Fluorine-based solvent compositions

Abstract

To provide a novel composition which has an excellent washing effect and also excellent safety.SOLUTION: A composition includes at least one selected from trans-dichloroethylene, hexamethyldisiloxane, and decafluoropentane, heptafluorocyclopentane, hexafluoro-2-butene, methoxyperfluoroheptene, and tetradecafluoroheptene. There is also provided a method for washing an article using the same.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a new solvent composition containing at least one selected from trans-dichloroethylene, hexamethyldisiloxane, and decafluoropentane, hexafluoro-2-butene, methoxyperfluoroheptene, and tetradecafluoroheptene. The solvent composition of the present invention is particularly rich in solubility for silicone oil.

Background Art

[0002] Coating the surface of medical devices / components made of glass or elastomers with silicone (polyalkylsiloxane), particularly silicone oil in a liquid state at room temperature such as polymethylsiloxane, to improve the sliding property and water / oil repellent performance of the devices / components is widely used. When performing such coating with silicone or silicone oil, fluorinated solvents, particularly hydrochlorofluorocarbons (HCFCs), are widely used as solvents for dissolving them well (Patent Document 1). Representative examples of such HCFCs include 1,1-dichloro-1-fluoroethane (HCFC-141b), dichloropentafluoropropane (HCFC-225), and the like. However, since these HCFCs have a high ozone depletion potential, they are to be phased out in developed countries by 2020 and in developing countries by 2030 in principle from the perspective of ozone layer protection.

[0003] Therefore, hydrochlorofluoroolefins (HCFOs) such as (Z)-1-chloro-3,3,3-trifluoropropene and chlorine-based solvents have been proposed as alternatives to HCFCs. However, while HCFOs can effectively dissolve silicone oil, they cause significant damage to elastomers (i.e., they have a strong chemical attack effect on elastomers) (Patent Document 2). Therefore, they cannot necessarily be used as a substitute for HCFCs in applications where components containing elastomers are silicone-coated. Furthermore, chlorine-based solvents are widely known to have adverse effects on human health (toxicity), making their handling difficult (Non-Patent Document 1). Furthermore, while hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs) have been developed as alternatives to HCFCs, their use as substitutes for HCFCs is practically difficult due to their extremely low ability to dissolve silicone oil.

[0004] Furthermore, due to their water-repellent and lubricating properties, silicones and silicone oils are widely used as lubricants and mold release agents in industrial products. When silicones or silicone oils are used as lubricants or mold release agents, it is necessary to remove and clean any remaining silicone or silicone oil from the surface of the industrial product during maintenance. It is known that HCFCs, chlorinated solvents, dimethylsiloxane, and brominated solvents are used to remove and clean such silicones and silicone oils. The problems with the use of HCFCs and chlorinated solvents are as described above, and dimethylsiloxane has a low flash point and a high risk of ignition, requiring caution during use, while brominated solvents, like chlorinated solvents, have toxicity issues. Incidentally, perfluoroheptene (PFH) is known as a solvent with no flash point, low toxicity, zero ozone depletion potential, and low global warming potential. However, it has poor solubility for silicones and therefore cannot be used for the purpose of removing or cleaning silicones and silicone oils.

[0005] Furthermore, compositions consisting of a fluorine-based solvent and various other solvents (Patent Documents 3-7) are also known. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2019 / 078350 [Patent Document 2] International Publication No. 2019 / 082998 [Patent Document 3] Special Publication No. 2020-519710 [Patent Document 4] Special Publication No. 6-501949 [Patent Document 5] Special Publication No. 2013-514444 [Patent Document 6] Special Publication No. 2012-528922 [Patent Document 7] Japanese Patent Publication No. 2017-110035 [Patent Document 8] Japanese Patent Publication No. 2017-110035 [Non-patent literature]

[0007] [Non-Patent Document 1] http: / / www.jahcs.org / leaflet / Youzai_Ver.8.1.pdf [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a novel composition that can be used in a wide range of applications to solve the above problems, and in particular, to provide a fluorine-based solvent composition that is useful for use in silicone coating processes, as well as for removing and cleaning silicone. [Means for solving the problem]

[0009] Specifically, it includes the following aspects.

[0010] [1] A composition comprising (a) trans-dichloroethylene, (b) hexamethyldisiloxane, and (c) at least one fluorinated solvent selected from decafluoropentane, hexafluoro-2-butene, methoxyperfluoroheptene, and perfluoroheptene.

[0011] [2] The composition of [1] wherein (a) trans-dichloroethylene is (E)-1,2-dichloroethylene.

