WO2022009801A1

WO2022009801A1 - Composition and use thereof

Info

Publication number: WO2022009801A1
Application number: PCT/JP2021/025155
Authority: WO
Inventors: 洋輝速水; 宏明光岡
Original assignee: Ａｇｃ株式会社
Priority date: 2020-07-08
Filing date: 2021-07-02
Publication date: 2022-01-13
Also published as: CN115702235A; JPWO2022009801A1

Abstract

Provided are a composition and a use thereof, the composition not having any adverse effect on the global environment, and, when used as an aerosol, having exceptional object cleaning capabilities and not being prone to leaving liquid behind, and furthermore having little effect on the material of an article on which the composition is used.　A composition including prescribed amounts of: the Z-isomer of 1-chloro-2,3,3,3-tetrafluoropropene; nonafluorobutoxymethane or nonafluorobutoxyethane; and, as needed, the Z-isomer of 1-chloro-3,3,3-trifluoropropene.

Description

Compositions and their uses

The present invention relates to a composition and its use.

Conventionally, hydrochlorofluorocarbon (hereinafter, also referred to as HCFC) having excellent nonflammability, low toxicity, and stability has been used as a diluting solvent for cleaning liquids, lubricants, and the like used for cleaning oil stains and dust. However, since HCFCs have an adverse effect on the ozone layer, HCFC production is scheduled to be completely abolished in 2020 in developed countries.
As a solvent that does not adversely affect the ozone layer, perfluorocarbon (hereinafter, also referred to as PFC), hydrofluorocarbon (hereinafter, also referred to as HFC), hydrofluoroether (hereinafter, also referred to as HFE) and the like are known. However, due to the large global warming potential, HFCs and PFCs are regulated substances under the Kyoto Protocol. Further, HFCs, HFEs and PFCs have lower solubility of fats and oils as compared with HCFCs, and their application range is narrow as a solvent application.

Patent Document 1 proposes a solvent composition that does not adversely affect the global environment, has a small effect on the resin material, has sufficient drying property, and has excellent solubility in oils and fats.

Japanese Patent No. 6699112

When the cleaning liquid used for cleaning oil stains and dust is used as an aerosol together with a propellant, it is required that the liquid does not easily remain, the cleaning property of the target object is excellent, and the influence on the material of the target article is small.
The solvent composition described in Patent Document 1 could not solve the above three problems at the same time.

The present invention provides a composition and its use which does not adversely affect the global environment, does not leave a liquid easily when used as an aerosol, has excellent detergency of an object, and has a small effect on the material of the object. Is the subject.

As a result of diligent studies, the present inventors have found that the problem can be solved by the following configuration.
[1] The Z isomer (A) of 1-chloro-2,3,3,3-tetrafluoropropene, nonafluorobutoxymethane (B), and
It contains the optional component Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The Z isomer of 1-chloro-2,3,3,3-tetrafluoropropene (A), the Z isomer of nonafluorobutoxymethane (B) and the Z isomer of 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxymethane (B). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of 1-chloro-3,3,3-trifluoropropene (C) is
First coordinates (A, B, C = 34.7% by mass, 65.3% by mass, 0.0% by mass), second coordinates (A, B, C = 74.0% by mass, 26.0) Mass%, 0.0 mass%), third coordinate (A, B, C = 44.4 mass%, 0.3 mass%, 55.3 mass%), fourth coordinate (A, B, C) = 25.7% by mass, 10.7% by mass, 63.6% by mass), fifth coordinates (A, B, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), It is a value in the area surrounded by a line connecting the sixth coordinates (A, B, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) in this order by six straight lines. ,Composition.
[2] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxymethane. In the phase diagram of the three values of the content (% by mass) of (B) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the seventh coordinate (A, B, C = 29.0% by mass, 66.0). Mass%, 5.0% by mass), 8th coordinate (A, B, C = 71.3% by mass, 23.7% by mass, 5.0% by mass), 3rd coordinate (A, B, C) = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinates (A, B, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, B, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, B, C = 5.0 mass%, 67.6 mass%) The composition according to [1], which is a value in a region surrounded by a line connecting six straight lines in this order (% by mass, 27.4% by mass).
[3] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxymethane. In the phase diagram of the three values of the content (% by mass) of (B) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the ninth coordinate (A, B, C = 12.9% by mass, 67.0). Mass%, 20.1% by mass), 10th coordinate (A, B, C = 16.4% by mass, 65.8% by mass, 17.8% by mass), 11th coordinate (A, B, C) = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinates (A, B, C = 53.3% by mass, 35.5% by mass, 11.2% by mass), 13th coordinate (A, B, C = 67.1% by mass, 20.1% by mass, 12.8% by mass), 3rd coordinate (A, B, C = 44.4% by mass, 0.3) Mass%, 55.3 mass%), 4th coordinate (A, B, C = 25.7 mass%, 10.7 mass%, 63.6 mass%), 5th coordinate (A, B, C) = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th coordinates (A, B, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) The composition according to [1] or [2], which is a value in a region surrounded by a line connected by nine straight lines in this order.
[4] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxymethane. In the phase diagram of the three values of the content (% by mass) of (B) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the 14th coordinate (A, B, C = 24.2% by mass, 43.1). Mass%, 32.7 mass%), 15th coordinate (A, B, C = 15.0 mass%, 26.7 mass%, 58.3 mass%), 16th coordinate (A, B, C) = 5.0% by mass, 35.6% by mass, 59.4% by mass), 17th coordinates (A, B, C = 5.0% by mass, 47.0% by mass, 48.0% by mass) The composition according to any one of claims 1 to 3, which is a value in a region surrounded by a line connected by four straight lines in this order.
[5] The Z isomer (A) of 1-chloro-2,3,3,3-tetrafluoropropene, nonafluorobutoxyethane (D), and
It contains the optional component Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The Z isomer of 1-chloro-2,3,3,3-tetrafluoropropene (A), the Z isomer of nonafluorobutoxyethane (D) and the Z isomer of 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxyethane (D). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the first coordinate (A, D, C = 34.7% by mass, 65.3). Mass%, 0.0 mass%), second coordinates (A, D, C = 86.0 mass%, 14.0 mass%, 0.0 mass%), third coordinates (A, D, C) = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinates (A, D, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, D, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, D, C = 5.0 mass%, 67.6 mass%) A composition which is a value in the region surrounded by a line connecting 6 straight lines in this order (% by mass, 27.4% by mass).
[6] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxyethane. In the phase diagram of the three values of the content (% by mass) of (D) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the seventh coordinate (A, D, C = 29.0% by mass, 66.0). Mass%, 5.0 mass%), 8th coordinate (A, D, C = 82.3 mass%, 12.7 mass%, 5.0 mass%), 3rd coordinate (A, D, C) = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinates (A, D, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, D, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, D, C = 5.0 mass%, 67.6 mass%) The composition according to [5], which is a value in a region surrounded by a line connecting 6 straight lines in this order (% by mass, 27.4% by mass).
[7] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxyethane. In the phase diagram of the three values of the content (% by mass) of (D) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the ninth coordinate (A, D, C = 12.9% by mass, 67.0). Mass%, 20.1% by mass), 10th coordinate (A, D, C = 16.4% by mass, 65.8% by mass, 17.8% by mass), 11th coordinate (A, D, C) = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinates (A, D, C = 53.3% by mass, 35.5% by mass, 11.2% by mass), 13th coordinate (A, D, C = 69.5% by mass, 17.4% by mass, 13.1% by mass), 14th coordinate (A, D, C = 75.6% by mass, 10.5) Mass%, 13.9 mass%), third coordinate (A, D, C = 44.8 mass%, 0.1 mass%, 55.1 mass%), fourth coordinate (A, D, C) = 25.7% by mass, 10.7% by mass, 63.6% by mass), fifth coordinates (A, D, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), It is a value in the area surrounded by a line connecting the sixth coordinates (A, D, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) in this order by 10 straight lines. , [5] or [6].
[8] The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the Z isomer (C) and the nonafluorobutoxyethane. In the phase diagram of the three values of the content (% by mass) of (D) and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyethane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is
Fifteenth coordinates (A, D, C = 51.1% by mass, 37.7% by mass, 11.2% by mass), twelfth coordinates (A, D, C = 53.3% by mass, 35.5) Mass%, 11.2 mass%), 16th coordinate (A, D, C = 66.3 mass%, 20.9 mass%, 12.8 mass%), 17th coordinate (A, D, C) = 33.2% by mass, 10.5% by mass, 56.3% by mass), 18th coordinates (A, D, C = 5.0% by mass, 35.6% by mass, 59.4% by mass),. It is a value in the region surrounded by a line connecting the 19th coordinates (A, D, C = 5.0% by mass, 47.0% by mass, 48.0% by mass) in this order by five straight lines. , [5] to [7].
[9] An aerosol composition containing the composition according to any one of [1] to [8].
[10] The aerosol composition according to [9], which comprises at least one propellant selected from the group consisting of liquefied gas and compressed gas.
[11] A cleaning method for removing stains adhering to the surface of the article by bringing the composition according to any one of [1] to [8] into contact with the surface of the article.
[12] The cleaning method according to [11], wherein the material of the article is at least one selected from the group consisting of fibers, metals, resins, rubber, glass, and ceramics.

