JPWO2008081804A1 - Cleaning agent and cleaning method containing fluorinated cyclic unsaturated hydrocarbon - Google Patents

Abstract

The present invention is a cleaning method for an article comprising a cleaning agent containing a fluorinated cyclic unsaturated hydrocarbon represented by the following formula (1), and a step of bringing the article into contact with the cleaning agent. . ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning method which is excellent in detergency, nonflammability, stability, and has a very small load to a global environment, a freezing point is low, and is easy to handle, and the washing | cleaning method using this detergent are provided. . In the following formula (1), X, Y and Z each independently represent a fluorine atom or a hydrogen atom. However, at least one of X, Y, and Z is a hydrogen atom. n is 2 or 3.

Description

  The present invention relates to a cleaning agent containing a fluorinated cyclic unsaturated hydrocarbon, and a cleaning method using the cleaning agent.

  This application claims priority based on Japanese Patent Application No. 2006-353915 for which it applied to Japan on December 28, 2006, and uses the content here.

  Conventionally, chlorocarbons such as trichloroethane and chlorofluorocarbons such as trichlorotrifluoroethane, which are excellent in incombustibility and stability, have been used as industrial cleaners for articles made of various materials. However, in recent years, perfluorocarbons containing no chlorine have been used instead of these compounds from the viewpoint of ozone layer destruction and global warming.

In recent years, new detergents mainly composed of fluorine compounds containing hydrogen atoms such as hydrofluorocarbons and hydrofluoroethers have been used. For example, a detergent mainly composed of chain-like decafluoropentane (CF ₃ CHFCHFCF ₂ CF ₃ ) described in Patent Document 1 and nonafluorobutyl methyl ether (C ₄ F ₉ OCH described in Patent Document 2) ₃ ) Detergents containing fluorinated ethers having an ether structure in the molecule are known.

Since the chain-like fluorine compounds containing hydrogen atoms described in these documents do not contain chlorine atoms, they do not cause destruction of the ozone layer and have a global warming potential (GWP; 100-year integrated value). However, it is said that it is small compared to perfluorocarbons and the like that have been used conventionally, and the burden on the global environment is small.
However, the GWP of decafluoropentane described in Patent Document 1 is 1800, and the GWP of nonafluorobutyl methyl ether described in Patent Document 2 is 390, which is still not sufficient from the viewpoint of protecting the global environment. .

Patent Document 3 describes a detergent containing a fluorinated cyclic saturated hydrocarbon such as heptafluorocyclopentane having a cyclic structure. Moreover, it describes that fluorinated cyclic unsaturated hydrocarbon may be mixed as an additive solvent with heptafluorocyclopentane.
The heptafluorocyclopentane described in this document has a small GWP value, excellent cleaning properties, non-flammability and excellent stability in the presence of water.
However, since the cleaning agent described in Patent Document 3 has a high freezing point of fluorinated cyclic saturated hydrocarbon, which is a main component, of 0 ° C. or higher, handling properties may be a problem when used in cold regions. there were. Further, the properties of the fluorinated cyclic unsaturated hydrocarbon as the additive solvent and the performance as a cleaning agent are unknown.

Japanese translation of PCT publication No. 6-501949 JP-T-2002-517557 JP 10-316598 A

  The present invention has been made in view of such a state of the art, and is inferior in terms of non-combustibility, stability, cleanability, and the like as compared with a conventional detergent using a fluorine compound. It is an object of the present invention to provide a cleaning agent that has a very low load on the global environment, has a low freezing point, and is easy to handle, and a method for cleaning an article using the cleaning agent.

In order to solve the above-mentioned problems, the present inventors diligently studied a cleaning agent containing a fluorine compound. As a result, it has been found that when a specific fluorinated cyclic unsaturated hydrocarbon is used, a cleaning agent which is kind to the earth, excellent in nonflammability, detergency and stability, and has a low freezing point can be obtained.
Further, when the fluorinated cyclic unsaturated hydrocarbon and the alcohol having 1 to 5 carbon atoms are contained, the fluorinated cyclic unsaturated hydrocarbon and the alcohol form an azeotrope composition, and are washed in a liquid state. The present inventors have found that the cleaning agent can be recycled by steam cleaning and is excellent in economic efficiency, and has completed the present invention.
Thus, according to the first aspect of the present invention, the following cleaning agents (1) to (4) are provided.
(1) Formula (1)

(Wherein X, Y and Z each independently represent a fluorine atom or a hydrogen atom, provided that at least one of X, Y and Z is a hydrogen atom; n is 2 or 3). A detergent containing the fluorinated cyclic unsaturated hydrocarbon represented.
(2) The cleaning agent according to (1), wherein the content of the fluorinated cyclic unsaturated hydrocarbon is 70% by weight or more.
(3) The cleaning agent according to (1) or (2), further comprising at least one kind of alcohol having 1 to 5 carbon atoms and being an azeotropic mixture composition.

(4) The cleaning agent according to (3), which is a composition having a boiling point of 40 to 120 ° C.
(5) The fluorinated cyclic unsaturated hydrocarbon is 1,3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene, or The cleaning agent according to any one of (1) to (4), which is 3,3,4,4,5,5-hexafluorocyclopentene.

According to the second aspect of the present invention, the following cleaning method (6) is provided.
(6) A method for cleaning an article comprising the step of bringing the article into contact with the cleaning agent of the present invention.

It is the schematic of an example of the apparatus used for implementation of the washing | cleaning method of this invention. It is the schematic of an example of the apparatus used for implementation of the washing | cleaning method of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Immersion washing tank, 2 ... Steam generation tank, 3 ... Cooling pipe, 4 ... Moisture separator, 5 ... Ultrasonic generator, 6 ... Filtration circulation pump, 7 ..Filtration filter, 8 ... heater, 9 ... steam flow, 10 ... steam zone, 11 ... first cleaning tank, 12 ... second cleaning tank, 13 ... rinse Cleaning tank, 14 ... Separation tank, 15 ... Steam cleaning tank, 16 ... Cleaning agent tank, 17 ... Cleaning agent tank of the present invention, 18 ... Steam zone, 19 ... Heating device 20 ... Ultrasonic generators, 21, 22 ... Circulation pump, 24 ... Rinse liquid transfer pump, 25 ... Distillation tower

Hereinafter, the present invention will be described in detail by dividing it into 1) a cleaning agent and 2) a method for cleaning an article.
1) Cleaning Agent The cleaning agent of the present invention contains a fluorinated cyclic unsaturated hydrocarbon represented by the formula (1) (hereinafter referred to as “fluorinated cyclic unsaturated hydrocarbon”). .

In formula (1), X, Y, and Z each independently represent a fluorine atom or a hydrogen atom. However, at least one of X, Y, and Z is a hydrogen atom.
n is 2 or 3.