[0012] [3] The composition of [1] wherein (c) the fluorinated solvent is decafluoropentane and is 1,1,1,2,3,4,4,5,5,5-decafluoropentane.

[0013] [4] The composition of [1] wherein (c) the fluorinated solvent is hexafluoro-2-butene and is at least one selected from Z-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,4,4,4-hexafluoro-2-butene.

[0014] [5] The composition of [1] wherein (c) the fluorinated solvent is methoxyperfluoroheptene and is (Z)-1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxyhept-3-ene, (E)-1,1,1,2,2,3,5,5,6,-six,7,7,7-tridecafluoro-4-methoxyhept-3-ene, or a mixture thereof.

[0015] [6] The composition of [1] wherein (c) the fluorinated solvent is perfluoroheptene and is at least one selected from 2-perfluoroheptene and 3-perfluoroheptene.

[0016] [7] A coating composition obtained by dissolving silicone oil in the composition of [1].

[0017] [8] A composition for removing silicone oil, comprising the composition of [1].

Advantages of the Invention

[0018] The composition of the present invention has an ozone depletion potential (ODP) of 0, a global warming potential (GWP) of about 100 or less, preferably 50 or less, more preferably 10 or less, and is friendly to the global environment. Here, ODP and GWP are defined in the report "Scientific Assessment of Ozone Depletion, 2002" of the World Meteorological Organization. Further, the composition of the present invention has extremely low toxicity (high safety), low flammability, and excellent compatibility with polymers such as butyl rubber (suppressed polymer attack). And, since the composition of the present invention has a high solubility of silicone / silicone oil, it can be used in the coating process of silicone / silicone oil for medical devices / members, etc., and can also be used for the removal and cleaning of silicone / silicone oil.

Embodiments for Carrying Out the Invention

[0019] Specifically, the present invention relates to (a) (E)-1,2-dichloroethylene and (b) hexamethyldisiloxane and (c) a composition comprising at least one fluorinated solvent selected from decafluoropentane, hexafluoro-2-butene, methoxyperfluoroheptene, and perfluoroheptene and.

[0020] In the present invention, it is preferable to add a third component to the mixture of trans-dichloroethylene and hexamethyldisiloxane in order to suppress the risk of ignition. The third component is preferably at least one selected from decafluoropentane, hexafluoro-2-butene, methoxyperfluoroheptene, and perfluoroheptene. Hereinafter, each component will be described.

[0021] (a) In the present invention, dichloroethylene can be 1,1-dichloroethylene, 1,2-dichloroethylene, or their isomers, but (E)-1,2-dichloroethylene (boiling point 48.7°C), which has extremely low toxicity among chlorine-based materials, is preferred. (E)-1,2-dichloroethylene is also called trans-1,2-dichloroethylene (t-DCE). [ka] It is a compound with the following structure. It is known to be used as an intermediate for other chlorine-based solvents, as an extraction solvent for resins, fragrances, and dyes, and as a cleaning agent. In the composition of the present invention, it is desirable that the component be present in an amount of 21% to 57%. More preferably, it is 28% to 50%, and even more preferably, 34% to 43%. A concentration exceeding 57% is undesirable because it increases the attack on the component, and a concentration below 21% is undesirable due to insufficient silicone oil solubility.

[0022] (b) Hexamethyldisiloxane (1,1,1,3,3,3-hexamethyldisiloxane) (HMDS) is [ka] Hexamethyldisiloxane is a linear siloxane, a type of organosilicon compound, having the structure shown, and is a volatile, highly flammable compound that is insoluble in water and soluble in organic solvents, with a boiling point of 99-101°C. As a commercially available product of hexamethyldisiloxane, for example, Shin-Etsu Silicone (registered trademark) KF-96L-0.65CS (manufactured by Shin-Etsu Chemical Co., Ltd., boiling point 100°C) can be used. In the composition of the present invention, it is desirable that it be contained in an amount of 0.1% to 21%. More preferably, it is 1.4% to 14%, and even more preferably, 1.4% to 10%. If it exceeds 21%, it is undesirable because the flammability increases and the drying properties deteriorate, and if it is less than 0.1%, it is undesirable because of the lack of solubility of the silicone oil.

