WO2016067933A1 - Fluorine-containing olefin composition and cleaning method using same - Google Patents

Abstract

[Problem] The present invention addresses the problem of providing a cleaning composition and a cleaning method, each of which removes fat or oil from a polycarbonate or soft polyvinyl chloride article to be cleaned, to which the fat or oil adheres, without deteriorating the transparency of the article to be cleaned. [Solution] The above-described problem is solved by using a composition having a HCFO-1233zd(Z)/HFC-365mfc mass ratio of from 4/96 to 60/40 for cleaning of a polycarbonate and by using a composition having a HCFO-1233zd(Z)/HFC-365mfc mass ratio of from 4/96 to 20/80 for cleaning of a soft polyvinyl chloride. These compositions have sufficiently high power of dissolving and removing a foreign material such as fat or oil and do not substantially deteriorate the transparency of the article to be cleaned.

Description

Fluorine-containing olefin composition and cleaning method using the same

The present invention relates to 1-chloro-3,3,3-trifluoropropene known as hydrochlorofluoroolefin (HCFO) and 1,1,1,3,3-pentafluorobutane known as hydrofluorocarbon (HFC). It relates to the composition containing this. In particular, the present invention relates to a method for cleaning an object including a resin using the composition.

In order to prevent global warming and ozone layer destruction, various CFC substitutes have been proposed. In order to protect the ozone layer, hydrofluorocarbons (HFCs) not containing chlorine, which is an ozone depleting element, have become popular. 1,1,1,3,3-Pentafluorobutane (hereinafter referred to as HFC-365mfc) also corresponds to this, and is an easily handled substance having a boiling point of 40 ° C. and nonflammability. However, on the other hand, HFC generally has a long atmospheric life and a great influence on the global environment such as global warming. Therefore, it is preferable to devise such as blending with other solvents to reduce the amount used as much as possible.

In recent years, fluorine-based fluorocarbon substitutes containing double bonds in the molecule have been proposed. Hydrofluoroolefin (HFO), hydrochlorofluoroolefin (HCFO), and chlorofluoroolefin (CFO) are applicable. Since these have a C═C double bond in the molecule, it is known that the atmospheric lifetime is short and the influence on the global environment is small. Cis-1-chloro-3,3,3-trifluoropropene (hereinafter sometimes referred to as HCFO-1233zd (Z)) corresponds to this and is a highly available compound. Among them, HCFO-1233zd (Z) is a particularly promising compound as a solvent and a cleaning agent because it has a boiling point of 39 ° C. and is particularly easy to handle near room temperature. HCFO-1233zd (Z) has a significantly higher boiling point than HCFO-1233zd (E) (boiling point 19 ° C.), which is a geometric isomer.

An azeotrope-like composition of HFC-365mfc and HCFO-1233zd (Z) is described in Patent Document 1, and by using this composition as a cleaning agent, oil and fat adhering to a stainless steel wire mesh can be removed. And a change in weight when an acrylic resin is immersed in the composition. However, it does not describe the influence on the polycarbonate resin or the soft vinyl chloride resin, and the state of maintaining transparency under severe conditions.

Further, although a mixed composition of HFC-365mfc and HCFO-1233zd (Z) is described in Patent Document 2 as a solvent for silicone application, there is no description regarding the transparency of the resin as in Patent Document 1.

JP 2010-248443 A JP 2011-046688 A

As disclosed in Patent Documents 1 and 2, the mixed composition of HFC-365mfc and HCFO-1233zd (Z) is rich in the ability to dissolve oils and fats, while the resin (polymer) is not easily eroded. It is useful as a cleaning agent for removing foreign substances such as fats and oils from resin (polymer) equipment.

However, the cleaning method described in the example of Patent Document 1 was under a relatively mild condition in which the contact time between the mixed composition and the equipment was 5 to 30 seconds, and the cleaning temperature was room temperature. Depending on how dirty the equipment is, cleaning under even more severe conditions may be necessary.

