JP3413517B2 - Azeotropic and azeotrope-like compositions - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an azeotropic composition and an azeotrope-like composition, and more specifically, an azeotropic composition and an azeotropic composition used as flux cleaning, degreasing cleaning, draining drying, solvent, etc. Such a composition.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons have been most well known as cleaning solvents for electronic parts, precision machine parts, resin processed parts, etc. It has characteristics as a hydrogen group. These halogenated hydrocarbons are less toxic,
It shows nonflammability when the number of halogen substitutions is large, is chemically and thermally stable, and has an appropriate solubility of dissolving waxes and fats and oils without eroding the surface of plastics and rubbers. Therefore, it is widely used in various industrial fields. Examples of these halogenated hydrocarbons include chlorine-based hydrocarbons such as trichloroethylene, tetrachloroethylene, and 1,1,1-trichloroethane, and 1,1,2-trichloro-1,2,2-trifluoroethane (CFC 113). CFC-based hydrocarbons are known. Particularly, the latter CFC-based hydrocarbons are used in a wide range of fields because they are less toxic, nonflammable, and chemically and thermally stable. However, since the CFC-containing hydrocarbons containing chlorine and 1,1,1-trichloroethane have chlorine atoms, a serious drawback of destroying the ozone layer in the stratosphere has been pointed out, and it is internationally necessary to stop their production and use. Has been decided. Also, regarding trichlorethylene and tetrachlorethylene, the issue of groundwater pollution has been highlighted, and based on the results of subsequent environmental pollution survey results and the results of the toxicity survey that chronic toxicity, etc. have been confirmed, since 1989, it has been designated as a Class 2 Specified Chemical Substance. Designated. Under such circumstances, the development of substances such as fluorocarbon-containing hydrocarbons containing chlorine and substances substituting for chlorine-based hydrocarbons is being actively conducted.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent properties such as cleanability and low toxicity of CFC-containing hydrocarbons containing chlorine and chlorine-containing hydrocarbons. Without damaging it, without worrying about ozone depletion,
Moreover, it is an object to provide a novel composition having a small greenhouse effect.

[0004]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, bis (2,2,2-trifluoroethyl) ether represented by the following formula (1) CF ₃ CH ₂ OCH ₂ CF ₃ (1) 80 to 95 wt. % And methanol 5 to 20% by weight
An azeotropic or azeotrope-like composition comprising: Well
Also, according to the present invention, bis (2,2,2-trifluoro
85% by weight of ethyl ether and 5% of ethanol
Or an azeotropic composition characterized by comprising 15% by weight or
An azeotrope-like composition is provided. Further according to the invention,
Bis (2,2,2-trifluoroethyl) ether 85
~ 95 wt%, 2-propanol 5-15 wt%
An azeotropic composition or an azeotrope-like composition characterized by comprising
Provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention is specifically as follows. The azeotropic composition means that the vapor composition and the liquid composition are the same, and there is no composition change of the composition after repeated evaporation and condensation. The azeotrope-like composition means that the vapor composition and the liquid composition are almost the same, and the compositional change of the composition after repeated evaporation and condensation changes only to a negligible degree. (1) Azeotropic composition comprising 80-95% by weight of bis (2,2,2-trifluoroethyl) ether and 5-20% by weight of methanol, preferably bis (2,2,2-trifluoroethyl) An azeotropic composition consisting of 87.63% by weight of ether and 12.37% by weight of methanol. The boiling point of this azeotropic composition is 5 at atmospheric pressure (760 mmHg).
It is 3.13 ° C. (2) An azeotrope-like composition composed of 85-95% by weight of bis (2,2,2-trifluoroethyl) ether and 5-15% by weight of ethanol, preferably bis (2,2,2-trifluoroethyl). An azeotropic composition consisting of 90.88% by weight of ether and 9.12% by weight of ethanol. The boiling point of this azeotropic composition is 58.70 at atmospheric pressure (760 mmHg).
It is 75 ° C. (3) An azeotrope-like composition consisting of 85-95% by weight of bis (2,2,2-trifluoroethyl) ether and 5-15% by weight of 2-propanol, preferably bis (2,2,2).
An azeotropic composition consisting of 91.35% by weight of trifluoroethyl) ether and 8.65% by weight of 2-propanol. The boiling point of this azeotropic composition is the atmospheric pressure (760 mmH
It is 61.01 ° C. in g). Bis (2,2,2-trifluoroethyl) ether according to the invention is a known substance, for example potassium-2,
It is easily obtained by the reaction of 2,2-trifluoroethanolate and 2,2,2-trifluoroethyl paratoluenesulfonate.

