WO2019123759A1

WO2019123759A1 - Solvent composition, cleaning method, coating forming composition, method for manufacturing coated substrate, aerosol composition, rinsing composition, method for cleaning member, and device for cleaning member

Info

Publication number: WO2019123759A1
Application number: PCT/JP2018/036103
Authority: WO
Inventors: 寿夫三木; 宏明光岡; 洋輝速水
Original assignee: Ａｇｃ株式会社
Priority date: 2017-12-22
Filing date: 2018-09-27
Publication date: 2019-06-27

Abstract

Provided are: a solvent composition which does not adversely affect the natural environment and which has excellent solubility for various organic compounds and drying properties; a cleaning method using the solvent composition; and a method for manufacturing a coated substrate using the solvent composition as a coating solvent. The solvent composition comprises a Z body of 1-chloro-2,3,3,3-tetrafluoro-1-propene.

Description

Solvent composition, cleaning method, composition for film formation, method for producing coated substrate, aerosol composition, rinse composition, method for cleaning member and method for cleaning member

The present invention relates to a solvent composition that does not adversely affect the global environment and is excellent in the solubility and drying properties of various organic compounds. Specifically, the present invention relates to a solvent composition that can be used in a wide range of applications, such as cleaning agents, coating solvents, and rinse agents.

Flux, processing oil, wax, mold release agent adhering to the parts after cleaning the parts with cleaning solvent in manufacturing process of IC, electronic parts, precision machine parts, optical parts, etc., assembly process, final finishing process, etc. Removal of dust, etc. is performed.

Moreover, as a manufacturing method of the articles | goods which have a coating film containing various organic compounds, such as a lubricant, for example, the solution which melt | dissolved the organic compound in the coating solvent is prepared, and this coating solution is apply | coated on a base material. There is known a method of evaporating to form a coating film. The coating solvent is required to be capable of sufficiently dissolving the organic compound and to have sufficient drying properties.

The solvent used for such applications is nonflammable, has low toxicity, is excellent in stability, does not attack the base material such as metal, plastic, elastomer, etc., and is excellent in chemical and thermal stability; Chlorofluorocarbons such as 2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as “CFCs”), 2,2-dichloro-1,1,1-trifluoroethane, 1,1 -Hydro-1-fluoroethane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, etc. Fluorine-based solvents containing chlorofluorocarbons (hereinafter referred to as "HCFCs") and the like have been used.

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

On the other hand, perfluorocarbons (hereinafter referred to as "PFCs") are known as solvents which do not have chlorine atoms and do not adversely affect the ozone layer. In addition, hydrofluorocarbons (hereinafter referred to as "HFCs"), hydrofluoroethers (hereinafter referred to as "HFEs") and the like have also been developed as substitute solvents for CFCs and HCFCs. However, HFCs and PFCs are regulated substances under the Kyoto Protocol because of their high global warming potential.

Under such circumstances, fluoroolefins having a carbon-carbon double bond have been proposed as new solvents to replace the solvents of HFCs, HFEs and PFCs. These fluoroolefins have an excellent property that they have a short life in the atmosphere because they are easily decomposed, and have a small effect on the global environment because they have low ozone destruction coefficients and global warming coefficients. For example, Patent Document 1 discloses that 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene (CFO-1214ya) is used as a cleaning solvent composition. In addition, Patent Document 2 describes that a cis-isomer of 1-chloro-3,3,3-trifluoro-1-propene (HCFO-1233zd (Z)) is used as a washing solvent.

However, the boiling point of the above-mentioned compound is about 46 ° C. for CFO-1214ya and about 40 ° C. for HCFO-1233zd (Z), and a solvent having a lower boiling point and excellent drying property has been desired.

JP, 2013-224383, A Japanese Patent Application Publication No. 2016-521194

The present invention relates to a solvent composition excellent in solubility and drying properties of various organic compounds without adversely affecting the global environment, a cleaning method using the solvent composition, and a composition for forming a coating film using the solvent composition It is an object of the present invention to provide an article, a method for producing a coated substrate, an aerosol composition, a rinse composition, a method for washing a member, and a device for washing a member.

The inventors of the present invention completed the present invention as a result of studying in view of the above points. That is, the present invention consists of the following.

[1] A solvent composition containing Z-form of 1-chloro-2,3,3,3-tetrafluoro-1-propene.
[2] The solvent composition according to [1], wherein the content of the Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene in the solvent composition is 50% by mass or more.
[3] Furthermore, it contains E form of 1-chloro-2,3,3,3-tetrafluoro-1-propene, Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene The content ratio of Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene relative to the total amount of E form of 1-chloro-2,3,3,3-tetrafluoro-1-propene is The solvent composition according to [1] or [2], which is 80% by mass or more and less than 100% by mass.

[4] The solvent composition according to any one of [1] to [3], further comprising an active ingredient other than Z-form of 1-chloro-2,3,3,3-tetrafluoro-1-propene.
[5] A cleaning method comprising: bringing the solvent composition according to any one of [1] to [4] into contact with the surface of an article to remove dirt attached to the surface of the article. Hereinafter, it is also referred to as a first cleaning method.
[6] The cleaning method according to [5], wherein the dirt is fat or oil or dust.
[7] A composition for forming a coating film, comprising a nonvolatile organic compound and the solvent composition according to any one of [1] to [4].

[8] [7] After applying the composition for forming a coating film on the surface of a substrate, the solvent composition is evaporated to form a coating film containing the non-volatile organic compound. A method for producing a coated substrate.
[9] The method for producing a coated film-coated substrate according to [8], wherein the material of the substrate is metal, resin, rubber, glass or ceramic.
[10] An aerosol composition comprising the solvent composition according to any one of [1] to [4].
[11] A rinse composition comprising the solvent composition according to any one of [1] to [4].

[12] A method of cleaning a member,
The member is washed with a cleaning composition containing at least one selected from N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone,
Rinsing the washed member with the rinse composition according to [11];
A method of cleaning a member, comprising: removing the rinse composition from the rinsed member by drying. Hereinafter, it is also referred to as a second cleaning method.

[13] The method for cleaning a member according to [12], wherein the cleaning composition comprises at least one selected from N-methyl-2-pyrrolidinone and cyclohexanone.
[14] The method for cleaning a member according to any one of [12] or [13], wherein the member is rinsed at 0 ° C. or more and 20 ° C. or less.
[15] The method for cleaning a member according to any one of [12] to [14], wherein the cleaning of the member is performed at 10 ° C. to 30 ° C.
[16] The method for cleaning a member according to any one of [12] to [15], wherein the member is a mask.

[17] The method for cleaning a member according to [16], wherein the mask is a mask used in a vacuum evaporation process at the time of manufacturing an organic EL element.
[18] The method for cleaning a member according to [17], wherein the organic EL element is a low molecular weight type.
[19] A cleaning tank capable of containing the cleaning composition and capable of containing the rinse composition according to [11], and a rinse tank for rinsing the above component after cleaning An apparatus for cleaning a member, comprising: a drying tank for drying the member; and the rinse composition.
The cleaning device for a member, wherein the rinse tank can hold the rinse composition in a liquid state.
[20] The apparatus for cleaning a member according to [19], wherein the rinse tank has a cooling means for cooling so as to keep the rinse composition in a liquid state.

The solvent composition of the present invention does not adversely affect the global environment, and is excellent in the solubility and drying properties of various organic compounds. The first cleaning method of the present invention does not adversely affect the global environment, and is excellent in the cleaning property and the drying property. The film-forming composition and the method for producing a film-coated substrate of the present invention do not adversely affect the global environment, and can form a uniform film with excellent drying properties. The aerosol composition of the present invention does not adversely affect the global environment, and is excellent in injectability when used in an injector. The rinse composition, the method for cleaning a member (second cleaning method) and the cleaning device for a member according to the present invention do not adversely affect the global environment, and are excellent in the cleaning property and the drying property.

It is a figure explaining the manufacturing method of an organic electroluminescence display. It is a figure which shows typically the formation aspect of the light emitting layer through a mask. It is the figure which showed schematic structure of the washing | cleaning apparatus of the mask of this embodiment.

