JPS63295699A - Azeotropic solvent composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. having excellent dissolving power and a low content of 1,1,2-trichloro-1,2,2-trifluoroethane (flon-113), by mixing 1,2- dichloro-1,1-difluoroethane with flon-113. CONSTITUTION:48.1wt.% 1,2-dichloro-1,1-difluoroethane having a b.p. of 46.8 deg.C (flon-132b) is mixed with 51.9wt.% 1,1,2-trichloro-1,2,2-trifluoroethane (flon-113) having a b.p. of 47.6 deg.C to prepare the title compsn. having a b.p. of 44.2 deg.C. If necessary, 0.1-10% stabilizer (e.g., nitromethane) is added to the compsn. This compsn. is useful for removal of fats and oils and grease, removal of wax for temporary fixing in cutting or polishing work of a silicon wafer, a ceramic, or the like, removal of a releasing agent, removal of a flux, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to 1,2-dichloro-1,1-difluoroethane (hereinafter referred to as Freon-132b) and 1,1,2-trichloro-1,2,2 - trifluoroethane (hereinafter referred to as Freon-113).

[Conventional technology] Freon-113, a chlorofluoroethane compound, is nonflammable and has low biotoxicity, and has the ability to dissolve oils, fats, grease, wax, etc. without attacking polymeric substances such as plastics and rubber. 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.

[Problems to be solved by the invention] In recent years, it has become clear that chlorofluoroethane compounds (hereinafter referred to as perhaloethane) in which all hydrogen has been replaced with chlorine and fluorine, such as Freon-113, are destroying the ozone layer surrounding the earth. Environmental pollution has become a problem, and there is an urgent need to reduce the use of perhaloethane.

Various substances have been studied to replace Freon-113, but no effective substitute has yet been found. On the other hand, mixed solvents of Freon-113 and other organic solvents have 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 able to be cleaned with steam. A mixed solvent that satisfies these requirements cannot be obtained simply by mixing two or more components, but must be a mixture that has an azeotropic point, that is, an azeotropic mixture.

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: 5.7%). , ethanol: 4%), which is therefore completely unsatisfactory in terms of reducing the amount of Freon-113 used.

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

The present invention provides a solution to CFC-113 while maintaining sufficient solvent performance.
An object of the present invention is to provide an azeotropic solvent composition that can reduce the amount of azeotropic solvent used.

[Means for Solving the Problems] The azeotropic solvent composition of the present invention contains 48.1% Freon-13.
2b and 51.9% Freon-113.

[Function and Examples] Freon-132b used in the present invention (boiling point: 4B,
An azeotropic mixture of 8°C) and Freon-113 (%3 point: 47.8°C) has an azeotropic point of 44.2°C.

Freon-132b is a compound that has two hydrogen atoms in addition to chlorine and fluorine atoms, and does not destroy the ozone layer. However, it has not been used as a solvent because it alone has too much dissolving power for plastics and rubber and corrodes those materials.

According to the present invention, since Freon-132b and Freon-113 are contained in a weight ratio of 48.1/51.9, the dissolving power of Freon-132b for organic materials can be suppressed, and at the same time, Freon-113 can be suppressed. Not only can the amount used be significantly reduced, but also the dissolving power of Freon-132b can be used to remove fluxes in the electronics industry that cannot be removed with Freon-113 alone.

Moreover, since it is in an azeotropic state, liquid management, recovery, and reuse are easy, and it can also be applied to steam cleaning.

Although the composition of the present invention is chemically stable, additional stabilizers may be added.

Preferable properties for such a stabilizer include, of course, having a large stabilizing effect on the composition of the present invention, but also those that are entrained in distillation operations and those that form an azeotrope. These are desirable, but not limited to.

Specific examples of the above-mentioned stabilizers include aliphatic nitro compounds such as nitromethane, nitroethane, and nitropropane, 8-methyl-1-butyn-3-ol, 3
- Acetylene alcohols such as methyl-1-pentyne-3-ol, glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, epoxides such as 2-butylene oxide, cyclohexene oxide, epichlorohydrin, dimethoxymethane, 1 .Ethers such as 2-dimethoxyethane, 1,4-dioxane, L, 3,54lioxane,
Unsaturated hydrocarbons such as hexene, heptene, octene, 2.4.44-limethyl-1-pentene, pentadiene, octadiene, cyclohexene, cyclopentene, allyl alcohol, 1-buten-3-ol, 3-methyl-1-butene Examples include olefinic alcohols such as -3-ol, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, etc.
These may be used alone or in combination of two or more. In addition, these and phenol, trimethylphenol, cyclohexylphenol, thymol, 2.6-di-t-
Phenols such as butyl-4-methylphenol, butylhydroxyanisole, isoeugenol, hexylamine, pentylamine, dipropylamine, diisopropylamine, diisobutylamine, triethylamine, tributylamine, pyridine, N-methylmorpholine, cyclohexylamine, It may be used in combination with amines such as 2,2.8.8-tetramethylpyridine and N,N'-diallyl-p-phenylenediamine, 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 solvent composition of the present invention, which has these advantages, can be used not only to remove oil and grease, but also to remove waxes used for temporary fixing during processing such as cutting and polishing of silicon wafers, crystals, and ceramics used in semiconductors, and for photo-removal. Yougetsu is a cleaning agent used for peeling off resist, removing flux, etc.