The composition of the present invention does not adversely affect the global environment, and when used as an aerosol, the liquid does not easily remain, the cleaning property of the object is excellent, and the influence on the material of the object is small.

FIG. 1 shows the Z isomer of 1-chloro-2,3,3,3-tetrafluoropropene (hereinafter, also referred to as HCFO-1224yd (Z)) of the component (A) and the nonafluorobutoxy of the component (B). Z isomers of methane (C ₄ F ₉ OCH ₃ , hereinafter also referred to as HFE-449s1) and 1-chloro-3,3,3-trifluoropropene of the component (C) (hereinafter, HCFO-1233zd (Z)). The content (% by mass) of HCFO-1224yd (Z) of the component (A), the content (% by mass) of HFE-449s1 of the component (B), and (C) with respect to the total mass of the component (A). It is a phase diagram of three values with the content (mass%) of HCFO-1233zd (Z) of a component, and shows the range of these three values of composition 1 of this invention. FIG. 2 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). Three values of the content of (Z) (% by mass), the content of HFE-449s1 of the component (B) (% by mass), and the content of HCFO-1233zd (Z) of the component (C) (% by mass). It is a phase diagram and shows the preferable range of these three values of composition 1 of this invention. FIG. 3 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). Three values of the content of (Z) (% by mass), the content of HFE-449s1 of the component (B) (% by mass), and the content of HCFO-1233zd (Z) of the component (C) (% by mass). It is a phase diagram and shows a more preferable range of these three values of composition 1 of this invention. FIG. 4 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). (Mass%), (B) component HFE-449s1 content (mass%), and (C) component HCFO-1233zd (Z) content (% by mass). Yes, it shows a more suitable range of these three values of the composition 1 of the present invention. FIG. 5 shows HCFO-1224yd (Z) of the component (A), nonafluorobutoxyethane (C ₄ F ₉ OC ₂ H ₅ , hereinafter also referred to as HFE-569sf 2) of the component (D), and the component (C). The content (% by mass) of HCFO-1224yd (Z) of the component (A), the content (% by mass) of HFE-569sf2 of the component (D), and (C) with respect to the total mass with HCFO-1233zd (Z). It is a phase diagram of three values of the content of HCFO-1233zd (Z) of a component, and shows the range of these three values of composition 2 of this invention. FIG. 6 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). It is a phase diagram of three values of the content (mass%) of (Z), the content (mass%) of HFE-569sf2 of the component (D), and the content of HCFO-1233zd (Z) of the component (C). , The preferred range of these three values of the composition 2 of the present invention is shown. FIG. 7 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). Three values of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 of the component (D), and the content (mass%) of HCFO-1233zd (Z) of the component (C). It is a phase diagram and shows a more preferable range of these three values of composition 2 of this invention. FIG. 8 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). Three values of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 of the component (D), and the content (mass%) of HCFO-1233zd (Z) of the component (C). It is a phase diagram and shows a more suitable range of these three values of composition 2 of this invention.

(Composition 1)
The first embodiment of the composition of the present invention (hereinafter referred to as composition 1 of the present invention) is a Z isomer of 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)). ) (A), nonafluorobutoxymethane (HFE-449s1) (B), and the optional component 1-chloro-3,3,3-trifluoropropene Z isomer (HCFO-1233zd (Z)) ( C) and. That is, the composition 1 of the present invention is a two-component composition containing HCFO-1224yd (Z) of the component (A) and HFE-449s1 of the component (B), or HCFO-1224yd (Z) of the component (A). ), HFE-449s1 of the component (B) and HCFO-1233zd (Z) of the component (C).

(HCFO-1224yd (Z))
HCFO-1224yd (CF ₃ CF = CHCl) is an olefin having a carbon atom-carbon atom double bond. Therefore, the life in the atmosphere is short, and the ozone depletion potential and global warming potential are small.

HCFO-1224yd is known to have a stereoisomer, HCFO-1224yd (Z) has a boiling point of 15 ° C., and HCFO-1224yd E isomer (hereinafter, also referred to as HCFO-1224yd (E)). The boiling point of.) Is 17 ° C. A known production method gives HCFO-1224yd (Z) and HCFO-1224yd (E) and mixtures thereof (usually a high proportion of HCFO-1224yd (Z)), which can be separated by distillation. The composition 1 of the present invention contains HCFO-1224yd (Z) among these isomers.

Since it has the above boiling point, HCFO-1224yd (Z) is excellent in volatility.
HCFO-1224yd (Z) has no flash point.
HCFO-1224yd (Z) has low surface tension and viscosity, and easily evaporates even at room temperature.
HCFO-1224yd (Z) is excellent for use as a cleaning agent or coating solvent.
HCFO-1224yd (Z) is intended for cleaning and removing mineral oil, silicone oil, fluorine oil, synthetic oil, mold release agent, dust, etc., and dissolving lubricants such as mineral oil, silicone oil, fluorine oil, synthetic oil, etc. Excellent applicability to objects.

Examples of the method for producing HCFO-1224yd include (1) a method of dehydrochlorinating 1,2-dichloro-2,3,3,3-tetrafluoropropane (hereinafter, also referred to as HCFC-234bb). And (2) a method of hydrogen-reducing 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter, also referred to as CFO-1214ya) and the like can be mentioned.
Hereinafter, each method will be described in detail.

(1) Dehydrochlorination reaction of HCFC-234bb In the liquid phase, HCFC-234bb is brought into contact with a base dissolved in a solvent, that is, a base in a solution state to carry out a dehydrochlorination reaction of HCFC-234bb. HCFC-234bb can be produced, for example, by reacting 2,3,3,3-tetrafluoropropene (hereinafter, also referred to as HFO-1234yf) with chlorine in a solvent.

(2) Method for reducing CFO-1214ya with hydrogen By reducing CFO-1214ya with hydrogen in the presence of a catalyst, it is reduced to HFO-1234yf, and HCFO-1224yd is obtained as an intermediate thereof. Further, in this reduction reaction, many kinds of fluorine-containing compounds are by-produced in addition to HCFO-1224yd. CFO-1214ya is prepared from, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane (hereinafter, also referred to as HCFC-225ca) in an alkaline aqueous solution in the presence of a phase transfer catalyst. Alternatively, a method of producing by defluoridating hydrogen by a gas phase reaction in the presence of a catalyst such as chromium, iron, copper, or activated carbon is known.

(HFE-449s1)
HFE-449s1 means a compound represented by _{C 4} F ₉ OCH _3. HFE-449s1 has four structural isomers, and the HFE-449s1 contained in the composition of the present invention may be only one of them or a mixture of two or more thereof. .. The HFE-449s1 contained in the composition of the present invention includes 1-methoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1-methoxy-1,1,2, A mixture with 2,3,3,4,4,4-nonafluorobutane is preferred. Examples of this mixture include the product "Novec7100" (manufactured by 3M Ltd.).