Hereinafter, embodiments of the present invention will be described.

In the present specification, for halogenated hydrocarbons, the abbreviation of the compound is indicated in the parenthesis after the compound name, and the abbreviation is used in place of the compound name as necessary. In addition, as the abbreviations, only numbers and lower case letters after a hyphen (-) may be used (for example, “1224yd” in “HCFO-1224yd”). Furthermore, (E) attached to the name of a compound having a geometric isomer and its abbreviation indicates an E form, and (Z) indicates a Z form. In the name of the compound, in the abbreviation, when the E form and the Z form are not specified, the name and the abbreviation mean a generic name including the E form, the Z form, and the mixture of the E form and the Z form.

In the present specification, hydrofluorocarbons (HFCs) in which a part of hydrogen atoms of a saturated hydrocarbon compound is replaced by fluorine atoms, and part of the hydrogen atoms of a saturated hydrocarbon compound are replaced by fluorine atoms and chlorine atoms Compounds are hydrochlorofluorocarbons (HCFCs), compounds having carbon-carbon double bond, compounds composed of carbon atom, fluorine atom and hydrogen atom are hydrofluoroolefins (HFOs), carbon-carbon double bond Is a compound composed of carbon atom, chlorine atom, fluorine atom and hydrogen atom is called hydrochlorofluoroolefins (HCFOs), has carbon-carbon double bond, and is composed of carbon atom and fluorine atom Compounds known as perfluoroolefins (PFOs), which have a carbon-carbon double bond Carbon atoms, a compound composed of a chlorine atom and a fluorine atom chloro fluoroolefins of (CFO acids).

In the present specification, the symbol “to” represents a range which is equal to or higher than the numerical value described before and lower than the numerical value which is described thereafter.

<Solvent composition>
The solvent composition of the present invention comprises Z-isomer of 1-chloro-2,3,3,3-tetrafluoro-1-propene (HCFO-1224yd (Z)). The solvent composition of the present invention may consist only of 1224yd (Z). The solvent composition of the present invention may further contain an E-isomer of 1-chloro-2,3,3,3-tetrafluoro-1-propene (HCFO-1224yd (E)).

Hereinafter, the solvent composition which is one embodiment of the present invention is explained.
<1224 yd (Z)>
1224 yd (Z) (Z form of CF ₃ —CF = CHCl) has a double bond between carbon atoms. The GWP of 1224yd (Z) is 1, and the ODP is 0, which is a compound with small environmental impact.

The boiling point of 1224 yd (Z) is 15 ° C., and the boiling point is lower than that of 1233 zd (Z) or the like conventionally used as a solvent, so that the drying property when using as a cleaning agent or a coating solvent is excellent. In addition, 1224 yd (Z) has excellent properties as a cleaning agent and a coating solvent, for example, it has no flash point and is low in surface tension and viscosity and thus excellent in permeability.

Although 1224 yd (Z) and 1224 yd (E) which are geometrical isomers exist in 1224 yd, 1224 yd (Z) has higher chemical stability than 1224 yd (E). Further, since the boiling point of 1224 yd (Z) is 15 ° C. and the boiling point of 1224 yd (E) is 16 to 17 ° C., 1224 yd (Z) is more excellent in the drying property. Moreover, 1224 yd (Z) is excellent also from the viewpoint of easiness of manufacture.

As a method of producing 1224yd (Z), for example, a method of subjecting (I) 1,2-dichloro-2,3,3,3-tetrafluoropropane (HCFC-234bb) to a dehydrochlorination reaction, and (II) And the like) and a method of hydrogen reduction of 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya).

(I) 234bb dehydrochlorination reaction 234bb is brought into contact with a base dissolved in a solvent, that is, a solution-like base in a liquid phase to carry out 234bb dehydrochlorination reaction. The 234bb can be produced, for example, by reacting 2,3,3,3-tetrafluoropropene (HFO-1234yf) with chlorine in a solvent.

(II) Method for hydrogen reduction of 1214 ya The catalyst is converted to 1234 yf by reducing 1214 ya with hydrogen in the presence of a catalyst, and 1224 yd is obtained as an intermediate thereof. In addition, in this reduction reaction, many kinds of fluorine-containing compounds are by-produced in addition to 1224yd. 1214 ya is prepared, for example, using 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) as a raw material, an alkaline aqueous solution in the presence of a phase transfer catalyst, or chromium, iron, copper There is known a method of dehydrofluorination reaction in a gas phase reaction in the presence of a catalyst such as activated carbon.

In any of the above manufacturing methods, 1224yd is obtained as a mixture of 1224yd (Z) and 1224yd (E). The resulting mixture may be used as it is as a solvent composition, or it may be purified by a known method to use 1224yd (Z) alone, or after 1224yd (Z) and 1224yd (E) are purified respectively. It may be adjusted to the mixing ratio and used.

The 1224yd (Z) obtained by the above method may contain impurities such as a raw material of 1224yd which can not be completely separated by purification, by-products in the production process. However, among the above-mentioned impurities, a component having the effect of enhancing the washing property, the solubility and the stability shall be treated as an active ingredient other than 1224yd described later. The content of impurities is preferably 1% by mass or less with respect to the total amount of 1224yd (Z).

The content of 1224yd (Z) in the solvent composition of the present invention is preferably 50% by mass or more, more preferably 75 to 99.9% by mass, and 80 to 99.8% by mass. Is more preferred. When the content of 1224 yd (Z) is 50% by mass or more, the solubility of various organic compounds in the solvent composition is excellent. The content of 1224yd (Z) in the solvent composition of the present invention may be 100% by mass. From the viewpoint of industrial easiness of production, the content of 1224yd (Z) is more preferably 99.9% by mass or less.

When the solvent composition contains 1224 yd (E), the content ratio of 1224 yd (Z) to the total amount of 1224 yd (Z) and 1224 yd (E) is 80% by mass or more and 100% by mass from the viewpoint of the stability of the solvent composition. It is preferably less than 90% by mass, more preferably 90 to 99.9% by mass, still more preferably 95 to 99.8% by mass, and particularly preferably 96 to 99.7% by mass from the viewpoint of easiness of production.

The solvent composition of the present invention may further contain an active ingredient other than 1224 yd (Z) depending on the use and various properties required as a solvent. An active ingredient other than 1224 yd (Z) refers to a compound having the effect of enhancing the washing properties, solubility, stability and drying properties of the solvent composition of the present invention. The active ingredients other than 1224 yd (Z) also include 1224 yd (E). Hereinafter, the active ingredients other than 1224yd (Z) and 1224yd (E), that is, the active ingredients other than 1224yd will be described.

As active ingredients other than 1224yd, hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, HFCs, HFEs, HCFOs other than 1224yd, HFOs, amines, phenols, epoxides And nitro compounds and triazoles. As an active ingredient other than 1224yd, one type may be used, or two or more types may be used.

As the hydrocarbons, hydrocarbons having 5 or more carbon atoms are preferable. The hydrocarbons having 5 or more carbon atoms may be linear or cyclic, and may be saturated hydrocarbons or unsaturated hydrocarbons.

Specific examples of hydrocarbons include n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane and n-heptane , 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,5-dimethylpentane, 3,4- Dimethylpentane, 3-ethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 2- Methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethyne Pentane, 2,2,3-trimethylpentane, 2-methylheptane, 2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, cyclopentane, methyl Cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, toluene, xylene, α-pinene, dipentene, decalin, tetralin, amylnaphthalene and the like.

As the alcohols, alcohols having 1 to 16 carbon atoms are preferable. The alcohols having 1 to 16 carbon atoms may be linear or cyclic, and may be saturated alcohols or unsaturated alcohols.

Specific examples of alcohols include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 1-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2 -Pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1- Pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1- Nonanol, 3,5,5-trimethyl-1-hexanol, 1-decanol, 1- Ndecanol, 1-dodecanol, allyl alcohol, 2-propyn-1-ol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol And 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol and the like.