  Specific examples of such compounds include the following formula:

1,3,3,4,4,5,5-heptafluorocyclopentene (boiling point 46 ° C.) represented by the following formula:

1,2,3,4,4,5,5-heptafluorocyclopentene (boiling point 51 ° C.) represented by the following formula:

3,3,4,4,5,5-hexafluorocyclopentene (boiling point 77 ° C.) represented by the following formula:

1,3,4,4,5,5-hexafluorocyclopentene (boiling point 74 ° C.) represented by the following formula:

A compound having 5 carbon atoms such as 2,3,4,4,5,5-hexafluorocyclopentene (boiling point 68 ° C.) represented by the following formula:

1,3,3,4,4,5,5,6,6-nonafluorocyclohexene (boiling point 64 ° C.) represented by the following formula:

1,2,3,4,4,5,5,6,6-nonafluorocyclohexene (boiling point 70 ° C.) represented by the following formula:

1,3,4,4,5,5,6,6-octafluorocyclohexene (boiling point 88 ° C.) represented by the following formula:

And a compound having 6 carbon atoms such as 3,3,4,4,5,5,6,6-octafluorocyclohexene (boiling point 86 ° C.) represented by the formula:
These compounds can be used alone or in admixture of two or more.

  Among these, in the present invention, 1,3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene, 3,3,4 , 4,5,5-hexafluorocyclopentene, 1,3,4,4,5,5-hexafluorocyclopentene, 2,3,4,4,5,5-hexafluorocyclopentene, and the like. Since it is preferably nonflammable, 1,3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene, 3,3,4 , 4,5,5-hexafluorocyclopentene, more preferably 1,3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene. Special Preferred.

The freezing point of these fluorinated cyclic unsaturated hydrocarbons is much lower than the freezing point of fluorinated cyclic saturated hydrocarbons as described in Patent Document 3, and is suitable for use in cold regions.
For example, 1,1,2,2,3,3,4-heptafluorocyclopentane has a freezing point of 20.5 ° C., whereas 1,2,3,4,4,5,5-heptafluorocyclopentene. The freezing point of is −80 ° C. or lower.

The fluorinated cyclic unsaturated hydrocarbon used in the present invention is environmentally friendly because it does not contain chlorine atoms.
As for the global warming potential (GWP) of the fluorinated cyclic unsaturated hydrocarbon used in the present invention, there is no numerical value at present. However, considering that GWP of octafluorocyclopentene, which is an analogous compound, is 90 (100-year integrated value), it is presumed to be similarly small. Octafluorocyclopentene is a compound that is known as a semiconductor gas but is not used as a cleaning agent.

  The content of the fluorinated cyclic unsaturated hydrocarbon in the cleaning agent of the present invention is not particularly limited, but is usually 70% by weight or more, and the upper limit is about 99% by weight. The content of the fluorinated cyclic unsaturated hydrocarbon in the cleaning agent of the present invention is preferably 80 to 98% by weight, more preferably 90 to 97% by weight. In the present invention, the desired effect of the present invention is manifested because a composition containing a high content of a specific fluorinated cyclic unsaturated hydrocarbon, which has not been conventionally used, is used as a cleaning agent.

The compound represented by the formula (1) can be produced by a conventionally known method. The obtained compound is purified according to a known method and used in the cleaning agent of the present invention.
In general, the compound represented by the formula (1) is obtained by reducing the fluorine atom bonded to the olefin carbon of the perfluorocycloalkene with a reducing agent such as a metal hydride or the like, or 1,2-dihydroperfluorocyclohexane. It can be produced by contacting an alkane or 1,1,2-trihydroperfluorocycloalkane with a base such as a metal hydroxide.

  Specifically, 1,3,3,4,4,5,5-heptafluorocyclopentene can be obtained according to Journal of American Chemical Society, Vol. 86, 5361 (1964) can be produced by contacting octafluorocyclopentene with a reducing agent such as sodium borohydride.

  1,2,3,4,4,5,5-Heptafluorocyclopentene is obtained by hydroxylating 1,2,3,3,4,4,5,5-octafluorocyclopentane according to the method described in US Pat. No. 3,449,304. It can be produced by contacting with potassium under heating.

3,3,4,4,5,5-hexafluorocyclopentene is described in Tetrahedron, Vol. 22, 433 (1966) can be produced by reducing octafluorocyclopentene with lithium aluminum hydride.
This can also be produced by contacting 1,1,2,2,3,3,4-heptafluorocyclopentane with an alkali metal hydroxide such as potassium hydroxide.

  1,3,3,4,4,5,5,6,6-nonafluorocyclohexene, 1,2,3,4,4,5,5,6,6-nonafluorocyclohexene, 1,3,4, 4,5,5,6,6-hexafluorocyclohexene and 3,3,4,4,5,5,6,6-octafluorocyclohexene are as described in Journal of Chemical Society, 1963, 4828. In addition, a mixture obtained by bringing the corresponding decafluorocyclohexene into contact with lithium aluminum hydride can be obtained by fractional distillation.

  The cleaning agent of the present invention may contain any organic solvent in addition to the fluorinated cyclic unsaturated hydrocarbon.

  The boiling point of the organic solvent is preferably 30 ° C to 120 ° C, more preferably 40 ° C to 100 ° C. If the boiling point is within such a range, loss to the atmosphere due to volatilization is suppressed, the economic burden is reduced, and drying is easy during drying, and energy consumption in the drying process can be reduced.

  Examples of the organic solvent include hydrocarbons, alcohols, ketone compounds, ether compounds, ester compounds, fluorinated hydrocarbons other than the fluorinated cyclic unsaturated hydrocarbon, and mixtures thereof having a boiling point in the above range. be able to.

Examples of the hydrocarbon include linear saturated hydrocarbons such as hexane, octane and isooctane; cyclic saturated hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as toluene and xylene;
Examples of the alcohol include alcohols having 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, isobutanol, s-butanol, and n-pentanol (amyl alcohol).
Examples of the ketone compound include acetone and methyl ethyl ketone.
Examples of the ether compound include dimethyl ether and diethyl ether.
Examples of the ester compound include vinyl acetate.
Examples of the fluorinated hydrocarbon other than the fluorinated cyclic unsaturated hydrocarbon include chain hydrofluorocarbons such as 1,1,1,2,2,3,4,5,5,5-decafluoropentane; Perfluorocarbons such as hexane and perfluoroheptane; and the like.

  These organic solvents can be used alone or in combination of two or more. The content of the organic solvent in the cleaning agent of the present invention is usually 30% by weight or less, preferably 20% by weight or less.

  The cleaning agent of the present invention is preferably an azeotrope composition containing at least one of the fluorinated cyclic unsaturated hydrocarbon and the alcohol having 1 to 5 carbon atoms. The azeotropic mixture composition may contain an organic solvent other than an alcohol having 1 to 5 carbon atoms.