[0023] (c) (c)-1 Decafluoropentane is C5H2F 10 The compound shown is known to be used, together with other solvents, as a cleaning agent, lubricant, and additive for electronic equipment and components (Patent Document 3). Decafluoropentane has multiple structural isomers, and these isomers may be used individually or as mixtures. 1,1,1,2,3,4,4,5,5,5-decafluoropentane (CF3CHFCHFCF2CF3; HFC43-10mee) is the most preferred because it is low in toxicity, has an ozone depletion potential of 0, a boiling point of approximately 55°C, and is non-flammable. It may be used alone or as a mixture of it with other decafluoropentane isomers. In the composition of the present invention, decafluoropentane is preferably contained in an amount of 40% to 60%, more preferably 45% to 55%. An amount exceeding 60% is undesirable due to poor silicone oil solubility, and an amount below 50% is undesirable because it increases flammability and causes greater damage to the components.

[0024] (c)-2 Hexafluoro-2-butene is a hydrofluoroolefin compound (a compound containing carbon atoms, hydrogen atoms, and fluorine atoms, and having a double bond in its molecule). Preferred compounds are at least one selected from cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzZ) and trans-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzzE). A more preferred compound is HFO-1336mzzZ. Examples of commercially available products include "Opteon® SF33" (manufactured by Mitsui Chemours Fluoroproducts Co., Ltd.). Opteon SF33 has an ozone depletion potential of 0 and a global warming potential of 2. The use of this component can reduce the flammability of the composition of the present invention. (This can be seen from the comparison between Example 4 and Comparative Example 6 described below.) Furthermore, because this component has a low boiling point, the composition of the present invention can be recycled. In the composition of the present invention, it is desirable that hexafluoro-2-butene be present in an amount of 40% to 60%, more preferably 45% to 55%. An amount exceeding 60% is undesirable due to insufficient solubility of the silicone oil, and an amount below 45% is undesirable due to concerns about increased flammability and damage to the components.

[0025] (c)-3 The following structures can be used as methoxyperfluoroheptene: (1) CF3(CF2)2CF=CFCF(OCH3)CF3 (2) CF3CF2CF = CF(CF2)2(OCH3)CF3 (3) CF3CF2CF = CFCF(OCH3)CF2CF3 (4) CF3CF = CFCF(OCH3)(CF2)2CF3 (5) CF3CF = CFCF2CF(OCH3)CF2CF3 (6) CF3CF2CF = C(OCH3)(CF2)2CF3 (7) CF3CF2C(OCH3) = CFCF2CF2CF3

[0026] Each of the above includes E and Z isomers, but a single isomer may be used, or a mixture of isomers may be used. More preferred compounds as methoxyperfluoroheptene are (Z)-1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxyhept-3-ene, (E)-1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxyhept-3-ene, as shown in (6) above, or mixtures thereof. A commercially available product is "Opteon® SF10" (manufactured by Mitsui Chemours Fluoroproducts Co., Ltd.). Opteon® SF10 has an ozone depletion potential of 0 and a global warming potential of less than 10. It is desirable to select a highly non-flammable methoxyperfluoroheptene. Methoxyperfluoroheptene can be produced, for example, by the method described in Japanese Patent Publication No. 2012-518010. In the composition of the present invention, it is desirable that methoxyperfluoroheptene be present in an amount of 40% to 60%, more preferably 45% to 55%. If it exceeds 60%, it is undesirable due to insufficient solubility of the silicone oil, and if it is less than 45%, it is undesirable due to concerns about increased flammability and damage to the components.

[0027] (c)-4 Perfluoroheptene (PFH) is C7F 14 The compound is represented by [formula]. There are no particular restrictions on the PFH used in the present invention; any structural isomer or stereoisomer can be used, and it may be a single isomer or a mixture thereof. Preferably, it is 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 at least one selected from their isomers. More preferably, it is (Z)-perfluoro-3-heptene, (E)-perfluoro-3-heptene, or a mixture containing them. In particular, (Z)-perfluoro-3-heptene or a mixture containing it is preferred. Examples of commercially available products include "Opteon® SF70" (manufactured by Mitsui Chemours Fluoroproducts Co., Ltd.). In the composition of the present invention, it is desirable that perfluoroheptene be present in an amount of 10% to 30%, more preferably 15% to 25%. An amount exceeding 30% is undesirable due to a lack of silicone solubility, and an amount less than 10% is undesirable due to concerns about increased flammability.

[0028] The compositions of the present invention may also contain, as necessary, alcohols, ketones, ethers, esters, hydrocarbons, amines, glycoethers, siloxanes, etc., in addition to the components (a) to (c), to the extent that they do not impair the characteristics of the present invention.

[0029] The composition of the present invention may optionally contain one or more nitroalkanes, epoxides, furans, benzotriazoles, phenols, amines, or phosphates as stabilizers, in an amount of 0.01 to 5.00% by mass, preferably 0.05 to 0.50% by mass, relative to the composition.