As the ketones, ketones having 3 to 9 carbon atoms are preferable. The ketones having 3 to 9 carbon atoms may be linear or cyclic, and may be saturated ketones or unsaturated ketones.

Specific examples of ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, diisobutyl ketone and mesityl oxide And pholon, 2-octanone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanedione, 2,5-hexanedione, diacetone alcohol, acetophenone and the like.

As the ethers, ethers having 2 to 8 carbon atoms are preferable. As long as it is an ether having 2 to 8 carbon atoms, it may be linear or cyclic, and may be saturated ether or unsaturated ether. However, epoxides described later are excluded.

Specific examples of the ethers include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, methyl anisole, furan, methyl furan, tetrahydrofuran, propylene glycol monomethyl ether, 1, 4-dioxane etc. are mentioned.

As the esters, esters having 2 to 19 carbon atoms are preferable. As long as it is an ester having 2 to 19 carbon atoms, it may be linear or cyclic, and it may be a saturated ester or an unsaturated ester.

Specific examples of the esters include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, propyl acetate, isopropyl acetate, butyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate , Pentyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, Isobutyl isobutyrate, ethyl 2-hydroxy-2-methylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, γ-butyrolactone, diethyl oxalate, dibutyl oxalate, dioxalate Pentyl, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate and the like.

As chlorocarbons, chlorocarbons having 1 to 3 carbon atoms are preferable. The chlorocarbons having 1 to 3 carbon atoms may be linear or cyclic, and may be saturated chlorocarbons or unsaturated chlorocarbons.

Specific examples of chlorocarbons include methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2 And 2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, 1,2-dichloropropane and the like.

As HFCs, linear or cyclic HFCs having 4 to 8 carbon atoms are preferable, and HFCs in which the number of fluorine atoms in one molecule is equal to or more than the number of hydrogen atoms are more preferable.

Specifically, HFCs include 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1 1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3 3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane Etc.

Examples of HFEs include (perfluorobutoxy) methane, (perfluorobutoxy) ethane, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane and the like.

As HCFOs other than 1224yd, for example, E-isomer of 1-chloro-3,3,3-trifluoropropene (HCFO-1233zd), 1233zd (Z), 1-chloro-2,3,3-trifluoropropene ( HCFO-1233yd) E form, 1233yd (Z), 1,3-dichloro-2,3,3-trifluoropropene (HCFO 1223yd) E form, 1223yd (Z).

Examples of HFOs include 1,1,1-4,4,4-hexafluoro-2-butene and methoxyperfluoroheptene ether (MPHE).

Specific examples of the amines include diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, tert-butylamine, α-picoline, N-methylbenzylamine, diallylamine, N-methylmorpholine and the like.

As phenols, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butyl catechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl- 2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,6-di-tert-butyl-p-cresol and the like.

Examples of epoxides include 1,2-propylene oxide, 1,2-butylene oxide, butyl glycidyl ether, phenyl glycidyl ether and the like.

Nitro compounds include nitromethane, nitroethane, nitropropane, nitrobenzene and the like.

Examples of the triazoles include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N, N-bis-2-ethylhexyl) aminomethyl] benzotriazole and the like.

As an active ingredient other than 1224 yd (Z), a compound soluble in 1224 yd (Z) is preferably used. The compound soluble in 1224 yd (Z) means a compound which can be mixed uniformly with 1224 yd (Z) so as to obtain a desired concentration, stirred at 10 ° C. and uniformly dispersed without causing separation into two layers or turbidity. .

Moreover, as an active ingredient other than 1224 yd (Z), it is preferable to use a compound which forms an azeotropic composition with 1224 yd (Z) from the viewpoint that the composition does not change even if the solvent composition is repeatedly used.

The solvent composition of the present invention has, as an active ingredient other than 1224 yd (Z), 2-methyl butane, n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, as an active ingredient other than 1224 yd (Z). Methylcyclopentane, methylcyclohexane, toluene, xylene, methanol, ethanol, isopropanol, acetone, 2-butanone, diethyl ether, diisopropyl ether, tetrahydrofuran, propylene glycol monomethyl ether, methyl acetate, ethyl acetate, methylene chloride, trans-1,2 Dichloroethylene, trichloroethylene, 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3 4,5,5,6,6-tridecafluorooctane, (perfluorobutoxy) methane, (perfluorobutoxy) ethane, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoro It is preferable to include at least one selected from ethoxy) ethane, 1233zd (E), 1233zd (Z), 1233yd (E), 1233yd (Z), 1223yd (E), 1223yd (Z), 1224yd (E).

In the case where the solvent composition of the present invention contains an active ingredient that improves the cleaning properties, solubility, etc., the content ratio of the active ingredient in the solvent composition is preferably 0.1 to 50% by mass. The content is more preferably 0.5 to 20% by mass, further preferably 1 to 10% by mass. If the content of the active ingredient other than 1224 yd (Z) is not less than the above lower limit value, the washability, solubility and the like of the solvent composition can be enhanced. When the content of the active ingredient other than 1224 yd (Z) is less than the above upper limit value, the excellent drying property of 1224 yd (Z) is not impaired.

From the viewpoint of enhancing the stability, the solvent composition of the present invention contains at least one selected from amines, phenols, epoxides, nitro compounds, and triazoles as an active ingredient other than 1224 yd (Z). preferable.

When the solvent composition of the present invention contains an active ingredient that improves stability, the content of the active ingredient is preferably 1 mass ppm to 10 mass% with respect to the total amount of the solvent composition, The content is more preferably 5 to 5% by mass, and further preferably 10 to 1% by mass. If the content of the active ingredient other than 1224yd is the above lower limit value or more, the stability of the solvent composition can be enhanced. When the content of the active ingredient other than 1224 yd is equal to or less than the above upper limit value, the excellent drying property of 1224 yd (Z) is not impaired.

When the solvent composition of the present invention is used as a rinse composition described later, a compound having a standard boiling point of 10 to 30 ° C., such as isopentane (boiling point: 27. 8 ° C), cyclobutane (boiling point: 12.5 ° C), 2-butyne (boiling point: 27 ° C), ethyl methyl ether (boiling point: 11 ° C), ethylene oxide (boiling point: 10.7 ° C), 1,1,1 And 3,3-pentafluoropropane (boiling point: 15.3 ° C.) may be used. When the rinse composition contains the above components, the content ratio of such components is preferably 20% by mass or less, more preferably 5% by mass or less, and 2% by mass or less with respect to the total amount of the rinse composition. It is further preferred that In the present specification, the standard boiling point refers to the boiling point measured at a pressure of 1.013 × 10 ⁵ Pa, and the boiling point in the present specification refers to the standard boiling point unless otherwise noted.

The solvent composition of the present invention described above does not adversely affect the global environment and is excellent in the solubility of various organic compounds.

The solvent composition of the present invention can be suitably used for applications in contact with members made of a wide range of materials such as metals, resins, rubbers, fibers, glasses, ceramics or composites of these.

The solvent composition of the present invention is particularly used as a cleaning agent for cleaning an article, a solvent for dry cleaning, a coating solvent for dissolving a non-volatile organic compound and applying it to a substrate, and a vacuum deposition process at the time of manufacturing an organic EL device. It is suitable as a rinse agent for rinsing and removing the cleaning composition of the mask used in

<Method of Cleaning Article (First Cleaning Method)>
In the method of cleaning an article using the solvent composition of the present invention (first cleaning method), the solvent composition of the present invention is brought into contact with the surface of the article to remove dirt adhering to the surface of the article.

The stains attached to the articles include the stains which are used when manufacturing the articles or parts constituting the articles and which must be finally removed or which adhere when the articles are used. Examples of the substance that forms dirt include greases, processing oils, silicone oils, fluxes, waxes, inks, mineral oils, oils and fats such as mold release agents including silicone oils, and dust. In particular, it can be suitably used for cleaning and removing processing oil and mold release agent adhering to the surface of an article.

