JPH01301796A - Azeotropic composition - Google Patents

Abstract

PURPOSE:To obtain an azeotropic composition steeply reducing using amount of trichlorotrifluoroethane having slight effect to plastic or rubber and exhibiting nonflammability and low toxicity, by mixing respective specific trichlorotrifluoroethane and chlorotetrafluoropropane in a specific ratio. CONSTITUTION:(A) 70-75wt.% 1,1,2-trichloro-1,2,2-trifluoroethane is mixed with (B) 30-25wt.% 1-chloro-2,2,3,3-tetrafluoropropane to obtain the aimed composition. Besides, furthermore stabilizer such as nitromethane, 3-methyl-1- butane-3-ol is preferably used in an amount of 0.1-10wt.% of (A)+(B). Said composition is useful for detergent in cutting of silicon wafer, ceramic or crystal, etc., or for removing of wax for tentative fixing in processing such as grinding, etc., furthermore, is used for solvents, dryer for strainer, medium of heat exchanger, working fluid, electric insulator or fire-extinguisher, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is based on 1,1,2-trichloro, 2,2-trifluoroethane (hereinafter referred to as Freon-113) and 1-chloro-2,2, 3,3-tetrafluoropropane (hereinafter referred to as
(referred to as Freon-244).

[Prior art] Freon-113, a chlorofluoroethane compound, has been known to be non-flammable and low in biological toxicity, and it does not attack polymeric substances such as plastics and rubber, and can be used against oils, fats, greases, and waxes. It has excellent selective solubility, and is widely used in solvents, cleaning agents, etc., either alone or in mixtures with other organic solvents, or in the form of azeotropic compositions.

[Problem to be solved by the invention] In recent years, chlorofluoroethane compounds such as Freon-113, in which all the hydrogen in ethane has been replaced with chlorine and fluorine (hereinafter referred to as barhaloethane), are destroying the ozone layer surrounding the earth. The global environmental pollution caused by the use of varhaloethane has become a problem, and there is an urgent need to reduce the amount of varhaloethane used.

Various substances have been studied to replace Freon-113, but no effective substitute has yet been found. On the other hand, a mixed solvent of Freon 13 and other organic solvents has also been put into practical use.

However, in order to use it as a solvent, it is important that it be easy to manage the liquid during use, and that it can be easily recovered and reused, and it is also desired that it be capable of steam cleaning. A mixed solvent that satisfies these requirements cannot be obtained simply by mixing two or more components; it must have an azeotropic point,
In other words, it is necessary to form a mixture in an azeotropic state.

Azeotropic mixtures with methanol and ethanol are known as azeotropic mixtures with Freon-113, but in both cases the alcohol component is less than 10% (wt%, the same applies hereinafter) (methanol 6%, ethanol = 4%), which is therefore completely unsatisfactory in terms of reducing the amount of Freon-113 used.

Also, 1=1 between Freon-113 and methylene chloride
Although azeotropic azeotropes have also been put into practical use, they are not desirable due to the high biotoxicity of methylene chloride.

The present invention provides an azeotropic composition in which the amount of Freon-113 used can be significantly reduced while utilizing the excellent properties of Freon-113.

[Means for Solving the Problems] The azeotropic composition of the present invention contains 70 to 75% of Freon-113.
and 30 to 25% of Freon-244.

[Function and Examples] Freon-113 used in the present invention (boiling point 47.6°C)
and Freon-244 (boiling point + 55.8 °C) has an azeotrope of 466-46.8 °C.

Freon-244 has traditionally been used for common uses of Freon, such as solvents, cleaning agents, heat exchange media, working fluids, electrical insulation materials,
It is known to be used as a fire extinguisher.

Since the composition of the present invention contains 25 to 30% of Freon-244, it is possible to significantly reduce the amount of Freon-113 used, and it has less effect on plastics and rubber, making it easier to wash items. It can be washed completely, and only stains such as oil and fat can be selectively dissolved. Furthermore, since it is an azeotropic mixture, liquid management, recovery, and reuse are easy, and it can also be applied to steam cleaning.

The compositions of the invention are non-flammable and have low toxicity. In addition, although it is chemically relatively stable, a stabilizer may be further added.

The properties necessary for such a stabilizer include, of course, that it has a large stabilizing effect on the composition of the present invention, but in addition to this, it also includes a stabilizer that can be entrained in a distillation operation,
Furthermore, those that form an azeotrope are desirable.