On the other hand, examples of equipment to be cleaned (objects to be cleaned) include equipment made of polycarbonate resin and soft vinyl chloride resin. “Transparency” is one of the characteristics of these resins, but these resins often lose their transparency when they come into contact with chemicals, and are transparent when the oil adhering to these transparent resins is washed with chemicals. In many cases, the property is impaired (hereinafter, the polycarbonate resin is omitted and simply referred to as “polycarbonate”, and the soft vinyl chloride resin is omitted as simply “soft polyvinyl chloride” or “soft vinyl chloride”). This is no exception in the mixed composition of HFC-365mfc and HCFO-1233zd (Z), and although it is less likely to cause problems in the case of cleaning under mild conditions, it is relatively harsh (for example, mixed composition and equipment) In the cleaning under the condition that the contact time is 30 minutes or more (which is a relatively long time), the transparency of the equipment may be affected (see the comparative example described later).

In this way, even under harsh cleaning conditions, oils and fats (sometimes referred to as oil or oil in this specification) can be removed from equipment made of polycarbonate or soft vinyl chloride resin, and the transparency of the resin can be improved. There remains a need for cleaning compositions and cleaning methods that are less detrimental.

The inventors have intensively studied to solve the above problems. It has been found that the above problem can be solved by a mixed solvent in which HFC-365mfc and HCFO-1233zd (Z) are mixed at a specific composition ratio.

That is, the present inventors have a sufficiently high ability to dissolve and remove foreign matters such as fats and oils, with a composition having a mass ratio of HCFO-1233zd (Z) / HFC-365mfc of 4/96 to 60/40, In addition, the present inventors have found a characteristic fact that the transparency of polycarbonate equipment is rarely impaired even under relatively severe cleaning conditions in which the equipment contact time is 30 minutes or more.

Furthermore, the inventors of the present invention have a sufficiently high ability to dissolve and remove foreign matters such as fats and oils, with a composition having a mass ratio of HCFO-1233zd (Z) / HFC-365mfc of 4/96 to 20/80, and They found the characteristic fact that the transparency of soft vinyl chloride equipment is rarely impaired even under relatively harsh cleaning conditions where the equipment contact time is 30 minutes or longer.

The HCFO-1233zd (Z) / HFC-365mfc mixed composition of these limited compositions exhibits particularly excellent physical properties as a cleaning solvent for removing oils and fats from polycarbonate equipment and soft vinyl chloride equipment. This has never been known before.

Since the mixed composition of the present invention uses HCFO-1233zd (Z) that minimizes HFC-365mfc, which is an HFC, and instead decomposes rapidly in the atmosphere, the influence on the global environment is small. Moreover, since these mixed compositions correspond to non-combustible substances under the Fire Service Law, they are excellent in terms of safety.

In this way, the present inventors can remove oils and fats (sometimes referred to as oil or oil in this specification) from polycarbonate and soft vinyl chloride equipment even under relatively harsh cleaning conditions. In addition, the present inventors have found an excellent cleaning composition and cleaning method that do not substantially impair the transparency of the resin, and have completed the invention.

That is, the present invention includes the following inventions.

[Invention 1]
A cleaning composition for removing fats and oils from an article to be cleaned containing polycarbonate, wherein the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 4/96 to 60/40.

[Invention 2]
A cleaning composition for removing fats and oils from an article to be cleaned containing a soft vinyl chloride resin having a mass ratio of HCFO-1233zd (Z) / HFC-365mfc of 4/96 to 20/80.

[Invention 3]
The cleaning composition according to Invention 1 or Invention 2, wherein the article to be cleaned is an article to be cleaned containing a transparent resin.

[Invention 4]
The step of bringing the cleaning composition according to any one of the first to third aspects of the invention into contact with the “article to be cleaned containing a transparent resin”, and separating the cleaning composition from the article to be cleaned in a liquid state A method for cleaning the article to be cleaned.

The composition of the present invention reduces the amount of HFC-365mfc that has a large global warming potential, is nonflammable, and is suitable for use as a cleaning solvent. In particular, the composition of the present invention has a sufficiently high ability to dissolve and remove foreign matters such as fats and oils, and since it is difficult to impair the transparency of the transparent resin, the transparent resin (polycarbonate, soft vinyl chloride) is used as a constituent component. There exists an effect that it can be used conveniently as a washing | cleaning solvent of the to-be-cleaned article (work) containing.

