JP3360107B2 - Azeotropic and azeotropic compositions comprising fluorinated ketones and alcohols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azeotropic composition and an azeotropic composition, and more particularly, to an azeotropic composition and an azeotropic composition used as flux cleaning, degreasing cleaning, draining and drying, and a solvent. -Like compositions.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons are the most well-known solvents for cleaning electronic parts, precision machine parts, resin processed parts, etc., and chlorine atoms or carbon atoms obtained by substituting chlorine atoms for fluorine atoms. It has characteristics as a hydrogen group. These halogenated hydrocarbons are less toxic,
High substitution number of halogen shows nonflammability and is chemically and thermally stable, and has appropriate solubility to dissolve waxes and oils without eroding the surface of plastics and rubber. Therefore, it is widely used in various industrial fields. For example, these halogenated hydrocarbons include chlorinated hydrocarbons such as trichloroethylene, tetrachloroethylene and 1,1,1-trichloroethane, and 1,1,2-trichloro-1,2,2-trifluoroethane (Freon 113). Are particularly known, and the latter is used in a wide range of fields because of its low toxicity, nonflammability, and chemical and thermal stability. However, the serious disadvantage of destruction of the stratospheric ozone layer has been pointed out because such fluorocarbon hydrocarbons and 1,1,1-trichloroethane containing chlorine have chlorine atoms. Is decided. In addition, trichlorethylene and tetrachlorethylene have been designated as Class 2 Specified Chemical Substances since 1989 based on the results of surveys on environmental pollution and the harmfulness of chronic toxicity, etc., as the groundwater pollution problem was highlighted. Designated. Under such circumstances, the development of such chlorofluorocarbon-based hydrocarbons and substances that substitute for chlorinated hydrocarbons has been actively conducted.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides excellent properties such as chlorofluorocarbon-based hydrocarbons and chlorine-based hydrocarbons having excellent detergency and low toxicity. Without damaging, there is no worry of ozone layer destruction,
Another object of the present invention is to provide a novel composition having a small greenhouse effect.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, represented by the following formula _{(1) CF 3 CF 2 CF} 2 CF 2 CF 2 COCH 3 (1) 3,3,4,4,5,5,6,6,7, 7,
An azeotropic or azeotropic composition comprising 7-undecafluoroheptan-2-one and at least one alcohol selected from methanol, ethanol and 2-propanol is provided.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The composition of the present invention is specifically the following composition. The azeotropic composition means a composition having the same vapor composition and liquid composition and no change in the composition of the composition after repeated evaporation and condensation. Further, the azeotropic-like composition means a composition whose vapor composition and liquid composition are substantially the same and whose composition change after repeating evaporation and condensation changes to a negligible extent. (1) 3,3,4,4,5,5,6,6,7,7,7-
Undecafluoroheptane-2-one 60 to 70% by weight
And an azeotrope-like composition comprising ethanol and 30 to 40% by weight, preferably 3,3,4,4,5,5,6,6,7,
7,7-undecafluoroheptane-2-one 63.6
An azeotropic composition consisting of 9% by weight and 36.31% by weight of ethanol. The boiling point of this azeotropic composition is at atmospheric pressure (76
0 mmHg). (2) 3,3,4,4,5,5,6,6,7,7,7-
Undecafluoroheptane-2-one 30 to 40% by weight
And an azeotropic composition comprising 60 to 70% by weight of methanol, preferably 3,3,4,4,5,5,6,6,7,
7,7-undecafluorohexan-2-one 36.5
An azeotropic composition comprising 5% by weight and 63.45% by weight of methanol. The boiling point of this azeotropic composition is at atmospheric pressure (76
0 mmHg) at 64.20 ° C. (3) 3,3,4,4,5,5,6,6,7,7,7-
Undecafluoroheptane-2-one 55-65% by weight
And an azeotropic composition comprising 15 to 25% by weight of 2-propanol, preferably 3,3,4,4,5,5,6,6,6
7,7,7-undecafluoroheptane-2-one 6
0.61% by weight and 39.39% by weight of 2-propanol
An azeotropic composition consisting of The boiling point of this azeotropic composition is
It is 78.52 ° C. at atmospheric pressure (760 mmHg).