In the present invention, the azeotrope composition refers to an azeotrope and an azeotrope-like mixture. An azeotrope is a single point in that the vapor produced by partial evaporation or partial distillation of the liquid has the same composition as the liquid (ie, the mixture distills without causing a change in composition). A constant boiling liquid mixture containing two or more substances that exhibit the physical properties of the compound. An azeotrope exhibits the highest or lowest boiling point compared to the boiling point of a non-azeotropic mixture of the same substance.
On the other hand, an azeotrope-like mixture is one in which the vapor produced by partial evaporation or partial distillation of the liquid has substantially the same composition as the liquid (i.e., the mixture remains without causing a substantial change in composition). A liquid mixture containing two or more substances that exhibit the physical properties of a single compound. Here, “the vapor has substantially the same composition as that of the liquid” means that, when compared with the content ratio of the component in the liquid, the fluctuation ratio of the content ratio of the component in the vapor is ± 5. %. An azeotrope-like mixture has the same constituents as an azeotrope, but the content ratio of the components is somewhat different, and exhibits physical properties similar to those of an azeotrope.

  The azeotrope composition can be recycled because it does not substantially change the composition even after repeated evaporation and condensation. In particular, since the azeotrope has no composition change, the azeotrope is more preferable as the cleaning agent of the present invention.

  Moreover, it is preferable that the said azeotrope composition is a composition whose boiling point is 40-120 degreeC, Preferably it is 40-100 degreeC. If the boiling point is within such a range, loss to the atmosphere due to volatilization is suppressed, the economic burden is reduced, and drying is easy during drying, and energy consumption in the drying process can be reduced.

  The azeotrope composition of the fluorinated cyclic unsaturated hydrocarbon and the alcohol having 1 to 5 carbon atoms can be appropriately prepared with reference to, for example, the method described in “Example 6” described later.

  Examples of the azeotropic mixture composition include the compositions shown in the following (a) to (i).

(A) 1,3,3,4,4,5,5-heptafluorocyclopentene and methanol are in a weight ratio of 1,3,3,4,4,5,5-heptafluorocyclopentene: methanol = 90 : An azeotrope-like mixture contained in a composition of 10 to 98: 2, preferably 1,3,3,4,4,5,5-heptafluorocyclopentene: methanol = 93.8: 6.2 Azeotrope. The boiling point of this azeotrope is 41.3 ° C. (atmospheric pressure 1 hPa).

(B) 1,3,3,4,4,5,5-heptafluorocyclopentene and ethanol in a weight ratio of 1,3,3,4,4,5,5-heptafluorocyclopentene: ethanol = 92 : An azeotrope-like mixture contained in a composition of 8 to 99: 1, preferably 1,3,3,4,4,5,5-heptafluorocyclopentene: ethanol = 96.7: contained in a composition of 3.3 Azeotrope. The boiling point of this azeotrope is 44.8 ° C. (atmospheric pressure 1 hPa).

(C) 1,2,3,4,4,5,5-heptafluorocyclopentene and methanol in a weight ratio of 1,2,3,4,4,5,5-heptafluorocyclopentene: methanol = 88 An azeotrope-like mixture comprising a composition of 12: 96: 4, preferably an azeotrope comprising a composition of 1,2,3,4,4,5,5-heptafluorocyclopentene: methanol = 92: 8. The boiling point of this azeotrope is 45.8 ° C. (atmospheric pressure 1 hPa).

(D) 1,2,3,4,4,5,5-heptafluorocyclopentene and ethanol in a weight ratio of 1,2,3,4,4,5,5-heptafluorocyclopentene: ethanol = 90 : An azeotrope-like mixture included in a composition of 10 to 98: 2, preferably included in a composition of 1,2,3,4,4,5,5-heptafluorocyclopentene: ethanol = 95.1: 4.9 Azeotrope. The boiling point of this azeotrope is 49.8 ° C. (atmospheric pressure 1 hPa).

(E) 3,3,4,4,5,5-hexafluorocyclopentene and methanol in a weight ratio of 3,3,4,4,5,5-hexafluorocyclopentene: methanol = 70: 30 to 90 : An azeotrope-like mixture contained in a composition of 10, preferably 3,3,4,4,5,5-hexafluorocyclopentene: methanol = 80.3: 19.7. The boiling point of this azeotrope is 58.5 ° C. (atmospheric pressure 1 hPa).

(F) 3,3,4,4,5,5-hexafluorocyclopentene and ethanol in a weight ratio of 3,3,4,4,5,5-hexafluorocyclopentene: ethanol = 75: 25-95 : An azeotrope-like mixture contained in a composition of 5, preferably 3,3,4,4,5,5-hexafluorocyclopentene: ethanol = 84.7: 15.3. The boiling point of this azeotrope is 66.6 ° C. (atmospheric pressure 1 hPa).

(G) 3,3,4,4,5,5-hexafluorocyclopentene and isopropanol in terms of weight ratio of 3,3,4,4,5,5-hexafluorocyclopentene: isopropanol = 75: 25-95 : An azeotrope-like mixture contained in a composition of 5, preferably 3,3,4,4,5,5-hexafluorocyclopentene: isopropanol = 85: 15. The boiling point of this azeotrope is 69.8 ° C. (atmospheric pressure 1 hPa).

(H) 3,3,4,4,5,5-hexafluorocyclopentene and t-butanol are in a weight ratio of 3,3,4,4,5,5-hexafluorocyclopentene: t-butanol = 75 : An azeotrope-like mixture contained in a composition of 25 to 95: 5, preferably 3,3,4,4,5,5-hexafluorocyclopentene: t-butanol = 83.9: 16.1 Azeotrope. The boiling point of this azeotrope is 70.3 ° C. (atmospheric pressure 1 hPa).

(I) 3,3,4,4,5,5-hexafluorocyclopentene and n-propanol, by weight ratio, 3,3,4,4,5,5-hexafluorocyclopentene: n-propanol = 85 An azeotrope-like mixture contained in a composition of 15 to 98: 2, preferably 3,3,4,4,5,5-hexafluorocyclopentene: n-propanol = 92.8: 7.2 Azeotrope. The boiling point of this azeotrope is 72 ° C. (atmospheric pressure 1 hPa).

  Additives such as stabilizers and surfactants may be added to the cleaning agent of the present invention according to use conditions and purposes. These additives are preferably those that are entrained in the distillation operation or that form an azeotrope-like mixture.

Examples of such stabilizers include aliphatic nitro compounds such as nitromethane and nitroethane; aromatic nitro compounds such as nitrobenzene and nitrostyrene; dimethoxymethane, 1,2-dimethoxymethane, 1,4-diosan, 1,3,5 -Ether compounds such as trioxane; epoxide compounds such as glycidol, methyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, epichlorohydrin; unsaturated hydrocarbon compounds such as hexene, heptene, pentadiene, cyclopentene, cyclohexene; Olefinic alcohol compounds such as allyl alcohol and 1-buten-3-ol; acetylenic alcohol compounds such as 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol; It is done.
These stabilizers can be used alone or in combination of two or more.