The composition according to the present invention may further contain various stabilizers when used under severe conditions. As the stabilizer, those which are co-distilled by the distillation operation or those which form an azeotrope-like mixture are desirable. Specific examples of such stabilizers include aliphatic nitro compounds such as nitromethane and nitroethane, aromatic nitro compounds such as nitrobenzene and nitrostyrene, dimethoxymethane, 1,2.
-Dimethoxyethane, 1,4-dioxane, 1,3,5
-Ethers such as trioxane, glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 1,2-butylene oxide,
Epoxides such as cyclohexene oxide and epichlorohydrin, unsaturated hydrocarbons such as hexene, heptene, pentadiene, cyclopentene and cyclohexene, olefinic alcohols such as allyl alcohol and 1-buten-3-ol, 3-methyl-1-butyne Examples thereof include acetylenic alcohols such as -3-ol and 3-methyl-1-pentyn-3-ol, and acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate. Further, in order to obtain a synergistic stabilizing effect, phenols, amines and benzotriazoles may be used in combination. These stabilizers may be used alone or in combination of two or more kinds. The amount of the stabilizer used varies depending on the kind of the stabilizer and the like, but it should be such that the azeotrope-like properties are not hindered. The amount used is usually about 0.01 to 10% by weight of the composition of the present invention, and more preferably about 0.1 to 5% by weight.

In addition, various surfactants may be added to the composition of the present invention, if necessary, in order to further improve detergency, interface action and the like. Examples of the surfactant include sorbitan monooleate, sorbitan trioleate and other sorbitan fatty acid esters, polyoxyethylene sorbit tetraoleate and other polyoxyethylene sorbit fatty acid esters, and polyoxyethylene monolaurate and other polyethylene glycol fatty acids. Esters, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide The nonionic surface active agent may be used alone or in combination of two or more kinds. For the purpose of synergistically improving the detergency and the surface action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. Although the amount of the surfactant used varies depending on the type of the surfactant, it is usually 0.1% of the composition of the present invention as long as it does not hinder the azeotropic property.
Is about 20 to 20% by weight, and more preferably about 0.3 to 5% by weight.

The composition of the present invention can be widely used for known cleaning and drying applications, but in particular, it can be used as a flux cleaning agent, a cleaning solvent, a degreasing cleaning agent, and a desiccant desiccating agent. It is extremely useful as a substitute for 1-trichloroethane. Specific applications include flux, grease, oil, wax, ink and other removers, electronic parts (printed circuit boards, liquid crystal displays, magnetic recording parts, semiconductor materials, etc.), electrical parts, precision machine parts,
Examples include cleaning agents for resin-processed parts, optical lenses, clothing, draining desiccants, and the like. As the cleaning method, a conventionally used method such as dipping, spraying, boiling cleaning, ultrasonic cleaning, steam cleaning or a combination thereof can be adopted. Further, the composition of the present invention can be used for various applications such as a solvent for paints, an extractant, a heat medium and a foaming agent as in the case of conventional CFCs.

[0009]

EXAMPLES Examples will be shown below to further clarify the features of the present invention. Of course, the invention is not limited by these examples.

Example 1 The vapor-liquid equilibrium and azeotropic point of bis (2,2,2-trifluoroethyl) ether and methanol were measured using a vapor-liquid equilibrium measuring device. A mixed sample having a constant composition of bis (2,2,2-trifluoroethyl) ether and methanol was placed in the sample container section and heated. Then, heating was adjusted so that the dropping rate of the vapor-phase condensate was appropriate, and stable boiling was maintained for 40 minutes or more. After making sure that the pressure and boiling point were stable, they were measured. Further, the liquid phase and the gas phase condensate were sampled, and the composition of the sampling liquid was analyzed by gas chromatography. The measurement results are shown in Table 1, FIG. 1 and FIG. From this result, screw (2,
The compositions of the present invention in the range of 80-95% by weight of 2,2-trifluoroethyl) ether and 5-20% by weight of methanol are azeotrope-like compositions. Here, screw (2, 2,
The composition consisting of 87.63% by weight of 2-trifluoroethyl) ether and 12.37% by weight of methanol is an azeotropic composition, the boiling point of which is 5 at atmospheric pressure (760 mmHg).
It is 3.13 ° C.

[0011]

[Table 1] * 1: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in liquid phase * 2: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in gas phase

Example 2 Measurement was carried out by the same apparatus and procedure as in Example 1 except that bis (2,2,2-trifluoroethyl) ether, methanol and ethanol were used instead of the composition of Example 1. It was The measurement results are shown in Table 2, FIG. 3 and FIG. From this result, the composition of the present invention in the range of 85-95% by weight of bis (2,2,2-trifluoroethyl) ether and 5-15% by weight of ethanol is an azeotrope-like composition. The composition consisting of 90.88% by weight of bis (2,2,2-trifluoroethyl) ether and 9.12% by weight of ethanol is an azeotropic composition whose boiling point is atmospheric pressure (76
It is 58.75 degreeC in 0 mmHg).

