JPH03173835A - Stabilization of azeotropic and azeotropy-like composition comprising trichlorodifluoroethane as main ingredient - Google Patents

Abstract

PURPOSE:To thermally stabilize an azeotropic and an azeotropy-like composition comprising trichlorodifluoroethane as a main ingredient hydrocarbon, alcohol, etc., by adding a stabilizer such as nitro compound, phenol, amine, etc. CONSTITUTION:An azeotropic and an azeotropy-like composition comprising trichlorodifluoroethane as a main ingredient and a hydrocarbon, an alcohol, a ketone, an ether, an ester, a halogenated hydrocarbon, etc., having a boiling point (45-110 deg.C) close to that of the main ingredient is blended with a stabilizer such as a nitro compound, a phenol, an amine, an ether, an amylene, an ester, an organic phosphite, an epoxide, a furan or an alcohol b give heat stability in vapor cleaning. The amount of the stabilizer added is 100ppm-3% (weight) based on the azeotropic composition. The azeotropic composition is useful as a flux detergent, a de-fatting detergent, detergent for dry cleaning, water- removing solvent, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for stabilizing fluorocarbon azeotropic and azeotrope-like compositions.

[Prior art and problems to be solved by the invention] Fluorinated hydrocarbon compounds (hereinafter simply referred to as fluorocarbons) are often less toxic and chemically stable, and various types of fluorocarbons with different standard boiling points are available. Taking advantage of these properties, it is widely used in many applications such as solvents, blowing agents, propellants, and refrigerants.

Among these, trichlorodifluoroethane, which is used as the main agent in the present invention, is particularly important for CF, which is involved in the recent problem of ozone layer depletion.
The present inventors have previously proposed that this is a useful alternative substance as a countermeasure against C regulations (Japanese Patent Application No. 62-288442).
(See Japanese Patent Application No. 62-285425, etc.).

Furthermore, according to U.S. Pat. It is known that an azeotropic composition consisting of n-hexane, n-hexane, and
- Forming an azeotropic composition with hydrocarbons such as hebutane, Japanese Patent Application No. 1-159464, Japanese Patent Application No. 1-163827
proposed forming an azeotropic composition with chlorinated hydrocarbons such as trichlorethylene and 1゜1.1-trichloroethane, and Japanese Patent Application No. 141 in Japanese Patent Application No. 141. There is.

These azeotropic compositions are mixtures of 1,1,2-trichloro-2,2-difluoroethane, which is a fluorocarbon compound with relatively low dissolving power, and an organic compound with relatively high dissolving power, so they are particularly It is expected to improve cleaning performance when used as a solvent. Furthermore, these azeotropic compositions have many advantages, such as the ability to perform steam cleaning, which is widely used as a cleaning method for IC parts, precision machinery parts, and various other articles, since the liquid composition and vapor composition are constant. have.

However, when used with heat such as steam cleaning, the thermal stability is not necessarily sufficient, and there are concerns about thermal decomposition of these compositions and corrosion of metal members by acids that are decomposition products.

[Means for Solving the Problems] The present invention has been made to improve the above-mentioned stability, and uses trichlorodifluoroethane as a main ingredient, and contains hydrocarbons, alcohols, ketones, ethers, and halogenated hydrocarbons. azeotropic and azeotrope-like compositions consisting of one or more of the following, nitro compounds, phenols,
A compound characterized in that at least one stabilizer selected from the group of amines, ethers, amidines, esters, organic phosphites, epoxides, furans, alcohols, ketones, and triazoles is added. The present invention relates to a method for stabilizing boiling and azeotrope-like compositions.

The azeotrope and azeotrope-like compositions stabilized according to the invention are those based on trichlorodifluoroethane;
The main ingredients are 1,1,2-trichloro-2,2-difluoroethane (R122), 1,2,2-trichloro-1,
2-difluoroethane (R122a) and l.

1,1-Trichloroq-2,2-difluoroethane (R
Any one of the isomers of 122b) may be used alone or a mixture of two or more thereof may be used.

In addition, as an adjuvant for the composition stabilized according to the present invention, a compound that improves the dissolving power of trichlorodifluoroethane and exhibits an azeotrope or azeotrope-like property can sufficiently exhibit the stabilizing effect of the present invention. It is possible. In addition, when considering the stabilizing effect, for example, from the viewpoint of stabilizing both the solvent liquid and the solvent vapor during steam cleaning, the three components of the composition, the main agent, the adjuvant, and the additive stabilizer, may be azeotropic or synchronous. Since it is desirable to form a boiling point, it has been confirmed that azeotropic and azeotrope-like compositions in which the following compounds are used as adjuvants have better stabilizing effects.