According to the present invention, 3, 3, 4, 4, 5, 5,
6,6,7,7,7-Undecafluoroheptane-2-
ON is a known substance, for example, commercially available 2,2,3,3
It is easily obtained by reacting 4,4,5,5,6,6,6-undecafluorocaproic acid with methylmagnesium bromide.

The composition according to the present invention may further contain various stabilizers when used under severe conditions. As the stabilizer, those which are entrained by distillation or those which form an azeotropic mixture are desirable. Specific examples of such a stabilizer include aliphatic nitro compounds such as nitromethane and nitroethane; aromatic nitro compounds such as nitrobenzene and nitrostyrene; dimethoxymethane;
-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 Acetylenic alcohols such as -3-ol and 3-methyl-1-pentyn-3-ol; and acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate. In order to further 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. The amount of the stabilizer used depends on the type of the stabilizer and the like, but is set to such an extent that the azeotropic property is 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.

[0008] Various surfactants can be added to the composition of the present invention, if necessary, in order to further improve detergency, interfacial action and the like. As the surfactant, sorbitan fatty acid esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as polyoxyethylene sorbite tetraoleate; and polyethylene glycol fatty acids such as polyoxyethylene monolaurate 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 Nonionic surfactants may be used alone or in combination of two or more. For the purpose of synergistically improving the detergency and the interfacial action, a cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. The amount of the surfactant to be used varies depending on the kind and the like, but it is an amount which does not hinder the azeotropic property, and is usually 0.1% of the composition of the present invention.
About 20% by weight, more preferably about 0.3 to 5% by weight.

The composition of the present invention can be widely used for known washing and drying applications. In particular, it can be used as a flux detergent, a washing solvent, a degreasing detergent and a draining desiccant. It is extremely useful as a substitute for 1-trichloroethane. Specific applications include flux, grease, oil, wax, and ink removers, electronic components (printed boards, liquid crystal displays, magnetic recording components, semiconductor materials, etc.), electrical components, precision machinery components,
Examples include detergents for resin-processed parts, optical lenses, clothing, and the like, and drainers and desiccants. As the cleaning method, a conventionally used method such as immersion, 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 uses such as a solvent for a paint, an extractant, a heating medium, and a foaming agent, similarly to the conventional chlorofluorocarbon.

[0010]

The following examples are provided to further clarify the features of the present invention. Of course, the present invention is not limited by these examples.

Example 1 Using a vapor-liquid equilibrium measuring apparatus, 3,3,4,4,5,5,5
6,6,7,7,7-Undecafluoroheptane-2-
The on-liquid equilibrium and azeotropic point were measured. 3,3,4
A mixed sample having a constant composition of 4,5,5,6,6,7,7,7-undecafluoroheptane-2-one and ethanol was placed in a sample container and heated. The heating was adjusted so that the dropping rate of the vapor-phase condensate became appropriate, and stable boiling was maintained for 40 minutes or more. After ensuring that the pressure and boiling point were stable, they were measured. The liquid phase and the gas phase condensate were sampled, and the composition of the sampled solution was analyzed by gas chromatography. The measurement results are shown in Table 1, FIG. 1 and FIG. from this result,
3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptan-2-one 60-70% by weight of the composition according to the invention and 30-40% by weight of ethanol The product is an azeotropic-like composition. Where 3,3,4,4,5
5,6,6,7,7,7-Undecafluoroheptane-
The composition consisting of 63.69% by weight of 2-one and 36.31% by weight of ethanol is an azeotropic composition having a boiling point of 75.07 ° C. at atmospheric pressure (760 mmHg).

[0012]

[Table 1]

Example 2 The composition of Example 1 was replaced with 3,3,4,4,5,5
6,6,7,7,7-Undecafluoroheptane-2-
The measurement was performed using the same apparatus and procedure as in Example 1 except that ON was used. The measurement results are shown in Table 2, FIG. 3 and FIG. From these results, 3,3,4,4,5,5,6,
Compositions of the present invention in the range of 30-40% by weight of 6,7,7,7-undecafluoroheptan-2-one and 60-70% by weight of methanol are azeotrope-like compositions. Here, a composition consisting of 36.55% by weight of 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptan-2-one and 63.45% by weight of methanol is common. The composition has a boiling point of 6 at atmospheric pressure (760 mmHg).
4.20 ° C.