HFE-449s1 has a boiling point of 61 ° C., and even if it is boiled to become steam, it is 61 ° C., so that even parts that are easily affected by heat, such as rubber parts and resin parts, are unlikely to have an adverse effect.
HFE-449s1 has no flash point.
HFE-449s1 has low surface tension and viscosity, and easily evaporates even at room temperature.
HFE-449s1 has a small effect on rubber materials and resin materials.

HFE-449s1 can be produced by a known method.
For example, as described in Japanese Patent No. 2908033, CF ₃ CF ₂ CF ₂ C (O) F, CF ₃ CF (CF ₃ ) C (O) F and C ₂ F ₅ C (O) CF ₃ and These mixtures and any suitable source of anhydrous fluoride ions such as anhydrous alkali metal fluoride (eg, potassium fluoride or cesium fluoride) or anhydrous silver fluoride fluoride are available from Aldrich Chemical Company at ADOGEN 464. It can be produced by reacting with an alkylating agent such as dimethyl fluoride in an anhydrous polar aprotic solvent in the presence of a quaternary ammonium compound such as dimethylsulfate.

(HCFO-1233zd (Z))
Since HCFO-1233zd (CF ₃ CH = CHCl) is an olefin having a double bond between carbon atoms, it has a short life in the atmosphere and a small ozone depletion potential and global warming potential.

HCFO-1233zd is known to have a stereoisomer, HCFO-1233zd (Z) has a boiling point of about 40 ° C., and HCFO-1233zd has an E isomer (hereinafter, also referred to as HCFO-1233zd (E)). The boiling point of) is about 18 ° C. By a known production method, HCFO-1233zd (Z) and HCFO-1233zd (E) and a mixture thereof (usually, the ratio of HCFO-1233zd (Z) is high) can be obtained, and both can be separated by distillation. The composition 1 of the present invention contains HCFO-1233zd (Z) among these isomers.

Since it has the above boiling point, HCFO-1233zd (Z) is excellent in volatility.
Although HCFO-1233zd (Z) is an olefin, it is difficult to decompose even in the presence of oxygen and has high stability.
HCFO-1233zd (Z) has no flash point.
HCFO-1233zd (Z) has low surface tension and viscosity, and easily evaporates even at room temperature. HCFO-1233zd (Z) is excellent in cleaning and removing processing oil, fluorine oil, silicone oil, synthetic oil, mold release agent, dust and the like, and solubility of lubricants such as fluorine oil and silicone oil.

HCFO-1233zd can be produced by a known method.
For example, a method of defluoridating hydrogenating 3-chloro-1,1,1,3-tetrafluoropropane (hereinafter, also referred to as HCFC-244fa) in the presence of a catalyst can be mentioned (Japanese Patent Laid-Open No. 2009-263365). Gazette).

FIG. 1 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). 3 of the content (mass%) of (Z), the content (mass%) of HFE-449s1 of the component (B), and the content (mass%) of HCFO-1233zd (Z) of the component (C). It is a phase diagram of two values and shows the range of these three values of the composition 1 of this invention. In FIG. 1, the upper left coordinate is defined as the first coordinate, and the second coordinate, the third coordinate, the fourth coordinate, the fifth coordinate, and the sixth coordinate counterclockwise from the first coordinate.
In the composition 1 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-449s1 of the component (B) and HCFO-1233zd (Z) of the component (C) are the first in FIG. Coordinates (A, B, C = 34.7% by mass, 65.3% by mass, 0.0% by mass), second coordinates (A, B, C = 74.0% by mass, 26.0% by mass) , 0.0% by mass), 3rd coordinate (A, B, C = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinate (A, B, C = 25) .7% by mass, 10.7% by mass, 63.6% by mass), 5th coordinate (A, B, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th The coordinates (A, B, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) are the values in the region surrounded by the line connecting the six straight lines in this order.
In the composition 1 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-449s1 of the component (B) and HCFO-1233zd (Z) of the component (C) satisfy the above ranges. When used as an aerosol, the liquid does not easily remain, the object has excellent detergency, and the effect on the resin material is small.

FIG. 2 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). In the phase diagram of three values of (Z) content (mass%), (B) component HFE-449s1 content (mass%), and (C) component HCFO-1233zd content (mass%). Yes, it shows a suitable range of these three values of the composition 1 of the present invention. In FIG. 2, the upper left coordinate is defined as the seventh coordinate, and the eighth coordinate, the third coordinate, the fourth coordinate, the fifth coordinate, and the sixth coordinate counterclockwise from the seventh coordinate.
In the composition 1 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-449s1 of the component (B) and HCFO-1233zd (Z) of the component (C) are the seventh in FIG. Coordinates (A, B, C = 29.0% by mass, 66.0% by mass, 5.0% by mass), 8th coordinates (A, B, C = 71.3% by mass, 23.7% by mass) , 5.0% by mass), 3rd coordinate (A, B, C = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinate (A, B, C = 25) .7% by mass, 10.7% by mass, 63.6% by mass), 5th coordinate (A, B, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th (A, B, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) are the values in the area surrounded by the line connecting the six straight lines in this order. The content of HCFO-1233zd (Z) of the component (C) is 5.0% by mass or more. When the content of HCFO-1233zd (Z) of the component (C) is 5.0% by mass or more, in the examples described later, HCFO-1224yd (Z) and HCFO-1224yd (Z) of the component (A) in the composition 1 of the present invention. Compared with the two-component composition having the same content ratio of HFE-449s1 (HCFO-1224yd (Z) (mass%): HFE-449s1 (mass%)) of the component (B), the kauributanol value (hereinafter , KB value) is improved. Therefore, it is expected that the detergency of the object will be further improved.

FIG. 3 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). Three values of the content of (Z) (% by mass), the content of HFE-449s1 of the component (B) (% by mass), and the content of HCFO-1233zd (Z) of the component (C) (% by mass). It is a phase diagram and shows a more preferable range of these three values of composition 1 of this invention. In FIG. 3, the upper left coordinate is the ninth coordinate, and the tenth coordinate, the eleventh coordinate, the twelfth coordinate, the thirteenth coordinate, the third coordinate, and the fourth coordinate counterclockwise from the ninth coordinate. Coordinates, the fifth coordinate, and the sixth coordinate.
In the composition 1 of the present invention, the content of HCFO-1224yd (Z) of the component (A), HFE-449s1 of the component (B) and HCFO-1233zd (Z) of the component (C) is the ninth coordinate (Z). A, B, C = 12.9% by mass, 67.0% by mass, 20.1% by mass), 10th coordinate (A, B, C = 16.4% by mass, 65.8% by mass, 17. 8% by mass), 11th coordinate (A, B, C = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinate (A, B, C = 53.3% by mass) %, 35.5% by mass, 11.2% by mass), 13th coordinate (A, B, C = 67.1% by mass, 20.1% by mass, 12.8% by mass), 3rd coordinate (A, B, C = 67.1% by mass, 12.8% by mass) A, B, C = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinates (A, B, C = 25.7% by mass, 10.7% by mass, 63. 6% by mass), 5th coordinate (A, B, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th coordinate (A, B, C = 5.0% by mass) %, 67.6% by mass, 27.4% by mass) is the value in the region surrounded by the line connecting nine straight lines in this order, in the embodiment described later, in the composition 1 of the present invention. A two-component system having the same content ratio of HCFO-1224yd (Z) of the component (A) and HFE-449s1 of the component (B) (HCFO-1224yd (Z) (mass%): HFE-449s1 (mass%)). The KB value is improved by 10% or more as compared with the composition of. Therefore, it is expected that the detergency of the object will be further improved.