Examples of the method of bringing the solvent composition of the present invention into contact with an article include hand washing, immersion washing, spray washing, immersion rocking washing, immersion ultrasonic washing, steam washing, and a combination of these. Cleaning may be performed using the cleaning device described in WO 2008/149907.

Specific examples of the article to which the solvent composition of the present invention can be applied include electronic devices (eg, capacitors, diodes, printed circuit boards), optical devices (eg, lenses, polarizing plates), precision devices (eg, micromotors, bearings) Transport equipment, medical equipment, or parts thereof. Specific examples of electrical devices, precision machines, optical articles and parts thereof include ICs, capacitors, printed circuit boards, micromotors, relays, bearings, optical lenses, glass substrates, and the like.

Examples of the material to which the solvent composition of the present invention can be applied include metals, resins, rubbers, fibers, glasses, ceramics or composite materials thereof. Examples of the composite material include laminates of metal and resin, and the like.

In addition, the solvent composition of the present invention is also suitable for cleaning of a refrigeration cycle. Specifically, at the time of maintenance of the heat exchange system of the refrigeration cycle or replacement of the working medium, the inside of the system in which the working medium circulates is cleaned to remove dirt such as lubricating oil and sludge. Here, the system through which the working medium circulates refers to piping through which the working medium circulates, an evaporator, a condenser, an expansion valve, a compressor, and the like. The heat exchange system includes a cooling system and a heat pump system. Specifically, cooling-only air conditioners, household air conditioners, commercial air conditioners, vehicle air conditioners, ship air conditioners, air conditioners such as dehumidifiers, electric refrigerators, commercial refrigerators / freezers, food products Examples include a freezer / refrigerator system, an ice maker, a freezer / refrigerator for ships, a freezer / refrigerator for vehicles, a low-temperature distribution system, etc.

<Dry cleaning method>
The solvent composition of the present invention is suitable as a dry cleaning solvent for removing dirt attached to textiles.

Textile products include clothing such as shirts, sweaters, jackets, skirts, pants, jumpers, gloves, mufflers, stalls and the like.

The material of the fiber product may, for example, be cotton, hemp, wool, rayon, polyester, acrylic or nylon.

1224yd (Z) has high solubility in soil and has a low boiling point compared to dichloropentafluoropropane (HCFC-225), which is conventionally used as a solvent for dry cleaning, perchlorethylene and petroleum solvents, so after washing The drying rate of the fiber product is very fast, and the residual of the solvent composition on the fiber product is preferably small.

The solvent composition of the present invention can be used in combination with a soap. Soap is a surfactant used for dry cleaning, and it is preferable to use cationic, nonionic, anionic, and amphoteric surfactants. Specific examples of the cationic surfactant include quaternary ammonium salts such as dodecyldimethyl ammonium chloride and trimethyl ammonium chloride. Specific examples of nonionic surfactants include polyoxyalkylene nonyl phenyl ether, polyoxyalkylene alkyl ether, fatty acid alkanolamide, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, propylene glycol fatty acid ester, phosphoric acid and fatty acid Esters and the like. Examples of anionic surfactants include alkyl sulfates such as polyoxyethylene alkyl sulfates, carboxylates such as fatty acid salts (sand), and sulfonates such as α-olefin sulfonates and lauryl sulfates. Be Specific examples of the amphoteric surfactant include betaine compounds such as alkyl betaines.

When using the solvent composition of the present invention in combination with a soap, it is preferable to use 0.01 to 10% by mass of the soap relative to 100% by mass of the solvent composition of the present invention, and 0.1 to 5% by mass is more preferable. Preferably, 0.2 to 2% by mass is more preferable.

<Application for coating solvent>
The solvent composition of the present invention can be used as a coating solvent for non-volatile organic compounds. In the method for producing a coated substrate of the present invention, a composition for forming a coating film containing a non-volatile organic compound and the solvent composition of the present invention is applied to the surface of the substrate, and then the solvent composition is evaporated. Form a coating film containing a non-volatile organic compound.

As a non-volatile organic compound, for example, a lubricant for imparting lubricity to an article, an antirust agent for imparting a rustproof effect to metal parts, a moisture proof coating agent for imparting water repellency to an article, an article Examples of the antifouling agent for imparting antifouling performance to the skin include an anti-fingerprint agent and the like.

A lubricant can be dissolved in the solvent composition of the present invention to form a lubricant solution. The lubricant means one used to reduce friction on the contact surface and prevent heat generation and wear damage when the two members move in contact with each other. The lubricant may be in the form of liquid (oil), semi-solid (grease) or solid.

As a lubricant, a fluorine-based lubricant or a silicone-based lubricant is preferable from the viewpoint of excellent solubility in 1224 yd (Z). In addition, a fluorine-type lubricant means the lubricant which has a fluorine atom in a molecule | numerator. Moreover, a silicone type lubricant means a lubricant containing silicone. The lubricant contained in the lubricant solution may be of one type, or two or more types. The fluorine-based lubricant and the silicone-based lubricant may be used alone or in combination. Examples of fluorine-based lubricants include fluorine-based solid lubricants such as fluorine oil, fluorine grease and resin powder of polytetrafluoroethylene.

As the fluorine oil, a low molecular weight polymer of perfluoropolyether or chlorotrifluoroethylene is preferable. For example, product names “Clitex (registered trademark) GPL 102” (manufactured by DuPont Co., Ltd.), “Difluor # 1”, “Difilol # 3”, “Difilol # 10”, “Difilol # 20”, “Difilol # 50”, "Difloil # 100", "Demnum S-65" (above, made by Daikin Industries, Ltd.), "Fombrin Y06", "Fombrin Y15", "Fombrin Y25", "Fombrin M03", "Fombrin M07 "Fon Brin M 15", "Fon Brin M Lubricant", "Fon Brin Y Lubricant", "Fon Brin W Lubricant", "Fon Brin Z Lubricant" grades As mentioned above, Solvay Specialty Polymers Japan Co., Ltd. product etc. are mentioned.

As the fluorine grease, it is preferable to use a fluorine oil such as a low polymer of perfluoropolyether or chlorotrifluoroethylene as a base oil and to which a powder of polytetrafluoroethylene and other thickening agents are compounded. For example, product name "Klitex (registered trademark) Grease 240 AC" (manufactured by DuPont Co., Ltd.), "Daifuroil Grease DG-203", "Demnum L65", "Demnum L100", "Demnum L200" (above, Daikin stock Made in the company), "Sumitec F 936" (made by Sumiko Lubricant Co., Ltd.), "Molicoat (registered trademark) HP-300", "Molicoat (registered trademark) HP-500", "Molicoat (registered trademark) HP-870" And “MOLYCOAT (registered trademark) 6169” (manufactured by Toray Dow Corning Co., Ltd.).

As a silicone type lubricant, silicone oil and silicone grease are mentioned. As the silicone oil, dimethyl silicone, methyl hydrogen silicone, methyl phenyl silicone, cyclic dimethyl silicone, modified silicone oil having an organic group introduced to the side chain or terminal is preferable. For example, product names "Shin-Etsu Silicone KF-96", "Shin-Etsu Silicone KF-965", "Shin-Etsu Silicone KF-968", "Shin-Etsu Silicone KF-99", "Shin-Etsu Silicone KF-50", "Shin-Etsu Silicone KF-54" "Shin-Etsu Silicone HIVAC F-4", "Shin-Etsu Silicone HIVAC F-5", "Shin-Etsu Silicone KF-56A", "Shin-Etsu Silicone KF-995" (above, made by Shin-Etsu Chemical Co., Ltd.), "SH200" Toray Dow Corning Co., Ltd.

As the silicone grease, a product in which a thickener such as metal soap and various additives are blended with the various silicone oils listed above as a base oil 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 "(above, made by Shin-Etsu Chemical Co., Ltd.)," Molicoat " Registered trademark SH33L "," Molicoat (registered trademark) 41 "," Molicoat (registered trademark) 44 "," Molicoat (registered trademark) 822 M "," Molicoat (registered trademark) 111 "," Molicoat (registered trademark) high vacuum " Grease for "", "Molicoat (registered trademark) Thermal Diffusion Compound" (The above, Toray Dow Corning Co., Ltd. ), And the like.