The hydrocarbons used as adjuncts in the composition stabilized according to the present invention have a boiling point similar to that of trichlorodifluoroethane, the main ingredient, from the viewpoint of exhibiting an azeotrope or azeotrope-like behavior.
45°C to 110°C), particularly preferably n-hexane, 2-methylpentane, 3-methylpentane, n-hebutane, 2-methylhexane, 3-methylpentane,
Methylhexane, 2.2-dimethylpentane, 2.3-
Dimethylpenkune, 2.4-dimethylpenkune, 3.3
-dimethylpentane, 3-ethylpentane, 2.2.3
-)-limethylbutane, cyclohexane and methylcyclopenkune.

Alcohols as adjuvants in the composition stabilized according to the present invention are compounds having a boiling point similar to that of trichlorodifluoroethane (45°C to 110°C), which is the main ingredient, from the viewpoint of exhibiting an azeotrope or azeotrope-like behavior. are preferred, and particularly preferred are methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and isobutanol.

5ec-butanol, ter-butanol, ter-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol and propargyl alcohol.

The ketones used as adjuvants in the composition stabilized according to the present invention have a boiling point similar to that of the main ingredient trichlorodifluoroethane (4
5° C. to 110° C.), particularly preferred are acetone, methyl ethyl ketone, 2-pentanone and 3-pentanone.

Ethers used as adjuvants in the composition stabilized according to the present invention have a boiling point similar to that of trichlorodifluoroethane, the main ingredient, from the viewpoint of exhibiting an azeotrope or azeotrope-like property.
45°C to 110°C), particularly preferably dipropyl ether, diisopropyl ether, 2-methylfuran, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-jethoxyethane, 2-methoxyethanol, 2-ethoxy These are ethanol, 2-isopropoxyethanol and 2-butoxyshetanol. In the esters used as adjuvants in the composition stabilized according to the present invention, compounds having a boiling point similar to that of trichlorodifluoroethane (45°C to 110°C), which is the main ingredient, from the viewpoint of exhibiting an azeotrope or azeotrope-like property are used. are preferred, particularly preferably ethyl formate, propyl formate, butyl formate,
Isobutyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate,
5ec-butyl acetate, methyl propionate and ethyl propionate.

The halogenated hydrocarbons used as adjuvants in the composition stabilized according to the present invention have a boiling point similar to that of trichlorodifluoroethane (45°C to 110°C), which is the main ingredient, from the viewpoint of exhibiting an azeotrope or azeotrope-like behavior. Preferably, compounds having 1,1-trichloroethane, trichloroethylene, tetrachlorethylene, dichloromethane, 1-bromopropane, 2-bromopropane, 1.1
．． 2-Trichloro-1,2,2-)rifluoroethane (R
113), 1, 1, 2, 2. -tetrachloro-1,2
-dichloroethane (R112), 1,2-dichloro-
1-fluoroethane (R141), 1,2.2-trichloro-2-fluoroethane (R131a), 1,2-dichloro-1,2-dichloroethane (R132), 1.1
-dichloro-2,2-dichloroethane (R132a)
, 1.1-dichloro-2,2,3,3,3-pentafluoropropane (R225ca1, 1.3-dichloro0-
1.2,2゜3.3-pentafluoropropane (R225
cb), l-chloro-2,2,3,3-tetrafluoropropane (R244ca), 1.3.3-trichloro-1
, 1,2,2-tetrafluoropropane (R224ca1
, 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R224cb), 1,3-dichloro-1
,1,2,2-tetrafluoropropane (R234cc)
.

1-chloro-1,2,2,3,3-pentafluoropropane (R235ca), 1,1-dichloro-1,2,2
-trifluoropropane (R243cc), 1,1-dichloro-2,2-difluoropropane (R252ca),
1.1-dichloro-2,2-dichloropropane (R25
2cb), l-chloro-2,2-dichloropropane (8
262ca), 1,1-dichloro-o-1,2,2,3,
3-Pentafluoropropane (R225cc), 1.4-
Dichloro-1,2,2,3-tetrafluoropropane (R
234ca), 1゜1-dichloro-2,2,3,3-tetra,fluoropropane (R234cb), 1.1-dichloro-1,2,2,3-tetrafluoropropane (R2
34cd1.1.3-dichloro-1,2,2-)-rifluoropropane (R243ca), 1,1-dichloro-2
゜2,3-) Rifluorobloban (R243cb), 1
-Chloro-1,2,2,3-tetrafluoropropane (R
244cb) and ■-chloro2.2.3-trifluoropropane (R253cal).