Specific examples of the above-mentioned stabilizers include aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane, 3-methyl-1-butyn-3-ol,
- Acetylene alcohols such as methyl-1-pentyne-3-ol, glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, epoxides such as 1,2-butylene oxide, cyclohexene oxide, epichlorohydrin, dimethoxymethane, 1 .2-dimethoxyethane, 1.4-dioxane, 1. ．． 3. Ethers such as 5-trioxane, hexene, heptene, octene, 2.4.4-trimethyl-1-pentene, pentadiene, octadiene,
Unsaturated hydrocarbons such as cyclohexene and cyclopentene, allyl alcohol, 1-buten-3-ol, 3-
Examples include olefinic alcohols such as methyl-1-buten-3-ol, and acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and these may be used alone or in combination of two or more. May be used together. Also, these and phenol, )・limethylphenol, cyclohexylphenol, thymol, 2.6-
Phenols such as di-t-butyl-4-methylphenol, butylhydroxyanisole, isoeugenol, hexylamine, pentylamine, dipropylamine, diisopropylamine, diisobutylamine, triethylamine, tributylamine, pyridine, N-methylmorpholine, Cyclohexylamine, 2,2. [i,
6-titramethylpiperidine, N,N”diallyl-p-
Amines such as phenylenediamine, benzotriazole, 2-(2'-hydroquine-5°-methylphenyl)
It may be used in combination with triazoles such as benzotriazole and ryolobenzotriazole, and when used in combination, an even more excellent synergistic stabilizing effect is exhibited.

The amount of the stabilizer to be used cannot be determined unconditionally since it varies depending on the type of stabilizer, but it is usually preferably used in an amount of 0.1 to 10%, and 0.5 to 10%, based on the composition of the present invention.
It is more preferable to use 5%.

The azeotropic composition of the present invention, which has these advantages, can be used not only for removing oils and greases, but also for removing temporary fixing waxes during cutting and polishing of silicon wafers, crystals, ceramics, etc. used for semiconductors. It is useful as a cleaning agent, and can also be used as a variety of solvents, draining and drying agents, heat exchange media, working fluids, electrical insulation, and fire extinguishing agents.

Next, the azeotropic composition of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example] 100g each of Freon-113 and Freon-244
200 g of the mixture was put into a distillation flask and distilled under normal pressure using a rectification column with 30 theoretical plates. As a result, an azeotrope was observed at 46.6-46.8°C, and when the fraction was analyzed by gas chromatography, the composition was 70-75% Freon-113 and 30-25% Freon-244. there were.

Example 2 The cleaning ability of the composition of the present invention against oils and fats was investigated in the following manner.

100 g of the washer with the spindle ura attached was immersed in a beaker containing 500 g of each solvent shown in Table 1, and the ultrasonic cleaning was repeated twice for 60 seconds, then the same solvent was used for 60 seconds.
Steam cleaned for seconds. The amount of residual oil in the washer after cleaning was measured using an oil concentration meter.

The results are shown in Table 1.

[Margin below] Table 1 Example 3 For each solvent shown in Table 2, the influence (swelling degree) on the material (plastic) was investigated in the following manner.

100% of the solvent shown in Table 2 in a 100cc pressure glass bottle
g and the plastic test piece shown in the same table (5X50x2+n
+n) and left in a constant temperature bath at a temperature of 51)'C for 4 hours, and after taking it out, the weight increase and volume increase were immediately examined.

The results are shown in Table 2.

The evaluation was as follows: 01 Weight or volume increase rate: Less than 2% ○: Weight or volume increase rate from 2% to less than 5% Δ: Weight or volume increase rate: 5% or more.

[Margins below] [Effects of the Invention] The azeotropic composition of the present invention can significantly reduce the amount of Freon-113 used, which is considered to be the cause of ozone layer destruction in perhaloethane, and can also reduce Freon-113. It is an extremely excellent composition that exhibits harmonious characteristics between CFC-244 and CFC-244, and also combines the advantages of an azeotrope with ease of handling during liquid management, recovery, and reuse. It can be used in various fields as a substitute for 113.

Patent applicant: Daikin Industries, Ltd.

Claims (1)

[Claims] 1 70-75% by weight of 1,1,2-trichloro-1,2,2-trifluoroethane and 1-chloro-2,2,3,
An azeotropic composition comprising 30 to 25% by weight of 3-tetrafluoropropane.