Moreover, as a fluorine type lubricant, as an example which can be illustrated also as a silicone type lubricant, fluorosilicone oil which is a modified silicone oil which substituted the terminal or a side chain with the fluoroalkyl group is mentioned. For example, product name "Unidyne (registered trademark) TG-5601" (manufactured by Daikin Industries, Ltd.), "Molicoat (registered trademark) 3451", "Molicoat (registered trademark) 3452" (all manufactured by Toray Dow Corning Co., Ltd.) “Shin-Etsu Silicone FL-5”, “Shin-Etsu Silicone X-22-821”, “Shin-Etsu Silicone X-22-822”, “Shin-Etsu Silicone FL-100” (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. .

The lubricant solution can be used for various substrates. For example, it can be used in industrial equipment where a fluorine-based lubricant is used, CD or DVD tray parts in personal computers and audio equipment, household equipment such as printers, copying equipment, flux equipment, office equipment and the like. Moreover, it can use for the injection needle and cylinder of a syringe in which a silicone type lubricant is used, medical tube parts, etc.

The content of the lubricant in the lubricant solution (100% by mass) is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and still more preferably 0.1 to 20% by mass. If the content of the lubricant is within the above range, it is easy to adjust the film thickness of the applied film when the lubricant solution is applied and the thickness of the lubricant coating film after drying to an appropriate range.

As a method of applying the lubricant solution, for example, application by brush, application by spray, application by immersing the article in the lubricant solution, contact with the lubricant solution to the inner wall of the tube or injection needle by sucking up the lubricant solution And the like.

The anticorrosion agent in the present invention refers to a substance which covers the surface of a metal which is easily oxidized by oxygen in the air to generate rust, and blocks the metal surface from oxygen to prevent the rust of the metal material. Examples of the rust inhibitor include mineral oil, and synthetic oils such as polyol esters, polyalkylene glycols and polyvinyl ethers.

The application method of the antirust agent is the same as that of the lubricating oil, and application by brush, application by spray, application by immersing the substrate in the antirust agent solution, and the like can be mentioned.

The content of the rust inhibitor in the rust inhibitor solution (100% by mass) is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and still more preferably 0.1 to 20% by mass .

In addition, a moisture-proof coating agent for imparting moisture-proofness and anti-staining properties to various substrates and an anti-smudge agent (such as an anti-fingerprint agent) can be applied to the surface of the substrate by the same method. Examples of the moisture-proof coating agent include Topas 5013, Topas 6013, Topas 8007 (manufactured by Polyplastics), Zeonoa 1020R, Zeonor 1060R (manufactured by Nippon Zeon), Appel 6011T, Appel 8008T (manufactured by Mitsui Chemicals, Inc.), SFE- Examples include DP02H, SNF-DP20H (manufactured by AGC Seimi Chemical Co., Ltd.), and SURECO CC Series (manufactured by AGC Co., Ltd.). Examples of antifouling agents such as anti-fingerprint agents include Optool DSX, Optool DAC (product of Daikin Industries, Ltd.), Florosurf FG-5000 (product of Fluoro Technology), SR-4000A (product of AGC Seimi Chemical Co., Ltd.), SURECO Examples include AF Series (manufactured by AGC).

The moisture-proof coating agent and the antifouling agent can be used in combination with the solvent composition of the present invention in the same manner as the lubricant and the rust inhibitor, and the coating method to the substrate can also be the same. As a base material to which a lubricant, an antirust agent, a moisture proof coating agent, and an antifouling agent are applied, a base material of various materials such as metal, resin, rubber, glass, and ceramics can be adopted. The substrate may be composed of these composite materials.

<Aerosol composition>
The solvent composition of the present invention is preferably used in the form of an aerosol composition, from the viewpoint of being nonflammable and having high vapor pressure at room temperature and containing 1224 yd (Z).

Specifically, an injector including an aerosol composition, a container for containing the aerosol composition, and a jetting unit for jetting the aerosol composition to the outside of the container is used. By spraying a solvent-forming composition of the present invention or a non-volatile organic compound and a solvent composition according to the present invention from an injector, the article can be cleaned and the non-volatile organic compound can be applied to a substrate.

The aerosol composition comprises the solvent composition of the present invention. The aerosol composition may further comprise a vasopressor.

As a pressurizing agent, 1,3,3,3-tetrafluoropropene (HFO-1234ze), 1,2,2,2-tetrafluoroethane (HFC-134a), 2,3,3,3-tetrafluoropropene (HFO-1234yf), dimethyl ether, CO ₂ , methane, ethane, propane, isobutane and the like are preferable. The pressurizing agent may be used in the state of compressed gas or in the state of liquefied gas. It is preferable that the pressure-increasing agent has a small pressure fluctuation during use of the injector, and can uniformly and uniformly spray the article to be cleaned or the substrate to be coated.

The method used in the form of an aerosol composition can reduce the total amount of solvent composition used as compared to a method of dipping in a solvent composition in a common container to apply a composition for cleaning or film formation. it can.

Furthermore, even when the flammable pressure-increasing agent is contained, the aerosol composition contains 1224 yd (Z), so that the flammability can be suppressed. For example, an aerosol composition in which the mass ratio of dimethyl ether to 1224 yd (Z) is 50/50 can be used more safely because it can reduce the heat of combustion to 60% as compared to the case of using dimethyl ether alone. Can.

<Method of Cleaning Parts (Second Cleaning Method)>
The method for cleaning a member of the present invention (second cleaning method) comprises at least one member selected from N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone The member washed with the cleaning composition and rinsed is rinsed with the rinse composition comprising the solvent composition of the present invention, and the rinse composition is removed by drying from the rinsed member.

As a member used here, it is a member which consists of glass, a metal, an alloy etc., For example, the mask etc. which are used at the process of manufacturing the member for electronic devices, the member for electronic devices, etc. are mentioned. In particular, the mask used at the time of organic EL element manufacture is preferable. Above all, it is suitable as a method of cleaning a mask used in a vacuum deposition process at the time of manufacturing an organic EL element. Hereinafter, this preferable aspect is demonstrated. First, the mask to be cleaned will be described.

The mask to be cleaned by the second cleaning method of the present invention is, for example, one used in a vacuum evaporation process at the time of manufacturing an organic EL element in the manufacturing process of the organic EL display described below.

Hereinafter, a method of manufacturing the organic EL display device will be described with reference to FIGS. In manufacturing the organic EL element, a TFT (thin film transistor) and a transparent electrode are formed on a glass substrate, and a hole transport layer is further formed. The glass substrate 10 on which the TFT, the transparent electrode, and the hole transport layer are formed is inserted into the vacuum chamber with the vertical direction downward. In the vacuum chamber, on the glass substrate 10, light emitting layers corresponding to the respective primary colors R, G, B as color display devices are formed. This process is separately performed corresponding to each primary color R, G, B as a color display device. That is, the glass substrate 10 is sequentially inserted into separate vacuum chambers for forming light emitting layers corresponding to the respective primary colors R, G, B.

In each vacuum chamber, a mask 20 which has been opened in advance according to the shape of the light emitting layer is disposed in the manner shown in FIG. The mask 20 is fixed by a mask frame 21 disposed on the holding table 24.

In each vacuum chamber, a portion corresponding to a transparent electrode (anode) used for light emission of a predetermined primary color corresponding to one of R, G and B of the transparent electrodes (anode) as a mask 20 Only the mask is opened. Thereby, in each chamber, the light emitting layer corresponding to each primary color can be formed at a predetermined position.