FIG. 4 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-449s1 of the component (B), and the HCFO-1233zd (Z) of the component (C). Three values of the content of (Z) (% by mass), the content of HFE-449s1 of the component (B) (% by mass), and the content of HCFO-1233zd (Z) of the component (C) (% by mass). It is a phase diagram and shows a more suitable range of these three values of composition 1 of this invention.
In FIG. 4, the upper left coordinate is the 14th coordinate, and the 15th coordinate, the 16th coordinate, and the 17th coordinate counterclockwise from the 14th coordinate.
In the composition 1 of the present invention, the content of HCFO-1224yd (Z) of the component (A), HFE-449s1 of the component (B), and HCFO-1233zd (Z) of the component (C) is the 14th coordinate (Z). A, B, C = 24.2% by mass, 43.1% by mass, 32.7% by mass), 15th coordinate (A, B, C = 15.0% by mass, 26.7% by mass, 58. 3 mass%), 16th coordinate (A, B, C = 5.0 mass%, 35.6 mass%, 59.4 mass%), 17th coordinate (A, B, C = 5.0 mass%) %, 47.0% by mass, 48.0% by mass) are the values in the region surrounded by the lines connecting four straight lines in this order, the residual liquid ratio, the evaporation rate, and KB in the examples described later. The value, material influence evaluation, and solubility evaluation in various oils are all judged as A.

(Composition 2)
In the second embodiment of the composition of the present invention (hereinafter referred to as composition 2 of the present invention), HCFO-1224yd (Z) as a component (A) and nonafluorobutoxyethane (HFE-569sf2) as a component (D) are used. ) And HCFO-1233zd (Z), which is an optional component (C). That is, the composition 2 of the present invention is a two-component composition containing HCFO-1224yd (Z) of the component (A) and HFE-569sf2 of the component (D), or HCFO-1224yd (A). Z), a three-component composition comprising HFE-569sf2 as a component (D) and HCFO-1233zd (Z) as a component (C).

HCFO-1224yd (Z) and HCFO-1233zd (Z) are omitted because they have been described above.

(HFE-569sf2)
HFE-569sf2 means a compound represented by _{C 4} F ₉ OC ₂ H _5. HFE-569sf2 has four structural isomers, and the HFE-569sf2 contained in the composition of the present invention may be only one of them or a mixture of two or more thereof. .. The HFE-569sf2 contained in the composition of the present invention includes 1-ethoxy-2-trifluoromethyl-1,1,2,3,3,3-hexafluoropropane and 1-ethoxy-1,1,2, A mixture of 2,3,3,4,4,4-nonafluorobutane is preferred. Examples of this mixture include the product "Novec7200" (manufactured by 3M).

HFE-569sf2 has a boiling point of 76 ° C., and even if it is boiled to become steam, it is 76 ° C., so that even parts that are easily affected by heat, such as rubber parts and resin parts, are unlikely to have an adverse effect.
HFE-569sf2 has no flash point.
HFE-569sf2 has low surface tension and viscosity, and easily evaporates even at room temperature.
HFE-569sf2 has a small effect on rubber materials and resin materials.

HFE-569sf2 can be produced by a known method.
For example, as described in Japanese Patent No. 3068199, CF ₃ CF ₂ CF ₂ C (O) F, CF ₃ CF (CF ₃ ) C (O) F, and C ₂ F ₅ C (O) CF ₃ Also, ADOGEN 464 available from Aldrich Chemical Company with mixtures thereof and any suitable source of anhydrous fluoride ions such as anhydrous alkali metal fluoride (eg, potassium fluoride or cesium fluoride) or anhydrous silver fluoride fluoride. It can be produced by reacting with an alkylating agent such as diethyl fluoride in an anhydrous polar aprotic solvent in the presence of a quaternary ammonium compound such as.

FIG. 5 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). 3 of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 of the component (D), and the content (% by mass) of HCFO-1233zd (Z) of the component (C). It is a phase diagram of two values and shows the range of these three values of the composition 2 of this invention. In FIG. 5, the upper left coordinate is set as the first coordinate, and the second coordinate, the third coordinate, the fourth coordinate, the fifth coordinate, and the sixth coordinate are set counterclockwise from the first coordinate.
In the composition 2 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-569sf2 of the component (D) and HCFO-1233zd (Z) of the component (C) are the first in FIG. Coordinates (A, D, C = 34.7% by mass, 65.3% by mass, 0.0% by mass), second coordinates (A, D, C = 86.0% by mass, 14.0% by mass) , 0.0% by mass), 3rd coordinate (A, D, C = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinate (A, D, C = 25) .7% by mass, 10.7% by mass, 63.6% by mass), 5th coordinate (A, D, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th The coordinates (A, D, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) are the values in the region surrounded by the line connecting the six straight lines in this order.
In the composition 2 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-569sf2 of the component (D) and HCFO-1233zd (Z) of the component (C) satisfy the above ranges. When used as an aerosol, the liquid does not easily remain, the object has excellent detergency, and the effect on the material of the object is small.

FIG. 6 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). In the phase diagram of three values of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 (mass%) of the component (D), and the content (mass%) of HCFO-1233zd (Z) of the component (C). Yes, it shows a suitable range of these three values of the composition 2 of the present invention. In FIG. 6, the upper left coordinate is defined as the seventh coordinate, and the second coordinate, the third coordinate, the fourth coordinate, the fifth coordinate, and the sixth coordinate counterclockwise from the seventh coordinate.
In the composition 2 of the present invention, the contents of HCFO-1224yd (Z) of the component (A), HFE-569sf2 of the component (D) and HCFO-1233zd (Z) of the component (C) are the seventh in FIG. Coordinates (A, D, C = 29.0% by mass, 66.0% by mass, 5.0% by mass), 8th coordinates (A, D, C = 82.3% by mass, 12.7% by mass) , 5.0% by mass), 3rd coordinate (A, D, C = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinate (A, D, C = 25) .7% by mass, 10.7% by mass, 63.6% by mass), 5th coordinate (A, D, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th The coordinates (A, D, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) are the values in the area surrounded by the line connecting the six straight lines in this order. The content of HCFO-1233zd (Z) of the component (C) is 5.0% by mass or more. When the content of HCFO-1233zd (Z) of the component (C) is 5.0% by mass or more, in the examples described later, HCFO-1224yd (Z) and HCFO-1224yd (Z) of the component (A) in the composition 2 of the present invention. The KB value is improved as compared with the two-component composition having the same HFE-569sf2 content ratio (HCFO-1224yd (Z) (mass%): HFE-569sf2 (mass%)) of the component (D). .. Therefore, it is expected that the detergency of the object will be further improved.

FIG. 7 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). In the phase diagram of three values of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 (mass%) of the component (D), and the content (mass%) of HCFO-1233zd (Z) of the component (C). Yes, it shows a more suitable range of these three values of the composition 2 of the present invention. In FIG. 7, the upper left coordinate is the ninth coordinate, and the tenth coordinate, the eleventh coordinate, the twelfth coordinate, the thirteenth coordinate, the fourteenth coordinate, and the fifteenth coordinate counterclockwise from the ninth coordinate. , The 16th coordinate, the 17th coordinate, and the 18th coordinate.
The composition 2 of the present invention contains HCFO-1224yd (Z) as a component (A), HFE-569sf2 as a component (D), and HCFO-1233zd (Z) as a component (C). Coordinates (A, D, C = 12.9% by mass, 67.0% by mass, 20.1% by mass), tenth coordinates (A, D, C = 16.4% by mass, 65.8% by mass) , 17.8% by mass), 11th coordinate (A, D, C = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinate (A, D, C = 53) .3% by mass, 35.5% by mass, 11.2% by mass), 13th coordinates (A, D, C = 69.5% by mass, 17.4% by mass, 13.1% by mass), 14th Coordinates (A, D, C = 75.6% by mass, 10.5% by mass, 13.9% by mass), third coordinates (A, D, C = 44.8% by mass, 0.1% by mass) , 55.1 mass%), 4th coordinate (A, D, C = 25.7 mass%, 10.7 mass%, 63.6 mass%), 5th coordinate (A, D, C = 5) 9.0% by mass, 26.2% by mass, 68.8% by mass), 6th coordinates (A, D, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) in this order. The value in the region surrounded by the line connected by 10 straight lines is the value of the HCFO-1224yd (Z) and (D) components of the component (A) in the composition 2 of the present invention in the examples described later. The KB value is improved by 10% or more as compared with the two-component composition having the same HFE-569sf2 content ratio (HCFO-1224yd (Z) (mass%): HFE-569sf2 (mass%)). Therefore, it is expected that the detergency of the object will be further improved.