This azeotropic composition can be used as a solvent for various purposes, but
Flux cleaning agent, degreasing cleaning agent, wax removal cleaning agent,
When used as a detergent for dry cleaning, a water removal solvent, etc., steam cleaning may be performed and it is necessary to thermally stabilize it. In particular, if the object to be cleaned or the cleaning equipment is made of metal (iron, zinc, magnesium, aluminum, solder, copper, brass, phosphor bronze, silver, various alloys, etc.), the composition will become even more unstable due to the influence of this metal. This will cause decomposition of the material and corrosion of metal parts.

The present invention provides nitro compounds, phenols, amines,
By adding at least one member selected from the group of ethers, amitons, esters, organic phosphites, epoxides, furans, alcohols, ketones, and triazoles to the present azeotropic composition, it is possible to improve (stabilize) the azeotropic composition. These stabilizers can be used singly or as a mixture of two or more, and the azeotropic composition can be used under severe conditions.

When a high stabilizing effect is required, it is effective to use a mixture of stabilizers. The amount of the stabilizer added is not particularly limited, but is lppm-10%, preferably 10 ppm to 5%, based on parts by weight based on the present azeotropic composition.
More preferably, it is 1100 pp to 3%.

As the nitro compounds, those represented by the general formula R-NO, (R: a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms and a saturated or unsaturated bond) are preferred, and include nitromethane, nitroethane, l-nitro It is selected from propane, 2-nitropropane, nitrobenzene, etc. More preferred are nitromethane and nitroethane.

As phenols, those represented by the following general formula are preferable, (where R, R', R", R"' are OH or a chain or cyclic group having saturated or unsaturated bonds having 1 to 6 carbon atoms. Hydrocarbon group) Phenol, 0-cresol, m-cresol, p-cresol, thymol, p-ter-butylphenol, ter-butylcatechol, catechol, isoeugenol, 0-methoxyphenol, 4,4°-dihydroxyphenyl- 2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2.6-
It is selected from di-t-butyl-p-cresol and the like. More preferred are phenol, 4,4-dihydroxyphenyl-2,2-propane, and 2,6-di-t-butyl-p-cresol.

As the amines, those represented by the following general formula are preferable, R-N(R')i, (R), -N(R')z
, (R), -NR'(R)2N-R'-N-(R
")2 R-CHN (R'), -R"-N-(R'")2(
R)2N-R'-NH-R"-N-(R"')2(R
)2N-(R'N)I), -R'', R-N)I-
R', (R), -N-OR' [where R, R
', R', R'' is a hydrogen atom or a chain or cyclic hydrocarbon group having 1 to 8 carbon atoms and having a saturated or unsaturated bond] Pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine ,
Diallylamine, triethylamine, N-methylaniline, pyridine, picoline, morpholine, N-methylmorpholine, triallylamine, allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, Propylamine, butylamine, isobutylamine, sec-butylamine, tertiary-butylamine, dibutylamine, tributylamine,
Dibenzylamine, tripentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, It is selected from diethylhydroxylamyl and the like. More preferred are diisopropylamine and diallylamine.

The ethers are preferably those represented by the following general formula, HO-R-0-R', HO-R-0-R'-0-R'
, HO-R-OH.

R-0-R'-CH-R'R-0-R'-0
-R"L-→"R-0-CH-R',R-0-R'-(OR
”).

L-→" [Here, R, R', R' are chain or cyclic hydrocarbon groups having saturated or unsaturated bonds having 1 to 10 carbon atoms,] 1.4-dioxane, 1.2-butane Diol, isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl ether, ethyl isobutyl ether, ethyl isopropyl ether, ethyl isopentyl ether, ethyl naphthyl ether, ethyl vinyl ether,
Ethyl phenyl ether, anisole, anethole, ethyl propagyl ether, ethyl propyl ether, ethyl methyl ether, ethylene glycol, methyl glycidyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol monophenyl ether, ethylene glycol mono Butyl ether, ethylene glycol monobenzyl ether, diallyl ether, allyl ethyl ether, diisopentyl ether, diallyl ether, butyl glycidyl ether, allyl glycidyl ether, dipropyl ether, ethyl glycidyl ether, vinyl glycidyl ether,
It is selected from dimethyl ether, diethyl ether, di-normal propyl ether, dibutyl ether, 1,2-dimethoxyethane, 1,2-jethoxyethane, trimethoxyethane, triethoxyethane and the like.