  The amount of stabilizer used varies depending on the type of stabilizer used, but it does not impair detergency and nonflammability and does not hinder azeotrope-like properties. The content of the stabilizer in the cleaning agent of the present invention is usually 0.01 to 10% by weight, preferably 0.05 to 5% by weight.

  Furthermore, in order to obtain a synergistic stabilizing effect, a phenol compound, an amine compound, a benzotriazole compound or the like may be used together with a stabilizer.

The surfactant is added for the purpose of improving detergency, interfacial action and the like.
Surfactants include: sorbitan fatty acid ester compounds such as sorbitan monooleate and sorbitan trioleate; polyethylene glycol fatty acid esters such as polyoxyethylene monolaurate; polyoxyethylene alkylphenyl ether compounds such as polyoxyethylene nonylphenyl ether; Nonionic surfactants such as polyoxyethylene alkylamine fatty acid amide compounds such as siloxane ethylene amide;
These surfactants can be used singly or in combination of two or more.

  Further, for the purpose of synergistically improving the detergency and interfacial action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants.

  The amount of the surfactant used varies depending on the type of the surfactant used, but does not impair the detergency and nonflammability and does not hinder the azeotrope-like properties. As content of surfactant in the cleaning agent of this invention, it is 0.1 to 10 weight% normally, Preferably it is 0.3 to 5 weight%.

  The cleaning agent of the present invention is usually obtained by mixing and stirring the fluorinated cyclic unsaturated hydrocarbon, an organic solvent such as an alcohol having 1 to 5 carbon atoms, and optionally an additive by a conventionally known method. Can do.

  The cleaning agent of the present invention has a cleaning effect comparable to that of conventionally used chlorofluorocarbon-containing hydrocarbons. In addition, the cleaning agent of the present invention has no concern about the destruction of the ozone layer and has a short lifetime in the atmosphere, so that it has little involvement in global warming.

2) Article Cleaning Method The article cleaning method of the present invention includes a step of bringing the article into contact with the cleaning agent of the present invention.
In the present invention, the article to be cleaned is an object to be cleaned by the cleaning agent of the present invention, such as an article to which a pollutant is attached, or an article after the article to which the contaminant is attached is cleaned with a first cleaning agent described later. It is an article.

(1) Articles to be cleaned In the present invention, the articles to be cleaned are not particularly limited. For example, metals, ceramics, glass, etc. in the precision machine industry, metal processing industry, optical machine industry, electronics industry, plastic industry, etc. Examples include processed parts such as plastic and elastomer. Specifically, automotive parts such as bumpers, gears, mission parts, radiator parts, printed circuit boards, IC parts, lead frames, motor parts, electronic parts such as capacitors, bearings, gears, engineering plastic gears, watch parts, cameras Parts, precision machine parts such as optical lenses, printing machines, printing machine blades, printing rolls, rolled products, construction machines, large-scale machine parts such as glass substrates and large heavy machinery parts, daily products such as tableware, and textile products There are various examples.

(2) Pollutants The types of pollutants include, for example, cutting oils, quenching oils, rolling oils, lubricating oils, machine oils, pressing oils, stamping oils, drawing oils, assembly oils, drawing oils, Examples include greases, waxes, adhesives, oils and fats, mold release agents, molds, flacks after soldering, resists, solder pastes, dyes, and pigments.

(3) Cleaning method As a cleaning method, what is necessary is just to contact the articles | goods and the cleaning agent of this invention, and a normal cleaning method is employable. In the cleaning method of the present invention, as the cleaning agent, if available, a cleaning agent comprising 100% by weight of the fluorinated cyclic unsaturated hydrocarbon used in the present invention may be used. Specific examples of the cleaning method include hand wiping, dipping, spraying, showering, and the like. Of these, the dipping method is preferred. In these processes, physical means such as ultrasonic vibration, swinging, stirring, and brushing may be used in combination as desired.

More specifically, a cleaning method using the two-tank ultrasonic cleaning apparatus shown in FIG. 1 is illustrated.
1 is installed in an immersion cleaning tank 1, a steam zone 10 having a steam generation tank 2, a cooling pipe 3 and a water separator 4 connected to the steam zone, and the immersion cleaning tank 1. An ultrasonic generator 5, a filtration circulation pump 6 connected to the immersion cleaning tank 1, a filtration filter 7, a heater 8 installed in the steam generation tank 2, and the like.

  The cleaning agent of the present invention is charged into the immersion cleaning tank 1 and the steam generation layer 2. First, an article to be cleaned is placed in the immersion cleaning tank 1 for cleaning. At this time, as shown in FIG. 1, cleaning may be performed while an ultrasonic wave is generated by the ultrasonic wave generator 5. Moreover, you may heat with the heating apparatus which abbreviate | omitted illustration as needed. The temperature of the cleaning agent may be appropriately selected according to the properties of the article, but is usually in the range from room temperature to the boiling point, preferably in the range from 40 ° C. to the boiling point, more preferably in the range from 50 ° C. to the boiling point. . What is necessary is just to select washing | cleaning time suitably according to the kind of goods, the condition of dirt, etc.

  Next, the cleaned article is pulled up to the steam zone 10 to perform steam cleaning. In the steam zone 10, the cleaning agent in the steam generation tank 2 is heated by the heater 8 and is filled with the steam. After being steam cleaned in the steam zone 10, the article is pulled up and drained and dried.

On the other hand, the steam of the cleaning agent in the steam zone 10 is cooled by the cooling pipe 3 and carried to the moisture separator 4. Here, only the cleaning agent of the present invention is recycled to the immersion cleaning tank 1 due to the specific gravity difference.
Further, the cleaning agent in the immersion cleaning tank 1 is purified by removing impurities and the like by passing through the filtration filter 7 by the filtration circulation pump 6.

  In the cleaning method of the present invention, a step of cleaning with an organic solvent (first cleaning agent) different from the cleaning agent of the present invention may be provided before using the cleaning agent of the present invention.

  As such a cleaning method, for example, the first step of removing the contaminants of the article with the first cleaning agent and the first cleaning agent attached to the article after removing the contaminants are brought into contact with the cleaning agent of the present invention. Cleaning method (so-called co-solvent system) having a second step consisting of a step of rinsing and / or a step of steam cleaning in the steam of the cleaning agent of the present invention.

  The first step is a step of removing contaminants on the article with the first cleaning agent. Examples of the first cleaning agent include hydrocarbons, alcohols, ethers, volatile organic silicones, other ketones, esters, chlorinated hydrocarbons, and the like.

As hydrocarbons, linear saturated aliphatic such as pentane, hexane, peptane, octane, isooctane, nonane, decane, isodecane, undecane, dodecane, isododecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, isooctadecane, etc. Hydrocarbons: Cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclodecane, methylcyclodecane, cyclododecane, decalin, norbornane and other cyclic saturated hydrocarbons; heptene, heptadiene, octene, octadiene, nonene, nonadiene, decene , Decadiene, undecene, dodecene, dodecadiene, tridecene, tridecadiene, tetradecene, tetradecadiene, octadecene, octadecadiene, isoprene Chain-unsaturated hydrocarbons such as dimers of the above; cyclic unsaturated hydrocarbons such as terpenes such as α-pinene, β-pinene, γ-terbine, δ-3-carene, limonene, dipentene, terbylene Aromatic hydrocarbons such as toluene;
These hydrocarbons can be used singly or in combination of two or more.