FIG. 8 shows the HCFO-1224yd of the component (A) with respect to the total mass of the HCFO-1224yd (Z) of the component (A), the HFE-569sf2 of the component (D), and the HCFO-1233zd (Z) of the component (C). In the phase diagram of three values of the content (% by mass) of (Z), the content (mass%) of HFE-569sf2 (mass%) of the component (D), and the content (mass%) of HCFO-1233zd (Z) of the component (C). Yes, it shows a more suitable range of these three values of the composition 2 of the present invention. In FIG. 7, the upper left coordinate is the 15th coordinate, and the 12th coordinate, the 16th coordinate, the 17th coordinate, the 18th coordinate, and the 19th coordinate are taken counterclockwise from the 15th coordinate.
The composition 2 of the present invention contains HCFO-1224yd (Z) as a component (A), HFE-569sf2 as a component (D), and HCFO-1233zd (Z) as a component (C). Coordinates (A, D, C = 51.1% by mass, 37.7% by mass, 11.2% by mass), 12th coordinates (A, D, C = 53.3% by mass, 35.5% by mass) 11.2% by mass), 16th coordinate (A, D, C = 66.3% by mass, 20.9% by mass, 12.8% by mass), 17th coordinate (A, D, C = 33) .2% by mass, 10.5% by mass, 56.3% by mass), 18th coordinates (A, D, C = 5.0% by mass, 35.6% by mass, 59.4% by mass), 19th (A, D, C = 5.0% by mass, 47.0% by mass, 48.0% by mass) are the values in the area surrounded by the line connecting the six straight lines in this order. The residual liquid ratio, evaporation rate, KB value, material influence evaluation, and solubility evaluation in various oils in the examples described later are all judged as A.

The compositions 1 and 2 of the present invention do not adversely affect the global environment, and when used as an aerosol composition, the liquid does not easily remain, the object is excellent in detergency, and the effect on the material of the object is small.

The aerosol composition of the present invention contains the composition 1 or 2 of the present invention. The aerosol composition of the present invention preferably contains a propellant, and more preferably contains at least one propellant selected from the group consisting of liquefied gas and compressed gas. Examples of the liquefied gas in the aerosol composition include dimethyl ether (DME), liquefied petroleum gas (LPG), propane, butane, isobutane, 1,1-difluoroethane (HFC-152a), 1,1,1,2-tetrafluoroethane (1,1,1,2-tetrafluoroethane). HFC-134a), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,3,3,3-tetrafluoropropene (HFO-1234ze) and the like. On the other hand, examples of the compressed gas include nitrogen, carbon dioxide, compressed air, and nitrous oxide.

(Washing method)
The cleaning method of the present invention is characterized in that the composition 1 or 2 of the present invention is brought into contact with the surface of the article to remove stains adhering to the surface of the article.
As a specific cleaning method, the composition 1 or 2 of the present invention may be brought into contact with the surface of the article. Although not particularly limited, for example, a method of hand wiping, dipping, spraying, shaking, ultrasonic waves, steam cleaning, or a combination thereof can be adopted. When an aerosol composition is used, the aerosol composition may be sprayed on the surface of the article.

As the material of the article to which the compositions 1 and 2 of the present invention are applicable, at least one selected from the group consisting of fibers, metals, resins, rubbers, glasses, and ceramics is preferable, and the fibers are natural fibers and synthetic fibers. Fiber is mentioned. Further, the article may be an article made of a composite material having these two or more kinds of materials. Examples of the composite material include a laminate of metal and resin. In particular, the compositions 1 and 2 of the present invention use a rubber material such as styrene-butadiene rubber (SBR) or a resin material such as a polycarbonate (PC) resin or a polyphenylene ether (PPE) resin, which is affected by HCFO-1233zd (Z). It can also be used for articles containing.

Specific examples of articles include textile products, medical equipment, electrical equipment, precision machinery, optical equipment, vehicles / vehicles / transportation facilities and their parts. Specific examples of electrical equipment, precision machinery, optical articles and their components include ICs, capacitors, printed circuit boards, micromotors, relays, bearings, optical lenses, glass substrates and the like. Specific examples of vehicles, vehicles, transportation means and their parts include bodies, brake parts, suspensions, wheels and the like. In particular, the composition of the present invention can also be used for an article in which at least a part of the material on the surface of the article in contact with the composition contains a rubber material such as SBR and a resin material such as PC resin and PPE resin.

In the cleaning method of the present invention, the stains to be washed and removed include carbon, flux, processing oil, mold release agent, sebum, food oil, cosmetic oil, and other oils and fats adhering to various objects to be cleaned. Examples include dust and the like that have adhered to the surface. Examples of the processing oil include cutting oil, quenching oil, rolling oil, lubricating oil, machine oil, press processing oil, punching oil, drawing oil, assembly oil, drawing oil, brake fluid and the like. Examples of cosmetics include manicure and lipstick. Two or more of the above-mentioned stains may be attached to various objects to be cleaned. Since the composition of the present invention is superior in solubility in these oils, silicone oil, fluorine oil, etc. as compared with conventional solvent compositions such as HFC and HFE, it is used for cleaning stains composed of these oils. Is preferable. It was

When the compositions 1 and 2 of the present invention are used as an aerosol composition, the liquid does not easily remain, the influence on the material of the target article is small, and both the evaporation rate evaluation and the KB value evaluation shown in Examples described later are performed. Due to its superiority, it can also be used as a solvent for forming a coating film of a non-volatile organic compound by an aerosol (hereinafter, also referred to as a coating film forming solvent).
When used as a coating film forming solvent, the content of the non-volatile organic compound is preferably 0.01 to 50% by mass in the total of 100% by mass of the composition 1 or 2 of the present invention and the non-volatile organic compound. , 0.05 to 30% by mass, more preferably 0.1 to 20% by mass. When the content of the non-volatile organic compound is within the above range, the film thickness of the coating film when the non-volatile organic compound is applied and the non-volatile after evaporative removal of the coating film forming solvent (hereinafter, also referred to as drying). It is easy to adjust the thickness of the organic compound coating film to an appropriate range.

The non-volatile organic compound has a boiling point higher than that of the coating film forming solvent and remains even after the coating film forming solvent evaporates. Specific examples of the non-volatile organic compound include a lubricant for imparting lubricity to an article, a rust inhibitor for imparting a rust preventive effect on metal parts, and a moisture-proof coating agent for imparting water repellency to an article. Examples thereof include an antifouling coating agent such as a fingerprint adhesion preventive agent for imparting antifouling performance to an article. Among these, it is preferable to use a lubricant as the non-volatile organic compound from the viewpoint of solubility.

Lubricants are meant to be used to reduce friction on the contact surfaces and prevent heat generation and frictional damage when the two members move in contact with each other. The lubricant may be in the form of a liquid (oil), a semi-solid (grease), or a solid.
As the lubricant, a mineral oil-based lubricant, a synthetic oil-based lubricant, a fluorine-based lubricant, and a silicone-based lubricant are preferable because of their excellent solubility in a coating film-forming solvent. The fluorine-based lubricant means a lubricant having a fluorine atom in the molecule. Further, the silicone-based lubricant means a lubricant containing silicone. The lubricant may be one kind or two or more kinds. The fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination.