In FIG. 1, the material of the light emitting layer is heated and evaporated from a deposition source (source) 30 disposed below the holding table 24 to deposit the same material on the surface of the glass substrate 10 through the opening of the mask. Let The formation mode of the light emitting layer through the mask 20 is schematically shown in FIG. As shown in FIG. 2, the mask 20 covers the transparent electrodes (anodes) other than the formation regions of the transparent electrodes corresponding to the corresponding primary colors in each chamber. Then, the organic EL material corresponding to the corresponding primary color is heated and vaporized in the source 30 and vapor deposited on the glass substrate 10 (more precisely, the hole transport layer thereof) through the opening 20 h of the mask 20. . Examples of the material of the mask include stainless steel such as SUS, Ni alone, an alloy of Fe and Ni (for example, Fe—Ni alloy), or a semiconductor such as silicon.

In the vapor deposition step, various organic compounds made of vapor deposition material are attached to the mask, and the object to be cleaned in the second cleaning method of the present invention is, for example, a mask to which the organic compound after the vapor deposition step is attached. .

(Washing process)
In the second cleaning method of the present invention, in order to remove the organic compound, the member such as the mask to which the organic compound is attached is cleaned by the cleaning composition.

In the second cleaning method of the present invention, the cleaning composition used to clean the member is at least one selected from N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone. Contains active ingredients (detergents). Among them, from the viewpoint of detergency, it is preferable to include at least one selected from N-methyl-2-pyrrolidinone and cyclohexanone.

In the cleaning composition used in the method for cleaning a member of the present invention (second cleaning method), the content ratio of the active ingredient for cleaning is 80 to 100 mass in the cleaning composition from the viewpoint that the member can be sufficiently cleaned. % Is preferable, 95 to 100% by mass is more preferable, and 98 to 100% by mass is more preferable. When the cleaning composition contains a plurality of the above-mentioned active ingredients in combination, the total content ratio of these components is preferably in the above-mentioned preferable range in that the member can be sufficiently cleaned.

In the second cleaning method, the cleaning composition may contain components other than the above-mentioned active ingredients, as long as the effects of the present invention are not impaired. Components other than such active ingredients are, for example, butane, pentane, neopentane, isopentane, hexane, heptane, octane, nonane, cyclobutane, cyclopentane, cyclohexane, saturated hydrocarbons such as cyclohexane, 1-butene, 2-butene Unsaturated hydrocarbons such as 2-methylpropene, 1-pentene, 2-pentene, 1-butyne, 2-butyne, butadiene, pentene, cyclopropene, cyclobutene, cyclopentene, cyclohexene etc., methanol, ethanol, normal propyl alcohol Alcohols such as isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc., dimethyl ether, ethyl methyl ether, diethyl ether, diisocyanate Ethers such as pill ether, methyl-tert-butyl ether and tetrafluoroethanol, acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, ketones such as cyclopentanone and cyclohexanone, methyl formate, ethyl formate, propyl formate And esters such as methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate and γ-butyrolactone, amines such as monomethylamine, dimethylamine and trimethylamine, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene Chlorocarbons such as lene, trans-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, 1,2-dichloropropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3- Pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1 1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, HFCs (hydrofluorocarbons) such as 1,1,1,2,2,3,3,4,5,5,6,6-tridecafluorooctane, decafluorobutane, dodecafluoropentane, tetradecafluoro Hexane, He PFC (perfluorocarbons) such as sadadecafluoroheptane, octadecafluorooctane, etc., dichlorofluoromethane, dichloropentafluoropropane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane, 2,2, Examples thereof include HCFC (hydrofluorochlorocarbon) such as 2-dichloro-1,1,1-trifluoroethane and the like, but are not limited thereto. Also, these components may be contained singly or in combination of two or more.

When the cleaning composition contains components other than such active ingredients in the second cleaning method, the content ratio of these components in the cleaning composition is preferably 20% by mass or less, more preferably 5% by mass or less, 2 mass% or less is further more preferable.

Here, the cleaning may be performed by a known cleaning method, such as a method of immersing the member in the cleaning composition, a method of spraying the cleaning composition onto the member by a jet water flow, and the like. In addition, ultrasonic cleaning may be used in combination with the cleaning of the members, whereby the dissolving power can be improved and the cleaning time can be shortened.

The cleaning time may be, for example, about 5 to 15 minutes, although it depends on the size of the member and the kind and amount of the attached organic compound. The temperature of the cleaning composition in the cleaning step may be normal temperature without temperature control, preferably 10 to 30 ° C., and more preferably 15 to 25 ° C. Thus, by washing using the cleaning composition containing at least one selected from N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone in the above temperature range. Sufficient cleaning performance can be obtained, and at the time of cleaning, the members will not be deformed or distorted by heat.

In addition, in this cleaning step, one or more types of organic compounds adhering to the surface of various members can be sufficiently removed only by the cleaning composition by using the above-mentioned specific cleaning composition. Therefore, it is not necessary to prepare a plurality of different cleaning solutions, and it is sufficient to prepare at least one cleaning tank, which makes the cleaning process very simple.

The cleaning composition can be reused by distilling the used cleaning solution composition. Even when the cleaning composition contains components other than N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone, the used cleaning composition is distilled and recovered. It can be reused by adjusting the composition of the solution.

(Rinse process)
In the second cleaning method, the member cleaned by the cleaning composition is then rinsed with a rinse composition comprising the solvent composition of the present invention. The term "rinse" as used herein means that the cleaning composition attached to the member cleaned by the cleaning composition is rinsed away by the rinse composition.

As a method of rinsing the member after cleaning, a method of immersing the member in the rinse composition, a method of flowing the rinse composition to the member, and the like can be mentioned. By either method, the cleaning composition attached to the surface of the member after cleaning can be easily removed, and the surface of the member can be extremely cleanly rinsed.

The time for performing this rinse may be, for example, 5 to 15 minutes, although it depends on the size of the member. The temperature of the rinse composition in the rinse may be a temperature at which the rinse composition can be maintained in a liquid state, and may be a normal temperature without temperature control. Further, the rinse composition used here preferably has a boiling point of 10 to 30 ° C. In that case, cooling may be performed so that the temperature can be stably maintained at or below the boiling point of the rinse composition. The temperature of the rinse composition is preferably 0 to 20 ° C., and more preferably 10 to 20 ° C. As described above, since the rinse can be performed at a relatively low temperature, deformation, distortion and the like of the member due to heat do not occur.

Here, the temperature of the rinse composition may be lower than the temperature of the cleaning composition, or may be lower than normal temperature. Such a low temperature is preferable because drying in the next step can be carried out extremely easily.

N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone contained in the cleaning composition have excellent solubility in 1224 yd (Z) in the rinse composition The cleaning composition is very easily removed by the rinse composition. Moreover, when the rinse composition contains 1224yd (Z), the drying property is excellent.

The content ratio of 1224yd (Z) in the rinse composition used in the method for cleaning a member of the present invention (second cleaning method) is preferably 80 to 100% by mass from the viewpoint of sufficient rinsing of the member And 95 to 100% by mass, and more preferably 98 to 100% by mass. From the viewpoint of industrial easiness of production, the content of 1224yd (Z) is preferably 99.9% by mass or less.

In addition, when the rinse composition of this invention contains components other than 1224 yd (Z), it is preferable to use the compound which is not decomposed | disassembled by the component contained in washing | cleaning composition as components other than 1224 yd (Z). Fluorine ions and the like do not remain on the surface of the member after rinsing, and the member can be cleaned extremely cleanly.

(Drying process)
In the second cleaning method, after the rinsing, the member is dried by evaporation of the rinse composition adhering to the surface of the member, and the rinse composition is removed from the member to achieve the cleaning operation. Although the second washing method is characterized by good drying property, it does not exclude the combined use of operations and steps for further improving the drying property.

Here, as a method of drying the member, a known drying method such as a method of drying the member after rinsing by natural drying, a method of drying by air blow, a method of drying by reduced pressure, and the like can be used. Among them, a method of drying by reduced pressure is preferable in that the member can be dried more efficiently.

In the method of drying by air blowing, for example, dry air of preferably 10 to 40 ° C., more preferably 20 to 30 ° C. can be sprayed and dried. As described above, since drying can be performed at a relatively low temperature, deformation, distortion and the like of the member due to heat do not occur.