  Moreover, the hydrocarbon-type cleaning agent marketed as hydrocarbons can also be used. For example, Normal Paraffin Series, Isosol Series, Isolan Series (above made by Nippon Petrochemical Co., Ltd.), No. 0-5 Solvent, Teclean Series (above made by Nippon Petrochemical Co., Ltd.), NS Clean Series (made by Nikko Petrochemical Co., Ltd.) Can be used.

  When these hydrocarbons are used as cleaning agents, they can be used alone, or various additives based on hydrocarbons such as cutting oil, lubricating oil, machine oil, and press working oil. May be added.

  Alcohols include methanol, ethanol, propanol, isopropanol, butanol, hexanol, 1-hexenol, 2-ethylhexanol, cyclopentanol, cyclohexanol, decyl alcohol, ethylene glycol, 1,2-propanediol, 1,2- Examples include cyclopentanediol, ethylene glycol monomethyl ether, and ethylene glycol monobutyl ether.

Examples of ethers include diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, 1,3-dioxane, trioxane, cyclopentyl methyl ether, cyclohexyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and diethylene glycol dimethyl ether.
Further, as volatile organic silicones, the following formulas (1) and (2)

(Wherein R represents the same or different substituted or unsubstituted monovalent organic group, l represents an integer of 0 to 3, and m represents an integer of 3 to 5). And at least one low molecular weight polyorganosiloxane selected from organosiloxanes.

  R is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; an aryl group such as a phenyl group; a substituted alkyl group such as a trifluoromethyl group or a pentafluoroethyl group; a methoxy group, an ethoxy group, or the like Lower carbonyl groups; carbonyl-containing groups such as methoxycarbonyl group, ethoxycarbonyl group and acetyl group; amide groups; Among these, a methyl group, an ethyl group, a methoxy group, and an ethoxy group are preferable from the viewpoint of stability of the compound, and a methyl group is particularly preferable.

  l is preferably 1 or more in order to form a silicone skeleton. Further, m is preferably 3 or more in order to obtain ring stability. In addition, since l can be distilled within a practical range in order to recover and reuse as a cleaning agent, it is preferable that l is 3 or less and m is 5 or less.

Examples of such volatile organic silicones include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like. Of these, octamethylcyclotetrasiloxane is particularly preferred because of its suitable physical properties such as boiling point and surface tension.
These first cleaning agents may be added with the above-described surfactant, water, or the like as desired.

  In addition, when repeatedly used, a distilled and recovered product can be used. In this case, there is no problem even if a rinse liquid described later is partially mixed.

As a cleaning method, the article to be cleaned and the first cleaning agent may be brought into contact with each other, and a normal cleaning method can be employed. For example, methods such as hand wiping, dipping, spraying, showering and the like can be mentioned. Among them, the dipping method is preferable.
In the treatment by immersion, physical means such as ultrasonic vibration, rocking, stirring, brushing, etc. may be used in combination.

  The temperature of the cleaning agent may be appropriately selected according to the properties of the article, but is usually in the range from room temperature to the boiling point, preferably in the range from 40 ° C. to the boiling point, more preferably in the range from 50 ° C. to the boiling point. .

  The second step is a step of rinsing and / or steam cleaning the article to which the first cleaning agent is adhered using the cleaning agent of the present invention.

  As the rinse cleaning method, the article having the first cleaning agent attached thereto may be brought into contact with the cleaning agent of the present invention, and a normal rinse cleaning method can be employed. For example, methods such as hand wiping, dipping, spraying, showering and the like can be mentioned. Among them, the dipping method is preferable. In the treatment by immersion, physical means such as ultrasonic vibration, rocking, stirring, brushing, etc. may be used in combination.

  The temperature of the rinse cleaner may be appropriately selected according to the properties of the article, but is usually in the range from room temperature to the boiling point, preferably in the range from 40 ° C. to the boiling point, more preferably in the range from 50 ° C. to the boiling point. is there.

  Since the first cleaning agent removed from the article is mixed after the repeated use of the rinse cleaner (the cleaning agent of the present invention), it is preferable to separate and reuse the rinse cleaner. Examples of the method for separating the first cleaning agent from the rinse cleaning agent include a two-layer separation method and a distillation separation method.

In the two-layer separation method, when hydrocarbons are used as the first cleaning agent in the first step, there is a difference in specific gravity from the cleaning agent of the present invention used in rinsing cleaning. It separates into hydrogen and the underlying cleaning agent of the present invention. The hydrocarbon can be removed by newly adding the cleaning agent of the present invention into the container used for the two-layer separation to overflow the upper hydrocarbon layer.
In addition, a part of the cleaning agent after the rinse cleaning is transferred to another container, where it is separated into two layers, a hydrocarbon layer and a cleaning agent layer of the present invention, and separated by a method of recovering the lower cleaning agent layer of the present invention. May be. In the two-layer separation, a centrifugal separation method may be used.

The two-layer separation operation is preferably performed at a low temperature because the solubility is lowered. On the other hand, the lower limit temperature is preferably the melting point of the fluorinated cyclic unsaturated hydrocarbon or hydrocarbon used.
There is no particular limitation on the method of cooling the rinse cleaner, and any method of leaving at room temperature, cooling with a refrigerant, evaporating part of the fluorinated cyclic unsaturated hydrocarbon, and cooling with heat of evaporation, etc. Can also be used. Although the cooling rate is not limited, an active cooling method such as cooling from the outside or evaporation by reducing pressure is recommended in order to prevent efficiency loss and loss of cleaning liquid due to natural evaporation.

The cleaning agent layer of the present invention recovered by the two-layer separation is used as it is or after subjecting it to a treatment such as distillation, filtration, activated carbon treatment, drying, etc., as a rinse cleaner, or as a solvent for vapor cleaning described later. Can be used.
When the first cleaning agent is other than hydrocarbons, it is usually difficult to separate the two layers from the cleaning agent of the present invention, so that separation by distillation is preferable.

  Instead of the rinsing cleaning, steam cleaning can be employed in combination with the rinsing cleaning. When performing steam cleaning instead of rinsing cleaning, the cleaning agent of the present invention is used as the cleaning agent. When steam cleaning is used in combination with rinse cleaning, the cleaning agent for steam cleaning is not particularly limited, and a solvent for steam cleaning used in general steam cleaning can be used without any particular limitation. It is also possible to circulate as a rinse cleaner after steam cleaning. Steam cleaning can be performed according to a conventional method.