Examples of the fluorine-based lubricant include fluorine-based solid lubricants such as fluorine oil, fluorine grease, and resin powder of polytetrafluoroethylene. As the fluorine oil, a low polymer of perfluoropolyether or chlorotrifluoroethylene is preferable. For example, the product names "Critex (registered trademark) GPL102" (manufactured by DuPont Co., Ltd.), "Daikin", "Daikin # 3", "Daikin # 10", "Daikin # 20", "Daikin # 50", Examples thereof include "Daifuroil # 100" and "Demonum S-65" (manufactured by Daikin Industries, Ltd.). As the fluorine grease, a fluorine oil such as a low polymer of perfluoropolyether or chlorotrifluoroethylene is preferably used as a base oil, and a polytetrafluoroethylene powder or other thickener is blended. For example, product names "Kritex (registered trademark) Grease 240AC" (manufactured by DuPont Co., Ltd.), "Difloyl Grease DG-203", "Demnum L65", "Demnum L100", "Demnum L200" (above, Daikin shares). "Sumitec F936" (manufactured by Sumiko Lubricant Co., Ltd.), "Moricoat (registered trademark) HP-300", "Moricoat (registered trademark) HP-500", "Moricoat (registered trademark) HP-870" , "Moricoat (registered trademark) 6169" and the like.

Examples of the silicone-based lubricant include silicone oil and silicone grease. As the silicone oil, dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, and modified silicone oil having an organic group introduced into a side chain or a terminal are preferable. For example, product names "Shinetsu Silicone KF-96", "Shinetsu Silicone KF-965", "Shinetsu Silicone KF-968", "Shinetsu Silicone KF-868", "Shinetsu Silicone KF-99", "Shinetsu Silicone KF-50" , "Shinetsu Silicone KF-54", "Shinetsu Silicone HIVAC F-4", "Shinetsu Silicone HIVAC F-5", "Shinetsu Silicone KF-56A", "Shinetsu Silicone KF-995", "Shinetsu Silicone KF-868" , "Shinetsu Silicone KF-859" (above, manufactured by Shinetsu Chemical Industry Co., Ltd.), "SH200", "MDX4-4159" (above, manufactured by Toray Dow Corning Co., Ltd.) and the like. As the silicone grease, a product containing various silicone oils listed above as a base oil, a thickener such as metal soap, and various additives is preferable. For example, product names "Shin-Etsu Silicone G-30 Series", "Shin-Etsu Silicone G-40 Series", "Shin-Etsu Silicone FG-720 Series", "Shin-Etsu Silicone G-411", "Shin-Etsu Silicone G-501", "Shin-Etsu Silicone" "G-6500", "Shin-Etsu Silicone G-330", "Shin-Etsu Silicone G-340", "Shin-Etsu Silicone G-350", "Shin-Etsu Silicone G-630" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "Moricoat (Moricoat) "Moricoat (registered trademark) 41", "Moricoat (registered trademark) 41", "Moricoat (registered trademark) 44", "Moricoat (registered trademark) 822M", "Moricoat (registered trademark) 111", "Moricoat (registered trademark) high vacuum" Examples include "grease for silicon" and "Moricoat (registered trademark) heat diffusion compound" (all manufactured by Toray Dow Corning Co., Ltd.).

The rust inhibitor means an agent used to cover the surface of a metal that is easily oxidized by oxygen in the air to generate rust and to prevent the metal material from rusting by blocking the metal surface and oxygen. Examples of the rust preventive include mineral oils, polyol esters, polyalkylene glycols, and synthetic oils such as polyvinyl ether.

Examples of moisture-proof coating agents include Topas 5013, Topas 6013, Topas 8007 (above, manufactured by Polyplastics), Zeonoa 1020R, Zeonoa 1060R (above, manufactured by Nippon Zeon), Appel 6011T, Appel 8008T (above, Mitsui). (Made by Chemicals), SFE-DP02H, SNF-DP20H (all manufactured by Seimi Chemicals) and the like. Examples of antifouling coating agents such as anti-fingerprint agents include Optool DSX, Optool DAC (above, manufactured by Daikin Industries, Ltd.) Fluorosearch FG-5000 (above, manufactured by Fluoro Technology) SR-4000A (above, Seimi Chemical). (Manufactured by the company) and the like.

As the base material for forming the coating film of the non-volatile organic compound, a base material made of various materials such as metal, resin, rubber, glass and ceramics is adopted. Further, the solvent for forming a coating film can form a coating film of a non-volatile organic compound without affecting an article containing a rubber material or a resin material. It was

Specific examples of the base material on which the coating film of the non-volatile organic compound is formed include those using a fluorine-based lubricant, such as CD and DVD tray parts, printers, and copy equipment in industrial equipment, personal computers, and audio equipment. , Household equipment such as flux equipment, office equipment, and the like. Examples of those in which a silicone-based lubricant is used include syringes, cylinders, medical tube parts, metal blades, catheters and the like. Equipment used to impart moisture-proof and stain-proof properties to plastic materials, rubber materials, metal materials, glass materials, mounting recovery plates, etc., as examples of the use of moisture-proof coating agents and antifouling coating agents. Be done.

Hereinafter, the present invention will be described in detail by way of examples. The present invention is not limited to these examples. Examples 15-21, 26-32, 67-70, 72-74, 76-78, 80-83, 86-88, 90-92, 94-97, 99-103, 106, 107, 110-133, 135 136, 138 to 170 are examples of the compositions of the present invention, Examples 1 to 14, 22 to 25, 33 to 66, 71, 75, 79, 84, 85, 89, 93, 98, 104, 105, 108. , 109, 134, 137 are comparative examples.

(Preparation of HCFO-1224yd (Z))
An isomer mixture of HCFO-1224yd (E) and HCFO-1224yd (Z) was prepared according to the method described in WO 2017/118541. The above isomer mixture was purified by the method described in International Publication No. 2017/146190 to prepare HCFO-1224yd (Z) having a purity of 99.5%.

(Preparation of HFE-449s1 or HFE-569sf2)
3M ^TM NOVEC ^TM 7100 high-performance liquid (3M Japan Ltd., Japan) is used as HFE-449s1 for HFE-based nonflammable fluorine-based solvent, and 3M is used as HFE-569sf2 for HFE-based nonflammable fluorine-based solvent. ^TM NOVEC ^TM 7200 High-performance liquid (3M Japan Ltd., Japan) was purchased respectively.

(Preparation of HCFO-1233zd (Z))
HCFO-1233zd (Z) was produced by the method described in JP2013-87066A. After production, the product was purified to obtain HCFO-1233zd (Z) having a purity of 99.5%.

(Evaluation of residual liquid ratio by spraying)
HCFO-1224yd (Z), HCFO-1233zd (Z), and HFE-449s1 or HFE-569sf2 are filled in an aerosol container in order from the component having the highest boiling point so as to have the mass ratio shown in the table below. did. The filling amount was adjusted so that the liquid phase volume of the composition was about 80% by volume of the aerosol container volume. Then, the pressure in the aerosol container was adjusted by pressurizing with nitrogen and carbon dioxide so as to be 0.5 MPaG.
In a room at a temperature of 25 ° C. ± 2 ° C., the composition filled in the aerosol container was continuously sprayed from the liquid phase until it could not be sprayed from the aerosol container. The mass M'of the composition remaining in the aerosol container was measured, and the residual liquid ratio M with respect _{to the initial filling mass M 0 was calculated from the following formula.}
M = M'/ M ₀ x 100
The residual liquid ratio obtained from the above experiment was evaluated according to the following criteria. Good: Residual liquid ratio M less than 2.0% Defective: Residual liquid ratio M 2.0% or more

(Evaporation rate evaluation)
HCFO-1224yd (Z), HCFO-1233zd (Z), and HFE-449s1 or HFE-569sf2 in a stainless steel (SUS) pressure resistant container with a high boiling point so that the mass ratios are as shown in the table below. It was filled and mixed in order from. The filling amount was adjusted so that the liquid phase volume of the composition was about 80% by volume of the volume of the pressure-resistant container made of SUS.
A petri dish having an opening having a diameter of 90 mm and a height of 21 mm placed on the balance was filled with the prepared composition so as to have a total of 30 g.
Temperature 25 ° C. recorded volatile mass change due to the petri dish in the composition at room ± 2 ° C., defined as the evaporation time T _e the time from initial mass 30g to 0.3g of 1% by weight of the initial mass, The evaporation rate V _e was calculated from the following equation.
V _e = (30-0.3) / T _e
The calculated evaporation rate was evaluated according to the following criteria, with _{the evaporation rate V e} of HCFO-1233zd (Z) being 1.0.
A: 1.0 or less B: 1.0 or more, 1.5 or less C: 1.5 or more