It is a figure showing the composition dependence of KB value (kauri butanol value) of the composition which consists of HCFO-1233zd (Z) and HFC-365mfc (refer Example 1 mentioned later).

HCFO-1233zd (Z) and HFC-365mfc are known compounds that are readily available. In particular, HCFO-1233zd (Z) isomerizes (E) -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (E)), which is industrially produced as a next-generation blowing agent. [US Patent Application Publication No. 2010/152504].

As an index used as a measure of detergency against oily dirt, the KB value (kauributanol value) is known. The larger this value is, the stronger the detergency of fats and oils. However, in general, a cleaning agent having a large KB value has a strong ability to clean fats and oils, and at the same time tends to affect the transparent resin. On the other hand, a detergent having a small KB value hardly damages the polymer, but tends to have a small detergency of fats and oils.

In the present invention, when the KB value was measured by a method in accordance with the American Society for Test Material Standard (ASTM: D1133-13), the KB value of HCFO-1233zd (Z) was 36, and the KB value of HFC-365mfc was 13. It was. In other words, HCFO-1233zd (Z) can be said to be a solvent having a stronger dissolving power against oily soils than HFC-365mfc. However, as shown in the examples, the KB value of the multi-component system is not a simple arithmetic average of the composition ratio, but a numerical value that can be obtained for the first time by actually preparing and measuring the composition.

As shown in Example 1 to be described later, in the region where the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 0/100 to 60/40, particularly in the region of 0/100 to 20/80, HFC-365mfc alone It was found that the KB value changed remarkably in the region where the mass ratio of HCFO-1233zd (Z) / HFC-365mfc was 60/40 to 100/0.

The KB value is one of the most reliable indicators among several indicators of detergency evaluation in predicting the effect of fats and oils on detergency and transparent resin. Since it cannot be said that it is an excellent cleaning agent unless it is washed and the influence on the washing power and the transparent resin is confirmed, it is important to actually test the influence on the washing test and the transparent resin. As a result, it was recognized that HFC-365mfc alone was insufficient in detergency, but when HCFO-1233zd (Z) was 4% by mass or more, oil solubility was greatly improved.

In addition, if the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is up to 60/40, even under relatively severe cleaning conditions (for example, immersion for a relatively long time of 30 minutes to 1 hour). It has been found that erosion of articles to be cleaned containing polycarbonate can be suppressed. Further, if the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is up to 20/80, even under relatively harsh cleaning conditions (for example, immersion for a relatively long time of 30 minutes to 1 hour). It was found that erosion of articles to be cleaned containing soft vinyl chloride can be specifically suppressed.

That is, when the mass ratio of HCFO-1233zd (Z) / HFC-365mfc satisfies the conflicting performance requirements, specifically, the detergency of fats and oils and the minimization of devitrification into the transparent resin. There was found.

When the ratio of HCFO-1233zd (Z) in HCFO-1233zd (Z) / HFC-365mfc is higher than the above upper limit value, white turbidity of the article to be cleaned is observed in the long-time immersion.

Therefore, the cleaning composition of the present invention is particularly useful for removing oils and fats from the “article to be cleaned containing the transparent resin”.

The cleaning composition of the present invention can also be used for cleaning non-transparent polycarbonate and soft vinyl chloride resin.

In the present invention, “an article to be cleaned containing polycarbonate” and “an article to be cleaned containing soft vinyl chloride” are concepts including the following composite materials.
(1) An article made of a resin obtained by mixing (kneading) polycarbonate (or soft vinyl chloride) with another resin.
(2) A composite article in which a member made of polycarbonate (or soft vinyl chloride) and a member made of another resin are arranged on one substrate, for example.
(3) An article made of a resin in which polycarbonate (polycarbonate) and soft vinyl chloride (in some cases, other resins) are mixed (kneaded).
(4) A composite article in which a member made of polycarbonate, a member made of soft vinyl chloride, and (in some cases, a member made of other resin) are arranged on one substrate, for example.