FIG. 2 shows an example of a cleaning apparatus for performing the above method.
The article to which contaminants such as oil, wax, and flux are attached is immersed in the cleaning agent (first cleaning agent) in the first cleaning tank 11, where the contaminants attached to the surface of the article are removed. The first cleaning agent can be heated by the heating device 19 or ultrasonically cleaned by the ultrasonic generator 20 as necessary to improve the cleaning power.

Next, when a sufficient cleaning effect cannot be obtained in the first cleaning tank 11, the second cleaning tank 12 can perform cleaning with the second cleaning agent. The second cleaning agent may be the same as or different from the first cleaning agent. In the second cleaning tank 12, as in the first cleaning tank 11, the cleaning can be performed while heating or generating ultrasonic waves as necessary.
In addition, in FIG. 2, although two washing tanks were shown, there is no special limitation and it can be used combining 1 tank or 2 tanks or more as needed.

  After the cleaning is completed, the article to which the first and / or second cleaning agent (hereinafter referred to as “first cleaning agent”) is attached is immersed in the cleaning agent of the present invention in the rinse cleaning tank 13. The Here, in order to improve the rinsing cleaning power, ultrasonic cleaning can be used together with the ultrasonic generator 20 or shower cleaning or rocking cleaning can be used together as necessary.

  In the rinse cleaning tank 13, the first cleaning agent and the like adhering to the article surface is washed away from the article surface. The washed first cleaning agent and the like are transferred to the separation tank 14 and the distillation column 25 by the rinse liquid transfer pump 24, the overflow, or the flow of another rinse cleaning agent to be added.

  In the separation tank 14, it is separated into the first cleaning agent layer 16 in the upper tank and the lower cleaning agent layer 17 of the present invention due to the difference in specific gravity. By lowering the temperature of the separation tank 14, the purity of the recovered cleaning agent of the present invention can be increased, and the contamination of the cleaning agent of the present invention into the first cleaning agent layer can be greatly reduced. Therefore, the operation of the two-layer separation is performed at a temperature of usually 10 ° C. or lower, preferably 20 ° C. or lower, more preferably 30 ° C. or lower, of the temperature of the rinse washing tank 13.

  The lower cleaning agent layer 17 of the present invention separated into two layers is circulated by the circulation pump 21 to the rinse cleaning tank 13 and the steam cleaning tank 15 from the circulation pump 22.

Steam cleaning is performed when a high degree of cleaning is required or when it is desired to reduce the consumption of the cleaning agent of the present invention.
In the steam cleaning tank 15, the cleaning agent of the present invention is heated by the heating device 19 to form a steam zone 18. Then, the article pulled up from the rinse cleaning tank 13 is steam cleaned in the steam zone 18.

The cleaning agent of the present invention used for the steam cleaning is transferred to the rinse cleaning tank 13 due to aggregation or overflow, and is used for reuse.
Details of the individual cleaning method, the rinse cleaning method, the two-layer separation method, the steam cleaning method, and the like performed in the apparatus of FIG. 2 are not particularly limited to the above-described embodiments. In the present invention, other general methods can be used. In addition, the number of washing and rinsing can be increased or decreased as necessary.

  The cleaning agent of the present invention can be used as a gap cleaning agent and a draining cleaning agent in addition to the rinse cleaning agent and the steam cleaning agent as described above. Other applications include, for example, hollow fiber cleaning agents: dry cleaning solvents; silicon wafer substrates, metal substrates, glass substrates and other surface cleaning solvents; semiconductor IC chip manufacturing cleaning agents; printed circuit board surface treatments Solvent; Chemical mechanical polishing polishing solvent; Photoresist solvent; Developer solvent; Rinse solution composition;

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited by these Examples. Unless otherwise specified, “part” and “%” represent “part by weight” and “% by weight”, respectively.

In the following, analysis by gas chromatography was performed under the following conditions.
Device name: G-5000 manufactured by Hitachi, Ltd.
Column: Neutrabond-1 (manufactured by GL Sciences)
(60m × ID 0.25μm, 1.5μmdf)
Column temperature: 40 ° C → [20 ° C / min] → 240 ° C
Injection temperature: 200 ° C
Carrier gas: Nitrogen (flow rate 1mL / min)
Detector: FID (hydrogen flame ionization detector)

[Example 1] Production of 3,3,4,4,5,5-hexafluorocyclopentene 1,1,2,2,3,3,4-heptafluoro was added to a glass reactor equipped with a condenser and a stirrer. 790 parts of cyclopentane and 2000 parts of a 2M aqueous potassium hydroxide solution were charged, and the mixture was vigorously stirred at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature and allowed to stand. As a result of analyzing the lower layer by gas chromatography, the raw material 1,1,2,2,3,3,4-heptafluorocyclopentane disappeared. Therefore, the lower layer was separated, washed with water, dried over anhydrous magnesium sulfate, and the desiccant was removed by filtration to obtain 645 parts of product.

  When the product was analyzed by gas chromatography, the target product, 3,3,4,4,5,5-hexafluorocyclopentene was 96.1% in terms of GC area ratio. This mixture was purified by distillation using a Sulzer type distillation column (manufactured by Toshin Seiki Co., Ltd., theoretical plate number: 50 plates) to obtain 489 parts of 3,3,4,4,5,5-hexafluorocyclopentene as the target product. (Boiling point 77 ° C.). This was designated as Cleaning Agent 1 (3,3,4,4,5,5-hexafluorocyclopentene content: 98%).

[Example 2] Production of 1,3,3,4,4,5,5-heptafluorocyclopentene 1,3,3,4,4,5,5-heptafluorocyclopentene has been described in the literature (Journal of American Chemical Society, 1964, Vol. 86, 5361).
That is, 700 parts of anhydrous triethylene glycol dimethyl ether (manufactured by Aldrich) and 300 parts of octafluorocyclopentene (manufactured by Nippon Zeon) were charged into a glass four-necked reactor equipped with a stirrer and a dropping funnel, and acetone / dry ice was added. It was immersed in a bath and cooled to -30 ° C. Here, 62 parts of a triethylene glycol dimethyl ether solution (concentration 2 mol / L) of sodium borohydride was dropped from a dropping funnel. After completion of the dropwise addition, the whole volume was stirred for 2 hours at a temperature of -30 to -20 ° C, and further stirred for 6 hours while raising the temperature to room temperature.

  After completion of the reaction, 1500 parts of water was added little by little to the reaction solution, and the two layers were separated. The lower layer was taken out, washed with saturated aqueous sodium hydrogen carbonate, and dried over anhydrous magnesium sulfate. Magnesium sulfate was removed by filtration, and the obtained filtrate was purified using a KS distillation column (manufactured by Toshin Seiki Co., Ltd., 30 plates). The desired product 1,3,3,4,4,4 178 parts of 5,5-heptafluorocyclopentene were obtained (boiling point 46 ° C.). This was designated as Cleaning Agent 2 (1,3,3,4,4,5,5-heptafluorocyclopentene content: 97%).