(KB value evaluation)
HCFO-1224yd (Z), HCFO-1233zd (Z), and HFE-449s1 or HFE-569sf2 were placed in a constant temperature bath at a temperature of 25 ° C. so as to have the mass ratio shown in the table below, in 96 cc. The hyperglass cylinder (manufactured by Pressure Resistant Glass Industry Co., Ltd.) was filled in order from the composition having the highest boiling point, and the KB value was determined according to the method described in ASTM: D1133-13.
The obtained KB value was evaluated according to the following criteria.
A: 14 or more B: 10 or more, less than 14 C: less than 10

In the specification of the present application, the above-mentioned evaporation rate evaluation and KB value evaluation are used as indicators of the detergency of the object. When both the evaporation rate evaluation and the KB value evaluation are excellent, the detergency of the object is excellent.

(Evaluation of solubility in various oils)
Various oils (Brake fluid (Brake fluid 2500HA) manufactured by Fuji Chemical Research Institute, Inc., Silicone oil (Shin-Etsu Silicone KF-96-50cs) manufactured by Shin-Etsu Chemical Co., Ltd., or Fluorine manufactured by Nippon Solvay Co., Ltd. After adding 5 g of oil (FOMBLIN Y25) to a 96 cc hyperglass cylinder (manufactured by Pressure-Resistant Glass Industry Co., Ltd.) installed in a constant temperature bath at a temperature of 25 ° C., HCFO-1224yd (Z) and HCFO-1233zd ( Z) and HFE-449s1 or HFE-569sf2 were filled in order from the component having the highest boiling point so as to have the mass ratio shown in the table below, and the total mass was adjusted to 45 g. The composition and oils were mixed, and the state (solubility) of the solution after standing at 25 ° C. for 2 hours was evaluated for solubility according to the following criteria.
A: Transparent dissolution B: Lightly cloudy C: Cloudy / two-phase separation If the solubility evaluation is B, there is no problem in use, but if the solubility evaluation is C, it cannot be used.

(Material influence test)
Put three test pieces (20 mm x 37.5 mm x 2 mm thick) of polycarbonate (PC) resin or polyphenylene ether (PPE) resin into a 96 cc hyper glass cylinder (manufactured by Pressure Resistant Glass Industry Co., Ltd.), and then HCFO. -1224yd (Z), HCFO-1233zd (Z), and HFE-449s1 or HFE-569sf2 are filled in order from the component having the highest boiling point so as to have the mass ratio shown in the table below, and the total mass is 80 g. Adjusted to be.
Then, after allowing the hyperglass cylinder to stand at 25 ° C. for 30 minutes, the test piece was taken out and the appearance was evaluated according to the following criteria.
A: There is no change in the appearance of the test piece.
B: The test piece showed slight cracks or slight loss of transparency and discoloration.
C: Clear cracks, loss of transparency, discoloration, and dissolution were observed on the surface of the test piece.
If the evaluation of the material influence test is B, there is no problem in use, but if the evaluation is C, it cannot be used.

The results are shown in the table below.

Examples 15-21, 26-32, 67-70, 72-74, 76-78, 80-83, 86-88, 90-92, 94-97, 99-103, 106, 107, 110-133, 135 For 136 and 138 to 170, the results of the residual solution test were good, and the results of the evaporation rate, KB value, material influence evaluation, and solubility evaluation in various oils were B or higher.
A three-component composition comprising HCFO-1224yd (Z) as a component (A), HFE-449s1 as a component (B), and HCFO-1233zd (Z) as a component (C), and HCFO as a component (C). Examples 67 to 70, 72 to 74, 76 to 78, 80 to 83, 106 to 107, 110 to 117, 119 to 133 in which the content of -1233 zd (Z) is 5.0% by mass or more are HCFO-1224yd ( The KB value was improved as compared with the two-component composition having the same content ratio of Z) and HFE-449s1 (HCFO-1224yd (Z) (mass%): HFE-449s1 (mass%)). For example, in Example 115 where HCFO-1224yd (Z) (mass%): HFE-449s1 (mass%) is 38.0: 57.0, HCFO-1224yd (Z) (mass%): HFE-449s1 (mass%). )) The KB value was improved as compared with Example 18 of 40.0: 60.0.
A three-component composition comprising HCFO-1224yd (Z) as a component (A), HFE-569sf2 as a component (D), and HCFO-1233zd (Z) as a component (C), and HCFO as a component (C). Examples of examples with a content of -1233 zd (Z) of 5.0% by mass or more: 86 to 88, 90 to 92, 94 to 97, 99 to 103, 135, 136, 138 to 142, 144 to 148, 150 to 153, 155. -170 are compared with the two-component composition having the same content ratio of HCFO-1224yd (Z) and HFE-569sf2 (HCFO-1224yd (Z) (mass%): HFE-569sf2 (mass%)). The KB value has improved. For example, in Example 144 where HCFO-1224yd (Z) (% by mass): HFE-569sf2 is 38.0: 57.0, HCFO-1224yd (Z) (mass%): HFE-569sf2 (% by mass)) is 40. The KB value was improved as compared with Example 143 of 0.0: 60.0.
Examples of values for the contents of HCFO-1224yd (Z), HFE-449s1, and HCFO-1233zd (Z) in the region surrounded by a line connecting the nine coordinates of FIG. 3 with nine straight lines 67-69. 72-74, 76-78, 80-83, 106, 107, 111-114, 116, 117, 120, 121, 128-133 contain the contents of HCFO-1224yd (Z) and HFE-449s1 (HCFO-). The KB value was improved by 10% or more as compared with the composition of the two-component system in which 1224yd (Z) (mass%): HFE-449s1 (mass%)) was similar. For example, Example 116 in which HCFO-1224yd (Z) (% by weight): HFE-449s1 (% by weight) is 35.4: 53.0 has HCFO-1224yd (Z) (% by weight): HFE-449s1 (% by weight). )) Was 40.0: 60.0, the KB value was improved by 10% as compared with Example 18.
Examples of values 86, 90 for the contents of HCFO-1224yd (Z), HFE-569sf2, and HCFO-1233zd (Z) in the region surrounded by a line connecting the coordinates of FIG. 7 with 10 straight lines. , 91, 94-97, 99-103, 135, 136, 139-142, 145-148, 151-153, 156, 157, 164-170 are the content ratios of HCFO-1224yd (Z) and HFE-569sf2 ( The KB value was improved by 10% or more as compared with the composition of the two-component system in which HCFO-1224yd (Z) (% by mass): HFE-569sf2 (% by mass)) was similar. For example, in Example 145 where HCFO-1224yd (Z) (mass%): HFE-569sf2 is 35.4: 53.0, HCFO-1224yd (Z) (mass%): HFE-569sf2 (mass%)) is 40. The KB value was improved by 10% as compared with Example 143 of 0.0: 60.0.
Examples Among 67-69, 72-74, 76-78, 80-83, 106, 107, 110-114, 116, 117, 120, 121, 128-133, HCFO-1224yd (Z), HFE-449s1, And examples 72, 73, 107, 112, 113, 130-133 of the content of HCFO-1233zd (Z) in the region surrounded by the line connecting the four coordinates of FIG. 4 with four straight lines. , Residual liquid ratio, evaporation rate, KB value, material influence evaluation, and solubility evaluation in various oils were all judged as A.
Examples 86, 90, 91, 94-97, 99-103, 135, 136, 139-142, 145-148, 151-153, 156, 157, 164-170, among which HCFO-1224yd (Z), HFE- Examples of values for the content of 569sf2, and HCFO-1233zd (Z) in the region surrounded by the lines connecting the six coordinates of FIG. 8 with six straight lines 86, 90, 91, 95, 96, 136, For 140, 141, 146, 147, 151, 152, 166 to 170, the residual liquid ratio, evaporation rate, KB value, material influence evaluation, and solubility evaluation in various oils were all judged as A.