[0013]

[Table 2] * 1: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in liquid phase * 2: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in gas phase

Example 3 Measurement was carried out in the same manner as in Example 1 except that the composition of Example 1 was replaced with bis (2,2,2-trifluoroethyl) ether, methanol and 2-propanol. I went. The measurement results are shown in Table 3, FIG. 5 and FIG. From this result, bis (2,2,2-trifluoroethyl)
85 to 95% by weight of ether and 5-1 to 2-propanol
Compositions of the present invention in the 5 wt% range are azeotrope-like compositions. Here, the composition consisting of 91.35% by weight of bis (2,2,2-trifluoroethyl) ether and 8.65% by weight of 2-propanol is an azeotropic composition having a boiling point at atmospheric pressure (760 mmHg). It is 61.01 degreeC.

[0015]

[Table 3] * 1: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in liquid phase * 2: CF ₃ CH ₂ OCH ₂ CF ₃ concentration in gas phase

[0016]

Since the composition of the present invention contains no chlorine atom, there is no fear of ozone layer depletion. Further, since the composition of the present invention contains hydrogen atoms, it has high reactivity with hydroxyl radicals in the atmosphere and is easily decomposed in the troposphere, so that the greenhouse effect is small.

[Brief description of drawings]

FIG. 1 shows a liquid phase concentration / vapor phase concentration curve in vapor-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + methanol system.

FIG. 2 shows a liquid phase concentration / concentration curve in vapor-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + methanol system.

FIG. 3 shows a liquid phase concentration / vapor phase concentration curve in a vapor-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + ethanol system.

FIG. 4 shows a liquid phase concentration / concentration curve in vapor-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + ethanol system.

FIG. 5 shows a liquid phase concentration / vapor phase concentration curve in a gas-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + 2-propanol system.

FIG. 6 shows a liquid phase concentration / concentration curve in vapor-liquid equilibrium of a CF ₃ CH ₂ OCH ₂ CF ₃ + 2-propanol system.

Front page continuation (73) Patent holder 000157119 Kanto Denka Kogyo Co., Ltd. 1-2-1, Marunouchi, Chiyoda-ku, Tokyo (73) Patent holder 000002004 Showa Denko KK 1-13-9, Shibadaimon, Minato-ku, Tokyo ( 73) Patent holder 000002200 Central Glass Co., Ltd. 5253 Oki Ube, Ube City, Yamaguchi Prefecture (73) Patent holder 000002853 Daikin Industries, Ltd. 2-4-12 Nakazaki Nishi, Kita-ku, Osaka City, Osaka Umeda Center Building (73) Patent Right holder 000003034 Toagosei Co., Ltd. 1-14-1 Nishishinbashi, Minato-ku, Tokyo (73) Patent holder 000174851 Mitsui DuPont Fluorochemical Co., Ltd. 1-5-18 Sarugakucho, Chiyoda-ku, Tokyo (74) Above 8 Attorney 100074505 Patent Attorney Toshiaki Ikeura (72) Inventor Toshihiko Hiaki 3-1-47-406 Yatsu, Narashino, Narashino, Chiba (72) Inventor Junji Murata 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building 6F Institute for Global Environmental Technology Research New Refrigerants, etc. Project Room (72) Inventor Masahiko Yasumoto 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building 6F Institute for Global Environmental Technology Research Institute New Refrigerant Project Room (72) Inventor Takeshi Sako 1 East, Tsukuba City, Ibaraki Prefecture 1st Industrial Technology Institute, Institute of Materials Science and Technology (72) Inventor Akira Sekiya 1-1st East, Tsukuba City, Ibaraki Prefecture Institute of Industrial Science and Technology (56) Reference JP-A-11-256195 (JP, A) JP-A-4-227695 (JP, A) JP-A-10-324897 (JP, A) JP-A-6-220497 (JP, A) JP-A-11-92412 (JP, A) JP-A-8 −259995 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C11D ⁷ /00-7/60 B01D 12/00 C23G 5/00-5/036 H05K 3/26 CA (STN ) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. Bis (2,2,2-trifluoroethyl) ether 80-95% by weight and methanol 5-20
An azeotropic composition or an azeotrope-like composition, characterized in that 2. Bis (2,2,2-trifluoroethyl)
Ru) ether 85-95% by weight and ethanol 5-15
Azeotropic composition or azeotropic composition characterized by comprising
Like composition. 3. Bis (2,2,2-trifluoroethyl)
85-95% by weight of ether and 2-propanol 5
Azeotropic composition or
Is an azeotropic composition.