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

Example 1 150g each of Freon-132b and Freon-03
300 g of a mixture of 150 g and 150 g was placed in a distillation flask, and distilled under normal pressure using a rectification column with 30 theoretical plates. As a result, an azeotrope was observed at 44.2°C, and the fraction was analyzed by gas chromatography.
The composition is 48.1% Freon-132b and Freon-113.
was 51.9%.

Example 2 The solubility of waxes used as temporary fixing materials in silicon wafer processing was investigated in the following manner.

Each of the solvents shown in Table 1 has a capacity of 200
The mixture was placed in a cc beaker and heated to 40°C. Then, while stirring, powdered waxes such as electron wax and cane wax (both manufactured by Nikka Seiko ■) were gradually added to the mixture, and the solubility was observed.

The results are shown in Table 1.

Evaluation of solubility was carried out according to Haggi's standards.

◎: Melted to a flux level of 2% or more O: Melted to a wax concentration of 1% to 2% Δ: Melted to a flux level of 1% ×: Not dissolved Example 3 Printed circuit board made of phenolic resin with built-in electric circuit (BOX 50 mm) ) Apply Breflux (B-111B) made by Tamura Manufacturing Co., Ltd. to the entire surface, then apply Postflux (P-230V), and then apply approximately 2
It was fired for 2 minutes in an electric furnace at 50°C. After firing, the printed circuit board was taken out of the furnace and cooled to room temperature, and then washed using a two-tank immersion-steam cleaning machine [Model UP manufactured by Branson Corporation] containing the solvents shown in Table 1.
-12101 for 1 minute immersion cleaning (ultrasonic cleaning) and then steam cleaning for 30 seconds to determine the degree of flux removal at 7011. The degree of flux removal was visually observed.

The results are shown in Table 1.

In Table 1, 0: Good △: Slightly defective (white residue on the board surface) ×：Poor It is.

Example 4 For each solvent shown in Table 1, the influence (swelling degree) on the material (plastic) was investigated in the manner described below.

100% of the solvent shown in Table 1 in a 100cc pressure-resistant glass bottle
g and the plastic test piece shown in the same table (5X50X21
11) was placed in a constant temperature bath at a temperature of 50'C for 4 hours, and after taking it out, the weight increase and volume increase were immediately examined.

The results are shown in Table 1.

Evaluation 02 Weight or volume increase O ~ 2% ○: Mold weight or volume increase 2-5% Δ: Mold weight or volume increase 5% or more X: Dissolution And so.

[Effects of the Invention] The azeotropic solvent composition of the present invention can significantly reduce the amount of fluorocarbon-113 used, which is thought to be the cause of ozone layer destruction in fluorocarbon-based solvents. An extremely excellent solvent composition that exhibits the harmonious dissolving power of Freon-132b, is non-flammable, and also has the advantages of an azeotropic mixture, such as ease of handling during liquid management, recovery, and reuse. Furthermore, it has the excellent effect of expanding the range of substances to be dissolved.

Patent Applicant: Daikin Industries, Ltd. Procedural Amendment Seal: July 8, 1985 Commissioner of the Patent Office: Mr. Kunito Ogawa, Case I 萱1 Indication of Patent Application No. 131027, 1985 Name (285) Representative of Daikin Industries, Ltd. Mountain 1) Subject of the 5th amendment in the completed section (1) Contents of the 6th amendment in the "Detailed Description of the Invention" section of the specification (1) Changed "5.7%" on page 3, line 10 of the specification to "6%" and correct it.

('2J, p. 4, lines 10-11, ``Does not destroy the ozone layer'' is corrected to ``Has almost no effect on the destruction of the ozone layer.''

(3) "Organic" on page 4, line 17 is corrected to "polymer."

(4) "Chemically J" on page 5, line 5 is corrected to "chemically comparative."

(5) Correct “pyridine” in line 2 of page 7 to “piperidine”.

(6) "Amines" on page 7, line 3 is corrected to "amines, triazoles such as benzotriazole, 2-(2°-hydroxy-5-methylphenyl)benzotriazole, and chlorobenzotriazole."

(7') "Removal" on page 7, line 15 is corrected to "removal agent."

(8) On page 9, lines 10-12, “At about 250℃...
...After cooling, it was soldered at about 250°C.

Let this printed circuit board cool for one hour at room temperature.''

(9) [Steam cleaning type...] on page 9, lines 13-14.
... model UP-1210] is corrected to "with a two-tank steam cleaning machine."

(Foundation) Correct "30 seconds" on page 9, line 15 to "1 minute."

that's all

Claims (1)

[Claims] 1 1,2-dichloro-1,1-difluoroethane 48
．． 1% by weight and 51.9% by weight of 1,1,2-trichloro-1,2,2-trifluoroethane.