The composition of the present invention does not adversely affect the global environment, and when used as an aerosol, the liquid does not easily remain, the cleaning property of the target object is excellent, and the influence on the material of the target article is small. Useful for use.

Japanese Patent Application No. 2020-117686 filed on July 8, 2020, Japanese Patent Application No. 2021-047324 filed on March 22, 2021, and Japan filed on June 17, 2021. The entire contents of the specification, claims, drawings and abstracts of Patent Application No. 2021-100986 are cited herein and incorporated as disclosure of the specification of the present invention.

Claims

The Z isomer (A) of 1-chloro-2,3,3,3-tetrafluoropropene,
With nonafluorobutoxymethane (B),
It contains the optional component Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxymethane (B). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of the 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the first coordinate (A, B, C = 34.7% by mass, 65.3). Mass%, 0.0 mass%), second coordinates (A, B, C = 74.0 mass%, 26.0 mass%, 0.0 mass%), third coordinates (A, B, C) = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinates (A, B, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, B, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, B, C = 5.0 mass%, 67.6 mass%) A composition which is a value in the region surrounded by a line connecting 6 straight lines in this order (% by mass, 27.4% by mass).
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxymethane (B). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of the 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the seventh coordinate (A, B, C = 29.0% by mass, 66.0). Mass%, 5.0% by mass), 8th coordinate (A, B, C = 71.3% by mass, 23.7% by mass, 5.0% by mass), 3rd coordinate (A, B, C) = 44.4% by mass, 0.3% by mass, 55.3% by mass), 4th coordinates (A, B, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, B, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, B, C = 5.0 mass%, 67.6 mass%) The composition according to claim 1, which is a value in a region surrounded by a line connecting six straight lines in this order (% by mass, 27.4% by mass).
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxymethane (B). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of the 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the ninth coordinate (A, B, C = 12.9% by mass, 67.0). Mass%, 20.1% by mass), 10th coordinate (A, B, C = 16.4% by mass, 65.8% by mass, 17.8% by mass), 11th coordinate (A, B, C) = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinates (A, B, C = 53.3% by mass, 35.5% by mass, 11.2% by mass), 13th coordinate (A, B, C = 67.1% by mass, 20.1% by mass, 12.8% by mass), 3rd coordinate (A, B, C = 44.4% by mass, 0.3) Mass%, 55.3 mass%), 4th coordinate (A, B, C = 25.7 mass%, 10.7 mass%, 63.6 mass%), 5th coordinate (A, B, C) = 5.0% by mass, 26.2% by mass, 68.8% by mass), 6th coordinates (A, B, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) The composition according to claim 1 or 2, which is a value in a region surrounded by a line connected by nine straight lines in this order.
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxymethane (B) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxymethane (B). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of the 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxymethane (B), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the 14th coordinate (A, B, C = 24.2% by mass, 43.1). Mass%, 32.7 mass%), 15th coordinate (A, B, C = 15.0 mass%, 26.7 mass%, 58.3 mass%), 16th coordinate (A, B, C) = 5.0% by mass, 35.6% by mass, 59.4% by mass), 17th coordinates (A, B, C = 5.0% by mass, 47.0% by mass, 48.0% by mass) The composition according to any one of claims 1 to 3, which is a value in a region surrounded by a line connected by four straight lines in this order.
The Z isomer (A) of 1-chloro-2,3,3,3-tetrafluoropropene,
Nonafluorobutoxyethane (D) and
It contains the optional component Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxyethane (D). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the first coordinate (A, D, C = 34.7% by mass, 65.3). Mass%, 0.0 mass%), second coordinates (A, D, C = 86.0 mass%, 14.0 mass%, 0.0 mass%), third coordinates (A, D, C) = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinates (A, D, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, D, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, D, C = 5.0 mass%, 67.6 mass%) A composition which is a value in the region surrounded by a line connecting 6 straight lines in this order (% by mass, 27.4% by mass).
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxyethane (D). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the seventh coordinate (A, D, C = 29.0% by mass, 66.0). Mass%, 5.0 mass%), 8th coordinate (A, D, C = 82.3 mass%, 12.7 mass%, 5.0 mass%), 3rd coordinate (A, D, C) = 44.8% by mass, 0.1% by mass, 55.1% by mass), 4th coordinates (A, D, C = 25.7% by mass, 10.7% by mass, 63.6% by mass), Fifth coordinate (A, D, C = 5.0 mass%, 26.2 mass%, 68.8 mass%), sixth coordinate (A, D, C = 5.0 mass%, 67.6 mass%) The composition according to claim 5, which is a value in a region surrounded by a line connecting six straight lines in this order (% by mass, 27.4% by mass).
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxyethane (D). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyetane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is the ninth coordinate (A, D, C = 12.9% by mass, 67.0). Mass%, 20.1% by mass), 10th coordinate (A, D, C = 16.4% by mass, 65.8% by mass, 17.8% by mass), 11th coordinate (A, D, C) = 35.4% by mass, 53.0% by mass, 11.6% by mass), 12th coordinates (A, D, C = 53.3% by mass, 35.5% by mass, 11.2% by mass), 13th coordinate (A, D, C = 69.5% by mass, 17.4% by mass, 13.1% by mass), 14th coordinate (A, D, C = 75.6% by mass, 10.5) Mass%, 13.9 mass%), third coordinate (A, D, C = 44.8 mass%, 0.1 mass%, 55.1 mass%), fourth coordinate (A, D, C) = 25.7% by mass, 10.7% by mass, 63.6% by mass), fifth coordinates (A, D, C = 5.0% by mass, 26.2% by mass, 68.8% by mass), It is a value in the area surrounded by a line connecting the sixth coordinates (A, D, C = 5.0% by mass, 67.6% by mass, 27.4% by mass) in this order by 10 straight lines. , The composition according to claim 5 or 6.
The Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the nonafluorobutoxyethane (D) and the Z isomer of the 1-chloro-3,3,3-trifluoropropene. The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene with respect to the total mass of the body (C) and the nonafluorobutoxyethane (D). In the phase diagram of the three values of the content (% by mass) of 1 and the content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene.
The content (% by mass) of the Z isomer (A) of the 1-chloro-2,3,3,3-tetrafluoropropene, the content (% by mass) of the nonafluorobutoxyethane (D), and the above. The content (% by mass) of the Z isomer (C) of 1-chloro-3,3,3-trifluoropropene is
Fifteenth coordinates (A, D, C = 51.1% by mass, 37.7% by mass, 11.2% by mass), twelfth coordinates (A, D, C = 53.3% by mass, 35.5) Mass%, 11.2 mass%), 16th coordinate (A, D, C = 66.3 mass%, 20.9 mass%, 12.8 mass%), 17th coordinate (A, D, C) = 33.2% by mass, 10.5% by mass, 56.3% by mass), 18th coordinates (A, D, C = 5.0% by mass, 35.6% by mass, 59.4% by mass),. It is a value in the region surrounded by a line connecting the 19th coordinates (A, D, C = 5.0% by mass, 47.0% by mass, 48.0% by mass) in this order by six straight lines. , The composition according to any one of claims 5 to 7.
An aerosol composition containing the composition according to any one of claims 1 to 8.
The aerosol composition according to claim 9, which comprises at least one propellant selected from the group consisting of liquefied gas and compressed gas.
A cleaning method in which the composition according to any one of claims 1 to 8 is brought into contact with the surface of an article to remove stains adhering to the surface of the article.
The cleaning method according to claim 11, wherein the material of the article is at least one selected from the group consisting of fibers, metals, resins, rubber, glass, and ceramics.