 2. The cleaning composition according to claim 1, which comprises an azeotrope or azeotrope-like composition consisting of 45.0 to 55.0% by weight of perfluoroheptene and 45.0 to 55.0% by weight of 1-chloro-2,3,3-trifluoro-1-propene.

6. 3. The cleaning composition according to claim 2, which comprises an azeotrope or azeotrope-like composition consisting of 10.0 to 20.0% by weight of perfluoroheptene and 80.0 to 90.0% by weight of 1-chloro-3,3,3-trifluoro-1-propene.

7. A method for cleaning articles using the cleaning composition of claim 1 or 2.

Images