[Example 3] Production of 1,2,3,4,4,5,5-heptafluorocyclopentene 1,2,3,4,4, obtained by hydrogenating octafluorocyclopentene (manufactured by Nippon Zeon Co., Ltd.) 890 parts of 4,5,5-octafluorocyclopentane, 15 parts of n-tetrabutylammonium bromide, and 2000 parts of a 2.5M aqueous potassium carbonate solution were charged into a glass reactor equipped with a condenser and a stirrer and brought to 45 ° C. For 7 hours. The reaction mixture was cooled to room temperature and allowed to stand. As a result of analyzing the lower layer by gas chromatography (GC), 1,2,3,3,4,4,5,5-octafluorocyclopentane as a raw material disappeared. Therefore, the lower layer was separated, washed with water, dried over anhydrous magnesium sulfate, and the desiccant was removed by filtration. As a result, 790 parts of product was obtained.

  As a result of analysis by gas chromatography, the products were 1,3,3,4,4,5,5-heptafluorocyclopentene and 1,2,3,4,4,5,5-heptafluorocyclopentene. It was a mixture having a GC area ratio of 9: 1. This mixture was purified by distillation using a Sulzer type distillation tower (manufactured by Toshin Seiki Co., Ltd., theoretical plate number: 50 plates). Obtained (boiling point 51 ° C.). This was designated as Cleaning Agent 3 (1,2,3,4,4,5,5-heptafluorocyclopentene content: 97%).

(Measurement of freezing point)
About the fluorinated cyclic unsaturated hydrocarbon (cleaning agents 1-3) obtained in Examples 1-3, the freezing point was measured by the method shown next.
First, 10 g of each fluorinated cyclic unsaturated hydrocarbon was weighed in a test tube equipped with a thermometer and immersed in a methylene chloride bath. Dry ice or liquid nitrogen was added to the methylene chloride bath to gradually lower the temperature of the methylene chloride bath. The state of the fluorinated cyclic hydrocarbon in the test tube was visually observed, and the temperature at which it almost solidified and lost its fluidity was defined as the freezing point. The measurement results are shown together in Table 1 below together with the freezing point of commercially available 1,1,2,2,3,3,4-heptafluorocyclopentane (manufactured by Zeon Corporation).

  It can be seen that the fluorinated cyclic unsaturated hydrocarbon obtained in the Examples has a very low freezing point as compared with the fluorinated cyclic saturated hydrocarbon.

(Flash point measurement test)
When the flash point of the fluorinated cyclic unsaturated hydrocarbon obtained in Examples 1 to 3 was measured in accordance with JIS K2265 using a tag sealing type and Cleveland open type automatic flash point measurement tester, 1 3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene, and 3,3,4,4,5,5-hexafluoro In all of the cyclopentene, the flame was extinguished near the boiling point and no flash point was observed.

(Flammability test)
A test gas containing fluorinated cyclounsaturated hydrocarbons obtained in Examples 1 to 3, air and water vapor was prepared. , Vol. 41, p406-417 (2006), a flammability test was conducted to examine the flammability of the test gas. The results are summarized in Table 2 below. In Table 2, wet means a 50% humidity condition.

[Example 4]
1,2,3,4,4,5,5-heptafluorocyclopentene obtained in Example 3 and ethanol in a weight ratio of 1,2,3,4,4,5,5-heptafluorocyclopentene : Ethanol = 95.8: 4.9 so that cleaning agent 4 was obtained.

  About cleaning agents 1-4 obtained in Examples 1 to 4 and cleaning agents 5 to 8 of Comparative Examples 1 to 4 shown below, various cleaning properties tests (working fluid solubility test, punching oil degreasing cleaning test) , Degreasing cleanability test of silicone oil, cleanability test of epoxy resin adhesive, cleanability test of silicone grease).

[Comparative Example 1]
1,1,2,2,3,3,4-heptafluorocyclopentane (ZEROLA H, manufactured by Nippon Zeon Co., Ltd.) and detergent 5 (1,1,2,2,3,3,4-heptafluorocyclopentane) Content: 98%).
[Comparative Example 2]
Detergent is an azeotropic mixture of 1,1,2,2,3,3,4-heptafluorocyclopentane and t-amyl alcohol in a weight ratio of 95.8: 4.2 (ZEROLA HTA, manufactured by Nippon Zeon Co., Ltd.) It was set to 6.
[Comparative Example 3]
1,1,1,2,2,3,4,5,5,5-decafluoropentane as a cleaning agent 7 (1,1,1,2,2,3,4,5,5,5-decafluoro Pentane content: 99%).
[Comparative Example 4]
1,1,1,2,2,3,4,5,5,5-decafluoropentane and ethanol were mixed at a weight ratio of 96.0: 4.0 to obtain cleaning agent 8.
The detergency test method is as follows. The evaluation results of various detergency tests are summarized in Table 3 below.

(Working fluid solubility test)
The solubility of the machine oil in the cleaning agent was evaluated. It can be judged that the higher the solubility is, the better the degreasing performance of the machine oil is.
As the working oil, two types of punching oil (Demitsu Kosan Co., Ltd., Daphne Punch Oil) and silicone oil (Shin-Etsu Chemical Co., Ltd., KF-96 10 cSt) were used.

Put 3 mL of cleaning agent and 3 mL of working oil in a test tube, cap it with rubber, and stir it by hand at room temperature (23 ° C) for a predetermined time to make it transparent and uniform, cloudy, or separated into two layers Were visually observed to evaluate whether or not they were arbitrarily compatible.
In the case where it was not arbitrarily compatible at room temperature, the test tube was placed in a water bath and stirred occasionally while gradually warming, and the temperature at which it was arbitrarily compatible was examined. The heating upper limit temperature was set to the boiling point of the cleaning agent, and evaluation was performed according to the following evaluation criteria.

<Evaluation criteria>
◎: When compatibilized arbitrarily at room temperature ○: When compatibilized arbitrarily by heating Δ: When compatibilized arbitrarily by heating to near the boiling point ×: When almost compatible even when heated to the boiling point

(Evaluation of degreasing performance of punching oil)
Using a 2-tank ultrasonic cleaning apparatus equipped with an immersion cleaning tank 1 and a steam generation tank 2 shown in FIG.

  50 stamped parts (50 mm square made of stainless steel) are aligned, and the ones bundled with a wire are immersed in a beaker containing punching oil (Dafney Punch Oil, manufactured by Idemitsu Kosan Co., Ltd.) at room temperature. Ultrasonic was applied for 1 minute. The sample was allowed to stand at room temperature for a whole day and night, then pulled up on the punched oil and left for 5 minutes to drain the oil.

  The cleaning agent was charged into the two-tank ultrasonic cleaning apparatus shown in FIG. 1, and the cleaning evaluation sample was immersed in the immersion cleaning tank 1, and ultrasonic cleaning was performed for 5 minutes while heating at 40 ° C. Next, after steam cleaning was performed for 1 minute in the steam zone 10 filled with the cleaning agent steam, the liquid was dried slowly by pulling up slowly from the steam zone.