[0030] When the composition of the present invention is used for coating applications, silicon is used on medical devices / components. It is suitable for coating with silicone / silicone oil. Examples of substrates to be coated include polymers such as butyl rubber, urethane rubber, natural rubber, and EPDM rubber, or metals such as stainless steel, which are used in medical devices / components. The composition of the present invention has excellent solubility for silicone / silicone oil, and is therefore particularly suitable for coating medical devices / components containing butyl rubber with silicone / silicone oil. Because butyl rubber has high chemical resistance, it is used in medical stoppers and sealing materials for parts requiring chemical resistance. Examples of silicones include polyorganosiloxanes, which are liquid at room temperature (25°C). Polyorganosiloxanes include linear polyorganosiloxanes represented by the following chemical formulas: [ka] (In the formula, R independently represents a monovalent organic group, an SH group, a hydroxyl group, or a hydrogen atom, and n is an integer in the range of 1 ≤ n ≤ 1,000,000.) Alternatively, examples include cyclic polyorganosiloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and hexadecamethylcyclooctasiloxane. Examples of silicone oils include straight silicone oils, modified silicone oils such as reactive silicone oils and non-reactive silicone oils, or mixtures thereof. Examples of straight silicone oils include dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, and cyclic dimethyl silicone oil. Examples of reactive silicone oils include double-ended type (amino-modified, epoxy-modified, carbinol-modified, methacrylic-modified, polyether-modified, mercapto-modified, carboxyl-modified, silanol-modified, acrylic-modified, carboxylic acid anhydride-modified, etc.), side-chain type (amino-modified, epoxy-modified, carbinol-modified, mercapto-modified, carboxyl-modified, methylhydrogen-modified, etc.), single-ended type (epoxy-modified, carbinol-modified, diol-modified, methacrylic-modified, carboxyl-modified, etc.), and double-ended side-chain type (side-chain amino- and double-ended methoxy-modified, epoxy-modified, etc.). Examples of non-reactive silicone oils include side-chain type (polyether-modified, aralkyl-modified, fluoroalkyl-modified, long-chain alkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, phenyl-modified, etc.) and end-chain type (polyether-modified, etc.). A straight silicone oil is preferred, and a dimethyl silicone oil is more preferred. From the viewpoint of heat resistance, solubility, and film-forming properties, it is desirable to use a mixture of straight silicone oil and other silicone oils.

[0031] The composition of the present invention can also be used for cleaning purposes. In that case, examples of objects to be cleaned include silicone / silicone oil, fine particles and other foreign matter. It is particularly suitable for removing and cleaning silicone / silicone oil. The present invention will be described in detail below with reference to examples. [Examples]

[0032] The compounds used in the examples and comparative examples are as follows: (E)-1,2-dichloroethylene: Manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 48°C. Hexamethyldisiloxane: Manufactured by Shin-Etsu Industries Ltd., Shin-Etsu Silicone (registered trademark), KF-96L-0.65CS, boiling point 100℃. · 1,1,1,2,3,4,4,5,5,5-Decafluoropentane: Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., Bartrell® XF, boiling point 55°C. (Z)-1,1,1,4,4,4-Hexafluoro-2-butene: Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., Opteon® SF33, boiling point 33°C. • Methoxytridecafluoroheptene: Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., Opteon® SF10, boiling point 110°C. Tetradecafluoroheptene: Manufactured by Mitsui Chemours Fluoroproducts Co., Ltd., Opteon® SF70, boiling point 71.5°C. (Z)-1-chloro-2,3,3-trifluoro-1-propene: Manufactured by AGC Inc., AMOLEA® AS-300, boiling point 54°C, no flash point. (Z)-1-chloro-3,3,3-trifluoro-1-propene: Manufactured by Central Glass Co., Ltd., CELEFIN (registered trademark) 1233Z, boiling point 39°C, no flash point.

[0033] The abbreviations for each compound are shown in Table 1 below.

[0034] [Table 1]

[0035] [Silicone oil solubility] As a silicone oil, a mixture of a silicone solution (50% by mass silicone NA98, 40% by mass toluene, and 10% by mass isopropyl alcohol) and Shin-Etsu Silicone® Oil KF-96-100cs (manufactured by Shin-Etsu Industries Co., Ltd., viscosity 100 cSt) was prepared in a 2:1 ratio. 1.2 g of this oil was mixed with 10 ml of test solvent. After standing at room temperature for two weeks, a visual inspection was performed, and solutions that maintained a homogeneous state were judged to be soluble (○).