Examples of the “other resin” in the above (1) to (4) include acrylonitrile butadiene styrene resin (ABS resin), polyethylene, acrylic, polyvinyl chloride (hard), polypropylene, chloroprene, acrylonitrile butadiene rubber, fluoro rubber, Silicon rubber, butyl rubber, natural rubber, ethylene propylene rubber, Teflon (registered trademark), nylon 66, polyester glass, phenol, polycarbonate, polyacetal, chlorosulfonated polyethylene rubber, hydrogenated acrylonitrile butadiene rubber, polyvinylidene fluoride, nylon, styrene butadiene Examples thereof include rubber.

The cleaning time, cleaning temperature, frequency and intensity during ultrasonic cleaning can be adjusted in a timely manner according to the material of the article to be cleaned and the degree of contamination. Even if the composition is in a boiling state, it can be washed.

For example, when the workpiece (article to be cleaned) is an article containing polycarbonate, which is a transparent resin, it is important to set the washing temperature and washing time in the preliminary test because the polymerization degree and additives differ depending on the manufacturer and grade of the polycarbonate. It is. In a normal industrial cleaning process, the time during which the workpiece is in contact with the cleaning liquid is often 1 to 300 seconds. However, the composition of the present invention has a particularly remarkable effect in cleaning with relatively long immersion. Arise. Although there is no particular limitation on the immersion time, it is preferably 10 minutes to 3 hours, and particularly preferably 20 minutes to 2 hours. Typically, the immersion time is 30 minutes to 1 hour. The cleaning composition of the present invention is particularly suitable for such relatively long-time (harsh conditions) cleaning. Although there is no lower limit to the immersion time, it is very short, for example, in the case of light oil stains that can be removed even by immersion for about 1 second, the merit of the cleaning composition of the present invention having a strong cleaning action Is difficult to feel. Conversely, if the immersion time is extremely long, it is inefficient, and in some cases, the article to be cleaned (polycarbonate, soft polyvinyl chloride) may be gradually eroded. Therefore, it is desirable for those skilled in the art to optimize the immersion time while considering the degree of contamination.

The washing temperature can be from 0 ° C. to the boiling point of the washing liquid (approximately 40 ° C.), but the temperature around 20 ° C., 20 to 35 ° C., near normal temperature is not only easy to operate, but also washing It is preferable because of its high strength.

The cleaning method is not particularly limited, and a conventionally used method can be employed. It is recommended to perform rinsing and / or steam cleaning after ultrasonic cleaning and / or heat cleaning. If the cleaning composition is immediately vaporized and separated from the article to be cleaned after ultrasonic cleaning and / or heat cleaning, dirt in the cleaning composition may remain on the article to be cleaned. That is, it is preferable to separate the cleaning composition in a liquid state. Specifically, a method of rinsing and / or steam cleaning with a cleaning composition having a controlled concentration of soil is recommended.
In particular, steam cleaning is preferable because it is simple.

Specifically, the cleaning method of the present invention includes dipping, spraying, heat cleaning, ultrasonic cleaning, steam cleaning, or a combination thereof. In particular, as shown in the examples described later, a method of removing dirt by dipping is particularly preferable. Here, the dipping refers to bringing an object (object to be cleaned) to which dirt such as oil is attached into contact with the composition of the present invention. By immersing the object to be cleaned in the composition of the present invention, the dirt adhering to the object to be cleaned is dissolved in the composition, whereby the dirt can be removed from the object to be cleaned. In addition, the said immersion operation can also be combined with other cleaning operations (boiling cleaning, ultrasonic cleaning, etc.).

The type of workpiece (object to be cleaned) is not limited, but examples include electronic parts (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.), electrical parts, precision machine parts, resin processed parts, optical lenses, clothing Cleaning of goods etc. is mentioned. The type of dirt is not limited, but dirt that can be removed with CFC-113, HCFC-141b, and HCFC-225 has a mass ratio of HCFO-1233zd (Z) / HFC-365mfc in the range of 4/96 to 60/40. It can be removed by optimizing. As dirt, even if particles, grease, wax, flux, ink, etc. coexist with oils and fats (oil, oil), these dirts can be removed without any problem.