The pressure in the case of drying the member by depressurization requires a long time for depressurization, and if the adhesion amount of the rinse composition to the member is small, drying can be performed in the process of depressurization. It can set suitably by the adhesion amount. The pressure in the case of drying the member by reduced pressure is preferably set, for example, in the range of a vapor pressure of 10 ° C. or more of the rinse composition to less than 101.3 kPa. For example, when a rinse composition is comprised only by 1224yd, it is preferable to pressure-reduce to the pressure range of 72 kPa or more and less than 101.3 kPa in a drying process.

In the method for cleaning a member according to the present invention (second cleaning method), by using the above-mentioned specific rinse composition as the rinse composition, the cleaning composition attached to the member at the time of cleaning is removed by rinsing and then the member is removed The attached rinse composition can be easily dried and removed at a temperature around normal temperature.

According to the second cleaning method of the present invention described above, by using the specific rinse composition, the cleaning composition attached to the member at the time of cleaning is removed, and the drying of the rinse composition can be performed quickly and easily. Equipment and operation, and the parts can be cleaned very cleanly. The method for cleaning a member of the present invention (second cleaning method) is useful as a method for cleaning a member when manufacturing an organic EL device by a vacuum deposition method, but preferably the vacuum at the time of manufacturing a low molecular weight EL device It is used in a vapor deposition process.

(Washing device for parts)
Next, as an example of the member cleaning apparatus of the present invention, a mask cleaning apparatus used in a vacuum deposition process at the time of manufacturing an organic EL element will be described with reference to the drawings.

As shown in FIG. 3, the cleaning apparatus 1 for the mask of the present embodiment is capable of containing the cleaning composition, and the cleaning tank 2 for cleaning the mask 20 used in the vacuum deposition process at the time of manufacturing the organic EL element. And a rinse tank 3 for accommodating the rinse composition and for rinsing the mask 20 after washing, and a drying tank 4 for drying the rinsed mask 20. In the cleaning device 1, the rinse tank 3 can hold the rinse composition in a liquid state.

The cleaning tank 2 is a container for containing the cleaning composition, and immersing the mask 20 to be cleaned in the cleaning composition for cleaning. The cleaning tank 2 may be any one as long as it can stably contain the cleaning composition, and examples thereof include conventionally known cleaning tanks.

The rinse tank 3 is a container for containing the rinse composition, and immersing the mask 20 after being washed in the washing tank 2 in the rinse composition for washing. The rinse tank 3 may be any one as long as it can stably contain the rinse composition in a liquid state, and examples thereof include conventionally known rinse tanks.

In the present embodiment, since the rinse composition stored in the rinse tank 3 preferably has a relatively low boiling point of 10 to 30 ° C., evaporation of the rinse composition and the like are suppressed, and the composition is stabilized in a liquid state. In order to hold | maintain, it is preferable to equip the outer periphery of the rinse tank 3 with the cooling means 3a. At this time, the cooling temperature is preferably a temperature lower by 5 ° C. than the boiling point of the rinse composition, and more preferably a temperature lower by 10 ° C.

The drying tank 4 is a container that accommodates the mask 20 after being rinsed in the rinse tank 3 therein, and dries and removes the rinse composition attached to the surface of the mask 20. The drying tank 4 may be any one that can accelerate the removal of the attached rinse composition by drying with respect to the mask 20 of interest.

For example, dry air may be blown to the mask 20 or a sealed space may be formed, and the inside of the drying tank 4 may be under reduced pressure conditions, or the mask 20 may be dried. The drying tank 4 may have an air blowing mechanism for drying air, a pressure reducing mechanism inside the drying tank 4 and the like according to the drying means.

In order to clean the mask 20, for example, a mask transfer container 5 which can be sequentially transferred to the cleaning tank 2, the rinse tank 3 and the drying tank 4 while holding the mask 20 inside may be provided. The mask transfer container 5 may be any one as long as it can stably hold the mask 20, and it is preferable that the bottom and the side can pass a liquid or gas such as a mesh.

Next, reference examples and examples will be described. The present invention is not limited to these reference examples and examples.

(Production example: Production of 1224yd)
An isomer mixture of 1224yd (E) and 1224yd (Z) was prepared according to the method described in WO 2017/110851. The isomer mixture was purified by the method described in WO 2017/146190 to produce 1224 yd (Z) and 1224 yd (E).

(Preparation of solvent composition)
By mixing 1224yd (Z) and 1224yd (E) obtained in the production example, so that the mass ratio shown by 1224yd (Z) / 1224yd (E) is 99.5 / 0.5, an example (1- It was set as the solvent composition of 1). In addition, the solvent composition of Example (1-1) and the components shown in Table 1 are mixed so as to achieve the mass ratio shown in Table 1, and the solvent compositions of Examples (1-2) to (1-15) Was prepared. In Example (1-13), 1,1,1,3,3-pentafluorobutane (HFC-365) (manufactured by Japan Solvay, trade name: Solcan 365) as a component other than 1224 yd, Example (1-) In 14), 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (manufactured by AGC, ASAHIKLIN AE-3000); Perfluorobutoxy) methane (Nobec 7100 manufactured by 3M Japan Co., Ltd., indicated as "HFE-7100" in the table) was used.

(Cleanability test 1)
After immersing a test piece (25 mm × 30 mm × 2 mm) of stainless steel (SUS-304) in the product name “Daphne Marg Plus LA5” (made by Idemitsu Kosan Co., Ltd.) which is a cutting oil, it is removed from the cutting oil, The test piece to which the cutting oil adhered was produced. The test piece is immersed in 50 mL of the solvent composition of Examples (1-1) to (1-15) for a predetermined time, and then withdrawn from each solvent composition to visually observe the removal state of the cutting oil adhering to the test piece Then, the evaluation of washability was performed according to the following criteria. The evaluation results of the washability test 1 are shown in Table 1. In addition, the solvent composition adhering to the test piece dried immediately after withdrawal.

(Evaluation criteria)
S: It could be removed within 10 seconds after immersion.
A: It could be removed within 20 seconds after immersion for more than 10 seconds.

As can be seen from Table 1, all of the solvent compositions of Examples (1-1) to (1-15) are found to be excellent in the drying property and the cleaning property of the cutting oil.

(Cleanability test 2)
The solvent compositions of Examples (1-1) to (1-15) and dimethyl ether as a pressurizing agent were charged in a spray can so that the mass ratio represented by 1224 yd / dimethyl ether was 50/50. The solvent composition was sprayed from this spray can and sprayed onto a test piece (25 mm × 30 mm × 2 mm) of stainless steel (SUS-304) to which the same cutting oil as in the washability test 1 was attached. Was removed. Moreover, the solvent composition adhering to the test piece dried immediately.

(Evaluation of coating performance 1)
In the solvent compositions of Examples (1-1) to (1-15), a silicone lubricant, product name "Shin-Etsu Silicone KF-96-50CS" (Shin-Etsu Chemical Co., Ltd.), a solvent composition and a silicone When it was added so as to be 0.5% by mass with respect to the total amount of the system lubricant, all dissolved uniformly. Furthermore, when the same test was carried out with a product name “FOMBLIN M15” (manufactured by Nippon Solvay Co., Ltd.) which is a fluorine-based lubricant, all of them were uniformly dissolved.

Furthermore, the silicone lubricant solution obtained above is applied to the surface of a SUS-304 plate (25 mm × 30 mm × 2 mm) and air-dried at 19 to 21 ° C. to obtain SUS-304 A lubricant coating was formed on the surface. In any of the examples using the solvent compositions of Examples (1-1) to (1-15) as the coating solvent, the coating film was uniformly formed by visual evaluation. The same test was carried out for the fluorine-based lubricant, and as a result, the coating film was formed uniformly in all cases.