  After cooling the sample for evaluation after washing, remove the bundled wires and release them one by one, and then remove the punching oil with ink-boiled water (commercially available ink-boiled 10-fold diluted with pure water) According to the repellency test according to the following evaluation criteria.

<Evaluation criteria>
◎: When repelling is good ○: When repelling is almost satisfactory ×: When repelling is poor

(Degreasing test of silicone oil)
Evaluation was performed in the same manner as the evaluation of the degreasing detergency test of the punched oil except that the punched oil was replaced with silicone oil (KF-96 10 cSt, manufactured by Shin-Etsu Chemical Co., Ltd.).

(Detergency test of epoxy resin adhesive)
Apply an appropriate amount of epoxy resin adhesive (manufactured by Hiroki Co., Ltd., JU-100-5 for high-speed dispenser) to about half of one side of a slide glass (size: 76 mm x 26 mm x 1 mm), and the epoxy resin adhesive after standing overnight at room temperature. An uncured sample was used as a cleaning evaluation sample.

150 mL of cleaning agent is put in a 200 mL beaker, one sample for cleaning evaluation is immersed in the solution, and a room temperature (with a tabletop ultrasonic cleaner (UT-105H output: 100 W frequency: 40 KHz) manufactured by Sharp Corporation) is used. (23 ° C.) for 10 seconds.
The epoxy resin adhesive residue on the surface of the slide glass after washing was visually observed and evaluated according to the following evaluation criteria.

<Evaluation criteria>
◎: When there is no residue ○: When there is almost no residue ×: When there is residue

(Evaluation of detergency of silicone grease)
Applying 0.2 g of silicone grease (Shin-Etsu Chemical Co., Ltd., G40 series, for high-temperature lubrication) evenly to the entire surface of one side of a copper plate (size: 50 mm x 40 mm x 0.8 mm), and washing and evaluating what was left overnight at room temperature A sample was used.

150 mL of cleaning agent is put in a 200 mL beaker, one sample for cleaning evaluation is immersed in the liquid, and using a tabletop ultrasonic cleaner (manufactured by Sharp Corporation, UT-105H, output: 100 W, frequency: 40 KHz), Ultrasonic cleaning was performed for 1 minute while heating to 40 ° C.
The silicone grease residue on the copper plate surface after washing was visually observed and evaluated according to the following evaluation criteria.

<Evaluation criteria>
◎: When there is no residue ○: When there is almost no residue ×: When there is residue

  From Table 3, it can be seen that the cleaning agents 1 to 4 of Examples 1 to 4 exhibit excellent solubility and cleaning properties equivalent to or higher than the cleaning agents 5 to 8 of Comparative Examples 1 to 4.

[Example 5]
3,3,4,4,5,5-hexafluorocyclopentene obtained in Example 1 and ethanol in a weight ratio of 3,3,4,4,5,5-hexafluorocyclopentene: ethanol = 84 7: 15.3 was mixed to obtain the cleaning agent 9. Using the obtained cleaning agent 9, a draining and drying test was performed as follows.

A stainless steel wire mesh (30 mm × 15 mm, 40 mesh) is completely immersed in pure water, pulled up, immersed in a beaker containing 200 mL of cleaning agent 9 and left at room temperature for 1 minute, and then a stainless steel wire mesh. Raised. Next, this was immersed in a 100 mL bottle containing 25 mL of methanol, and the residual water adhering to the wire mesh was extracted with methanol. Next, when the amount of water increase from the methanol solution before extracting the water in this methanol solution was measured, it was 302 ppm. Moreover, it was 8734 ppm when only immersed in the pure water and not immersed in the cleaning agent 9.
From this result, the water removal rate by the cleaning agent 9 was 96.5%.

[Example 6]
A cleaning agent was prepared using the fluorinated cyclic unsaturated hydrocarbon and alcohol shown in Table 4 below. For each cleaning agent, the azeotropic composition (weight ratio), the azeotropic temperature, and the freezing point were measured by the following method. The results are shown in Table 4 below.

  For the measurement, a rectifying apparatus having a magnetic stirrer, an oil bath, a glass distillation kettle, a distillation tower with a reflux device having a theoretical plate number of 7 (manufactured by Toshin Seiki Co., Ltd., model KS), a cooler, and a fraction receiver. Used. In addition, a thermocouple temperature recorder was used to measure and record the oil bath temperature, the temperature in the distillation pot, and the temperature at the top of the distillation column. The specific procedure is shown below.

  A 200 mL distillation kettle was charged with 50 g of fluorinated cyclic unsaturated hydrocarbon and 50 g of alcohol and stirred. A distillation kettle was attached to the rectifier, the mixed solution was stirred, the oil bath was heated to 100 to 120 ° C., the tower top temperature rose, and the mixture was refluxed for 1 hour after reaching a certain temperature. Thereafter, the fraction was withdrawn into the receiver in 5 mL portions (fractions 1 to 5) at a reflux ratio of 2/40 sec. The composition ratio of each fraction was determined by gas chromatography analysis. In Table 4, the azeotropic temperature indicates the tower top temperature when the fraction 3 is extracted, and the azeotropic composition ratio indicates the composition ratio of the fraction 3.

  In Table 4, MeOH represents methanol, EtOH represents ethanol, i-PrOH represents isopropanol, t-BuOH represents t-butanol, and n-PrOH represents n-propanol. Moreover, -80> shows that it is less than -80 degreeC.

  Table 4 shows that the freezing point of the azeotrope of the present invention is very low.

Industrial applicability

ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning agent which is excellent in detergency, a nonflammability, and stability, and also has a very small load to a global environment, a low freezing point, and excellent handleability.
Since the cleaning method of the present invention uses the cleaning agent of the present invention, the cleaning method is excellent in detergency, the load on the global environment is extremely small, and can be advantageously used industrially.

Claims (6)

Formula (1)

(Wherein X, Y and Z each independently represent a fluorine atom or a hydrogen atom, provided that at least one of X, Y and Z is a hydrogen atom; n is 2 or 3). A detergent containing the fluorinated cyclic unsaturated hydrocarbon represented.   The cleaning agent according to claim 1, wherein the content of the fluorinated cyclic unsaturated hydrocarbon is 70% by weight or more.   The cleaning agent according to claim 1 or 2, further comprising at least one kind of alcohol having 1 to 5 carbon atoms and being an azeotropic mixture composition.   The cleaning agent according to claim 3, which has a boiling point of 40 to 120 ° C.   The fluorinated cyclic unsaturated hydrocarbon is 1,3,3,4,4,5,5-heptafluorocyclopentene, 1,2,3,4,4,5,5-heptafluorocyclopentene, or 3,3 , 4, 4, 5, 5-hexafluorocyclopentene, The cleaning agent according to claim 1.   A method for cleaning an article, comprising the step of bringing the article into contact with the cleaning agent according to any one of claims 1 to 5.

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