[0014]

[Table 2]

Example 3 The composition of Example 1 was changed to 3,3,4,4,5,5
6,6,7,7,7-Undecafluoroheptane-2-
The measurement was performed using the same apparatus and procedure as in Example 1 except that ON and 2-propanol were used. The measurement result is
It is shown in the table, FIG. 5 and FIG. From these results,
4,4,5,5,6,6,7,7,7-Undecafluoroheptan-2-one 55-65% by weight and 2-propanol 35-45% by weight of the composition of the present invention , An azeotropic composition. Where 3,3,4,4,5
5,6,6,7,7,7-Undecafluoroheptane-
60.61% by weight of 2-one and 2-propanol
The composition consisting of 39% by weight is an azeotropic composition having a boiling point of 78.52 ° C. at atmospheric pressure (760 mmHg).

[0016]

[Table 3]

[0017]

Since the composition of the present invention does not contain chlorine atoms, there is no fear of destruction of the ozone layer. Further, since the composition of the present invention contains a hydrogen atom, it has high reactivity with hydroxyl radicals in the atmosphere and is easily decomposed in the troposphere, and thus has an advantage that the greenhouse effect is small.

[Brief description of the drawings]

FIG. 1 C ₅ F ₁₁ COCH ₃ -ethanol system (760 mm
2 shows a gas-liquid equilibrium curve (liquid-gas phase) of Hg).

FIG. 2: C ₅ F ₁₁ COCH ₃ -ethanol system (760 mm
3 shows a gas-liquid equilibrium curve (liquid phase-boiling point) of Hg).

FIG. 3 shows a C ₅ F ₁₁ COCH ₃ -methanol system (760 mm
2 shows a gas-liquid equilibrium curve (liquid-gas phase) of Hg).

FIG. 4 shows a C ₅ F ₁₁ COCH ₃ -methanol system (760 mm
3 shows a gas-liquid equilibrium curve (liquid phase-boiling point) of Hg).

[5] C ₅ F ₁₁ COCH ₃ -2- propanol system (76
2 shows a gas-liquid equilibrium curve (liquid phase-gas phase) of 0 mmHg).

6 C ₅ F ₁₁ COCH ₃ -2- propanol system (76
2 shows a gas-liquid equilibrium curve (liquid phase-boiling point) of 0 mmHg).

──────────────────────────────────────────────────続 き Continued on the front page (73) Patent holder 000157119 Kanto Denka Kogyo Co., Ltd. 1-2-1, Marunouchi, Chiyoda-ku, Tokyo (73) Patent holder 000002004 Showa Denko Co., Ltd. 1-1-13 Shiba-Daimon, Minato-ku, Tokyo 9 No. 9 (73) Patent holder 000002200 Central Glass Co., Ltd. 73) Patent Holder 000003034 Toagosei Co., Ltd. 1-14-1 Nishi-Shimbashi, Minato-ku, Tokyo (73) Patent Holder 000174851 Mitsui-Dupont Fluorochemical Co., Ltd. 1-18-18 Sarakucho, Chiyoda-ku, Tokyo (74) 100074505 Attorney Toshiaki Ikeura (72) Inventor Yuji Kurokawa 2-40-17 Hongo, Bunkyo-ku, Tokyo Go-Wakai Building 6F Foundation for Global Environmental Technology Research, New Refrigerant Project Room (72) Inventor Junji Murata 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building 6F Foundation for Global Environmental Technology Research, New Refrigerant Technology Project Indoor (72) Inventor: Akira Sekiya 1-1-1, Higashi, Tsukuba, Ibaraki Pref., National Institute of Industrial Science and Technology (72) Inventor: Masanori Tamura 1-1-1, Higashi, Higashi, Tsukuba, Ibaraki Pref. 56) References JP-A-11-80791 (JP, A) JP-A-10-109954 (JP, A) JP-A-11-276634 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 7/50 C11D 7/26 C11D 7/28 C09K 3/00 C09K 5/04 CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1, 3, 3, 4, 4, 5, 5, 6, 6, 7,
An azeotropic or azeotrope-like composition comprising 7,7-undecafluoroheptane-2-one and at least one alcohol selected from methanol, ethanol and 2-propanol.