This composition can be used not only as a cleaning agent but also as a solvent, a silicone solvent, a foaming agent, and a working fluid. In working fluid applications, various resins and elastomers are used in heat pump equipment, but this composition has an effect of mitigating their deterioration as compared with the case of using HCFO-1233zd (Z) alone. Have.

It is possible to add various additives to the HCFO-1233zd (Z) and HFC-365mfc composition as desired by those skilled in the art. Also in this case, the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 4/96 to 60/40, more preferably 4/96 to 20/80.

Such additives include various surfactants to further improve detergency, interfacial action and the like. Examples of the surfactant include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as sorbit tetraoleate of polyoxyethylene; polyethylene such as polyoxyethylene monolaurate Glycol fatty acid esters; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide Nonionic surfactants such as the like. These surfactants may be used alone or in combination of two or more. For the purpose of synergistically improving the detergency and interfacial action, in addition to these nonionic surfactants, cationic surfactants or anionic surfactants may be added to the detergent containing the composition of the present invention. Good. The amount of the surfactant used varies depending on the type, but is usually 0.1% by mass or more and 20% by mass or less, and 0.3% by mass with respect to the composition of HCFO-1233zd (Z) and HFC-365mfc. The content is preferably 5% by mass or less.

In the detergent containing the composition of the present invention, various stabilizers may be further added as the additive. The kind of stabilizer is not particularly limited. Examples of the stabilizer include nitro compounds, epoxy compounds, phenols, imidazoles, amines, hydrocarbons and the like. The amount of the stabilizer used varies depending on the type, but is usually 0.1% by mass or more and 20% by mass or less, and 0.3% by mass or more with respect to the composition of HCFO-1233zd (Z) and HFC-365mfc. The content is preferably 5% by mass or less.

As the nitro compound, a known compound may be used, and examples thereof include aliphatic and / or aromatic derivatives. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As aromatic nitro compounds, for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o -, M- or p-nitroanisole and the like can be mentioned.

Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Mono-epoxy compounds such as 2-ethylhexyl glycidyl ether, polyepoxy compounds such as diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane tolglycidyl ether Compounds and the like.

The phenols include phenols containing various substituents such as an alkyl group, an alkenyl group, an alkoxy group, a carboxyl group, a carbonyl group, and a halogen in addition to the hydroxyl group. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol Monovalent phenol such as eugenol, isoeugenol, butylhydroxyanisole, phenol, xylenol or divalent such as t-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone Phenol and the like.

Examples of imidazoles include 1-methylimidazole, 1-n-butylimidazole, 1 to 18 carbon atoms having a straight chain or branched alkyl group, cycloalkyl group, or aryl group as a substituent at the N-position. -Phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl-2-methylimidazole, 1,2 -Dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2-methylimidazole and the like. Examples of amines include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methyl. Benzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, dipentylamine, tripentylamine, 2-ethylhexylamine, aniline, N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethyl Npentamin, benzylamine, dibenzylamine, diphenylamine, and diethylhydroxylamine and the like.

These may be used alone or in combination of two or more compounds.

The present invention will be explained by examples.

[Example 1]
A composition of HCFO-1233zd (Z) and HFC-365mfc having the mass ratio shown in Table 1 was prepared, and the KB value was determined according to the method described in ASTM: D1133-13. That is, a kauri resin-butanol solution was prepared, and the amount of sample in which the solution became cloudy was confirmed. The calibration curve is a solution in which heptane and toluene are mixed at a volume ratio of 75:25 (KB value = 40), CF ₃ CH ₂ CF ₂ CH ₃ (SOLKANE 365mfc, KB value = 13 manufactured by SOLVAY), C ₄ F ₉ OMe ( It was prepared using three points, manufactured by 3M, Novec7100, KB value = 10).
The results are shown in Table 1 and FIG.
(In the table of this example, HCFO-1233zd (Z) is abbreviated as 1233Z and HFC-365mfc is abbreviated as 365.)