(Evaluation 2 of application performance)
The silicone lubricant solution and the fluorine lubricant solution in which each lubricant obtained above is dissolved in a solvent composition are each represented by a weight ratio of 50/50 represented by 1224 yd / dimethyl ether as dimethyl ether which is a pressurizing agent. The spray can was filled to be When each lubricant solution was sprayed from this spray can and sprayed onto a test piece of stainless steel (SUS-304), the lubricant solution adhered to the surface of the test piece was used in any of the examples using the lubricant solution. The solvent composition was dried immediately, and it was confirmed that the lubricant was applied to the surface of the test piece.

(Evaluation of the washability of masks used in organic EL production)
(Reference Example 1)
HFE- used as a rinse agent and 1224yd (a composition containing 99.5% by mass or more and 1224yd (E) less than 0.5% by mass as the rinse composition; the same applies hereinafter) A comparison of boiling points and GWP (global warming potential) of 347 pcf and HFE-449 sl is shown in Table 2. It can be seen from Table 2 that HCFO-1224yd has a significantly lower environmental impact than currently used HFE-347pcf and HFE-449sl.

1224yd which is a rinse composition used in the present invention, and a cleaning agent for a mask used in a vacuum deposition process in producing three representative organic EL elements (N-methyl-2-pyrrolidinone, N, N-dimethyl The solubility of formamide and cyclohexanone at room temperature at 20 ° C. is compared with HFE-347pcf (manufactured by AGC, product name: AE-3000) and HFE-449sl (manufactured by 3M, product name: Novec 7100). It is shown in Table 3. From Table 3, the solubility of HCFO-1224yd in the detergent is equivalent to that of current HFE-347pcf and HFE-449sl, and does not cause any inconvenience in practical use.

(Example 1, Comparative Examples 1 and 2)
Three 25 mm × 30 mm × 2 mm metal (SUS) pieces whose mass was measured in advance at room temperature of 20 ° C. were prepared. A low molecular weight organic EL material is attached to these metal pieces and dipped in N-methyl-2-pyrrolidinone, and the attached low molecular organic material is washed and pulled up, and the N-methyl-2-pyrrolidinone falls. Let stand until no longer done.

Subsequently, these metal pieces were respectively added to 1224 yd (Example 1), HFE-347 pcf (Comparative Example 1) (manufactured by AGC, AE-3000) and HFE-449 sl (manufactured by 3M, Novec 7100) (Comparative Example 2). Immersed and manually rocked and rinsed.

Table 4 shows the results of measuring the time to return to the weight before the test under the environment of 20 ° C. and 101.3 Pa by pulling up the rinsed metal piece. According to the results in Table 4, 1224yd has the same rinse action as the conventional rinse agents HFE-347pcf and HFE-449sl, but the time to drying can be shortened to 1/3 or less and the extremely excellent fast drying property is achieved. It is understood that it has.

(Reference Example 2)
Hydrofluoroethers such as “Novec HFE 7100” (C ₄ F ₉ OCH ₃ ), which are known rinse agents, include, for example, N-methyl-2-pyrrolidinone and N, N-dimethylformamide, which are active components of cleaning compositions. It may decompose in the presence to generate fluorine ions (see, for example, JP 2009-518857A). Therefore, depending on the combination of the cleaning composition and the rinse composition, a decomposition product may be generated, which may adhere to the mask surface and not be cleaned for cleaning.

In this reference example 2, the degradability of the rinse composition by N-methyl-2-pyrrolidinone was examined. A solvent sample was prepared by adding 5% by mass of N-methyl-2-pyrrolidinone to each of HCFO-1224yd and HFE-449sl (manufactured by 3M, Novec 7100) (Comparative Example 2).

Each solvent sample was left in a room at 20 ° C. for 3 days and 7 days. The concentration of fluorine ions in each solvent sample after standing was measured with a fluorine ion meter (manufactured by Toa DKK, IM-55G, fluorine ion electrode: F-2021, manufactured by Toa DKK). The detection limit of the fluorine ion concentration was 0.5 ppm. The results are shown in Table 5.

The results show that HCFO-1224yd is stable and does not decompose even when it coexists with N-methyl-2-pyrrolidinone, so that the mask surface can be kept clean.

From the above, the method for cleaning a member according to the present invention (second cleaning method) cleans the organic compound adhering to the surface of the member, and subsequently rinses and dries the cleaning composition adhering to the surface of the member effectively and quickly It is an excellent method of cleaning parts.

The solvent composition of the present invention is a solvent composition which does not adversely affect the global environment and is excellent in the solubility of various organic compounds. This solvent composition is useful in a wide range of industrial applications such as cleaning, coating applications, rinse agents attached to members, etc., and can be used for substrates of various materials such as metals, resins, and elastomers.

DESCRIPTION OF SYMBOLS 1 ... Cleaning apparatus of a mask, 2 ... cleaning tank, 3 ... rinse tank, 3a ... cooling means, 4 ... drying tank, 5 ... mask transfer container, 10 ... glass substrate, 11 ... transparent electrode, 20 ... mask, 20h ... opening Part 21 21 Mask frame 24 Holder base 30 Source.

Claims

Solvent composition containing Z-form of 1-chloro-2,3,3,3-tetrafluoro-1-propene.
The solvent composition according to claim 1, wherein a content of Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene in the solvent composition is 50% by mass or more.
Furthermore, it contains E form of 1-chloro-2,3,3,3-tetrafluoro-1-propene, Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene and 1-chloro The content ratio of Z form of 1-chloro-2,3,3,3-tetrafluoro-1-propene relative to the total amount of E form of 2,3,3,3-tetrafluoro-1-propene is 80 mass The solvent composition of Claim 1 or 2 which is% or more and less than 100 mass%.
The solvent composition according to any one of claims 1 to 3, further comprising an active ingredient other than Z-form of 1-chloro-2,3,3,3-tetrafluoro-1-propene.
A cleaning method comprising: contacting the surface of an article with the solvent composition according to any one of claims 1 to 4 to remove dirt adhering to the surface of the article.
The cleaning method according to claim 5, wherein the dirt is fat or oil or dust.
A film-forming composition comprising a non-volatile organic compound and the solvent composition according to any one of claims 1 to 4.
After the composition for forming a coating film according to claim 7 is applied to the surface of a substrate, the solvent composition is evaporated to form a coating film containing the non-volatile organic compound. Method for producing a membrane-coated substrate
The manufacturing method of the base material with a coating film of Claim 8 whose material of the said base material is a metal, resin, rubber | gum, glass, or ceramics.
An aerosol composition comprising the solvent composition according to any one of the preceding claims.
A rinse composition comprising the solvent composition according to any one of claims 1 to 4.
A method of cleaning the member,
The member is washed with a cleaning composition containing at least one selected from N-methyl-2-pyrrolidinone, N, N-dimethylformamide, dimethylformamide, ethylene glycol dimethyl ether and cyclohexanone,
Rinsing the cleaned member with the rinse composition of claim 11;
A method of cleaning a member, comprising: removing the rinse composition from the rinsed member by drying.
The method for cleaning a member according to claim 12, wherein the cleaning composition comprises at least one selected from N-methyl-2-pyrrolidinone and cyclohexanone.
The member cleaning method according to claim 12, wherein the member is rinsed at 0 ° C. or more and 20 ° C. or less.
The method for cleaning a member according to any one of claims 12 to 14, wherein the cleaning of the member is performed at 10 ° C to 30 ° C.
The method for cleaning a member according to any one of claims 12 to 15, wherein the member is a mask.
The method for cleaning a member according to claim 16, wherein the mask is a mask used in a vacuum evaporation process at the time of manufacturing an organic EL element.
The member cleaning method according to claim 17, wherein the organic EL element is a low molecular weight type.
A cleaning tank capable of containing a cleaning composition and capable of containing a cleaning composition for cleaning a member, and a rinsing tank capable of containing a rinse composition as set forth in claim 11 for rinsing said component after cleaning An apparatus for cleaning a member, comprising: a drying tank for drying; and the rinse composition,
The cleaning device for a member, wherein the rinse tank can hold the rinse composition in a liquid state.
The apparatus for cleaning a member according to claim 19, wherein the rinse tank includes cooling means for cooling so as to keep the rinse composition in a liquid state.