[0036] [Butyl rubber damage] A butyl rubber test specimen (manufactured by AS ONE Corporation, rubber stopper for vials, model number: Standard, diameter approximately 14 mmΦ) was immersed in a test solvent (150 g) at room temperature for 1 minute and dried at 105°C for 2 hours. The weight change of the butyl rubber test specimen was measured before and after the test, and specimens with a weight change of 0.2% or less were judged to have no butyl rubber damage (○).

[0037] [Flammability] The solvent was poured into a Cleveland open-top cup up to the mark, and an ignition source was brought close to observe whether or not flame propagation occurred. If no flame propagation occurred, it was marked as non-flammable (○), and if flame propagation occurred, it was marked as flammable (×).

[0038] [Examples 1-6, Comparative Examples 1-8] Various compositions were prepared using the above compounds in the volume ratios listed in Table 2, and their silicone oil solubility, butyl rubber damage, and flammability were determined. The results are shown in Table 2.

[0039] [Table 2]

[0040] The solvent compositions of Examples 1 to 6, which include all of (a), (b), and (c), are silicone oils. The evaluation of its solubility, butyl rubber damage resistance, and flammability was satisfactory, confirming that it can be used in the silicone / silicone oil coating process for medical devices / components without flammability issues, and that it can also be used for removing and cleaning silicone / silicone oil. In contrast, the solvent compositions of Comparative Examples 6 and 8, which contained only (a) and (b), exhibited poor flammability. Furthermore, Comparative Examples 1 to 3 and 7, which contained only (a) and (c) (i.e., did not contain (b)), exhibited poor silicone oil solubility and / or butyl rubber damage (high butyl rubber damage). In addition, AS300 and 1233Z, used in Comparative Examples 4 and 5, are widely known as solvents for silicone oil and are useful for removing and cleaning silicone oil, but it was confirmed that they have high butyl rubber damage properties.

Claims

1. (a) transdichloroethylene, (b) Hexamethyldisiloxane, and (c) A coating composition obtained by dissolving a silicone oil in a composition comprising at least one fluorine-based solvent selected from (c-1) decafluoropentane, (c-2) hexafluoro-2-butene, (c-3) methoxyperfluoroheptene, and (c-4) perfluoroheptene, The composition containing (a) to (c) is, by volume ratio, (a) 21% to 57%, (b) 0.1% to 21%, and The coating composition comprising at least one selected from (c-1) 40% to 60%, (c-2) 40% to 60%, (c-3) 40% to 60%, and (c-4) 10% to 30%.

2. (a) transdichloroethylene, (b) Hexamethyldisiloxane, and (c) A composition for removing silicone oil comprising a composition containing at least one fluorine-based solvent selected from (c-1) decafluoropentane, (c-2) hexafluoro-2-butene, (c-3) methoxyperfluoroheptene, and (c-4) perfluoroheptene, The composition containing (a) to (c) is, by volume ratio, (a) 21% to 57%, (b) 0.1% to 21%, The silicone oil removal composition comprising at least one selected from (c-1) 40% to 60%, (c-2) 40% to 60%, (c-3) 40% to 60%, and (c-4) 10% to 30%.

3. (a) The coating composition according to claim 1, wherein transdichloroethylene is (E)-1,2-dichloroethylene, or the silicone oil removal composition according to claim 2.

4. (c) The coating composition according to claim 1, wherein the fluorine-based solvent is decafluoropentane, and is 1,1,1,2,3,4,4,5,5,5-decafluoropentane, or the silicone oil removal composition according to claim 2.

5. (c) The coating composition according to claim 1 or the silicone oil removal composition according to claim 2, wherein the fluorine-based solvent is hexafluoro-2-butene, and is selected from at least one of Z-1,1,1,4,4,4-hexafluoro-2-butene and E-1,1,1,4,4,4-hexafluoro-2-butene.

6. (c) The coating composition according to claim 1 or the silicone oil removal composition according to claim 2, wherein the fluorine-based solvent is methoxyperfluoroheptene, and is (Z)-1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxyhept-3-ene, (E)-1,1,1,2,2,3,5,5,6,6,7,7,7-tridecafluoro-4-methoxyhept-3-ene, or a mixture thereof.

7. (c) The coating composition according to claim 1 or the silicone oil removal composition according to claim 2, wherein the fluorine-based solvent is perfluoroheptene, and at least one selected from 2-perfluoroheptene and 3-perfluoroheptene.

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