Thus, the KB value of the composition of the present invention is not simply a weighted average of the KB values of HCFO-1233zd (Z) and HFC-365mfc, but the mass ratio of HCFO-1233zd (Z) / HFC-365mfc. In the region of 60/40 to 100/0 (particularly in the region where the mass ratio is 80/20 to 100/0 and HCFO-1233zd (Z) is relatively large), the KB value has changed remarkably. .

[Example 2, comparative example]
The test piece of polycarbonate resin was used as an article to be cleaned, and the mass ratio of HCFO-1233zd (Z) / HFC-365mfc was changed to examine the influence on each transparent resin and the state of oil removal.

A drop of cutting oil (Lube Cut B-35 manufactured by Japan Energy Co., Ltd.) was dropped on the center of a horizontally placed resin test piece and allowed to stand for 1 hour. Then, after putting in the composition of each mass ratio (%) of Table 2 for 30 minutes, it pulled up and sprayed compressed air, Then, the surface state was observed.
The cleaning evaluation was visually evaluated as x (unfavorable result) when the trace of the oil was confirmed, and ◯ (preferable result) when the trace was not confirmed. The evaluation of the effect on the transparent resin was carried out by visual evaluation. The case where the surface state maintained the same transparency as that of unwashed was set to 5, and the case where devitrification, significant erosion and dimensional change were observed was set to 1. 5 is a very preferable result, 4 is a preferable result, and 3 or less is a result that is not necessarily preferable in a long-time immersion as in this example. The results are shown in Table 2.

As described above, when the polycarbonate was washed under a slightly long immersion condition of 30 minutes, the mass ratio of HCFO-1233zd (Z) / HFC-365mfc was 4/96 to 60/40. Specifically, it was found that “oil removal performance” and “maintenance of the article to be cleaned” are compatible.

[Example 3, comparative example]
A cleaning experiment similar to that of Example 2 was performed using a test piece made of a soft polyvinyl chloride resin instead of polycarbonate. The results are shown in Table 3.

Thus, when the soft polyvinyl chloride was washed under the slightly long immersion conditions of 30 minutes, a composition in which the mass ratio of HCFO-1233zd (Z) / HFC-365mfc was 4/96 to 20/80. In particular, it was found that “oil removal performance” and “maintenance of the article to be cleaned” are both compatible.

[Example 4]
Example 2 using turbine oil (turbine oil ISO viscosity grade 68 manufactured by JX Nippon Oil & Energy Corporation) and lubricating oil (SUNISO 4GS manufactured by Nippon Sun Oil Co., Ltd.) instead of Lubcut B-35 manufactured by Japan Energy Co., Ltd. The same experiment as Comparative Example 1 was performed. As a result, the state of the polymer surface and the state of oil removal were exactly the same (the results were the same as in Examples 2 and 3, so the attachment of the table was omitted). In other words, in terms of the “solubility of fats and oils”, no significant dependence on the kind of fats and oils was observed.

In summary, it has been found that a composition having a mass ratio of HCFO-1233zd (Z) / HFC-365mfc of 4/96 or more has a detergency of various oils (cutting oil, turbine oil, lubricating oil, etc.). .

In the case of polycarbonate, a composition in which the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 4/96 to 60/40 is a very preferable composition range in which the oil and fat are washed well without impairing transparency. There was found. In the case of soft polyvinyl chloride, a composition in which the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 4/96 to 20/80 is a very preferable composition range in which the oil and fat can be washed well without impairing transparency. It turned out to be.

Claims (4)

1. A cleaning composition for removing oils and fats from articles to be cleaned containing polycarbonate, wherein the mass ratio of HCFO-1233zd (Z) / HFC-365mfc is 4/96 to 60/40.
2. A cleaning composition for removing oils and fats from articles to be cleaned containing a soft vinyl chloride resin having a mass ratio of HCFO-1233zd (Z) / HFC-365mfc of 4/96 to 20/80.
3. The cleaning composition according to claim 1 or 2, wherein the article to be cleaned is an article to be cleaned containing a transparent resin.
4. A step of bringing the cleaning composition according to any one of claims 1 to 3 into contact with an "article to be cleaned containing a transparent resin"; and the cleaning composition from the article to be cleaned in a liquid state A method for cleaning the article to be cleaned.

Images