More preferred are 1.4-dioxane, butyl glycidyl ether, 1.2-dimethoxyethane, and 1.2-jethoxyethane.

The amylenes are preferably selected from α-amylene, β-amylene, γ-amylene, α-isoamylene, β-isoamylene, etc., and β-amylene is more preferable.

The esters are preferably those represented by the following general formula, [where R, R', R'' are hydrogen atoms or carbon atoms 1 to 6]
Chain or cyclic hydrocarbon group having a saturated or unsaturated bond] Methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, acrylic acid It is selected from methyl, butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, ethyl carbamate, methyl carbamate, methyl salicylate, etc., and methyl acetate and methyl salicylate are more preferred.

As the organic phosphites, those represented by the following general formula are preferable, (RO)sP, (R4'-0)sP, (RO)
zPOR'.

[Here, R, R', R", R'" are hydrogen atoms or chain or cyclic hydrocarbon groups having 1 to 18 carbon atoms and having a saturated or unsaturated bond] Triphenylphosphite, tris(nonylphenyl)
Phosphite, triethyl phosphite, tris(2-
ethylhexyl) phosphite, tridecyl phosphite, tributyl phosphite, diphenyl mono(2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl monotridecyl phosphite,
Dilauryl hydrogen phosphite, diphenyl hydrogen phosphite, tetraphenyl dibrobylene glycol bentaerythritol tetraphosphite, trilauryl trithiophosphite, bis(tridecyl)
selected from pentaerythritol diphosphite, bis(norylphenyl)pentaerythritol diphosphite, tristearyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-d-ter-butylphenyl) phosphite, etc. be.

More preferred are triphenyl phosphite and tributyl phosphite.

The epoxides are preferably those represented by the following general formula: ROlXRO [Here, R is a chain or cyclic hydrocarbon group having 1 to 8 carbon atoms and having a saturated or unsaturated bond. X is a halogen atom] The epoxides are preferably selected from 1,2-butylene oxide, epichlorohydrin, propylene oxide, 2,3-butylene oxide, styrene oxide, etc., and more preferably 1,2-butylene oxide. , epichlorohydrin.

As the furans, those represented by the following general formula are preferable, [where R, R', R'' are hydrocarbon groups having saturated and/or unsaturated bonds having 1 to 2 carbon atoms] tetrahydrofuran, N -Methylvirol, 2-methylvirol, 3
-Methylvirol, etc., and N-methylvirol is more preferred.

As alcohols, those represented by the following general formula are preferable, R-OH, NHI-R-OH, R-0-R'-OH, R
-R'-OH [here, R, R' are chain or cyclic hydrocarbon groups having saturated and/or unsaturated bonds having 1 to 6 carbon atoms,] methanol, ethanol, l-propanol, 2- propatool, l-butanol, isobutanol, 5ec-
butanol, ter-butanol, allyl alcohol,
benzyl alcohol, ter-amyl alcohol, 1
-amino-2-propertool, propargyl alcohol,
inbutanol, butanol, 3-methyl-pentyne-
More preferably, it is selected from 3-ol, 1-methoxy-2-propatol, 3-methyl-1-butyl-3-ol, 2-methyl-3-butyn-3-ol, and the like.

5ec-butanol, propargyl alcohol.

As the ketones, those represented by the following general formula are preferable, and (R) zco, R-Go-R', (RNC
O) 2゜[Here, R, R', R'', R'' are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms and having saturated/unsaturated bonds] Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonate Amide, maleic hydrazide, phthalic hydrazine, formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylpropionamide, 2
-pyrrolidone, N,N.

It is selected from N', N'-tetramethylurea, N-methylpyrrolidone, etc., and more preferably methylisobutylketone and 2-pyrrolidone.

The triazoles are preferably those represented by the following general formula: -A chain or cyclic hydrocarbon group having 16 saturated or unsaturated bonds, X is a halogen atom, ]2-(2°-hydroxy-5°-methyl-phenyl)benzotriazole, 2-(2°-hydroxy -3'-ter-butyl-
5°-methylphenyl)-5-chloro-benzotriazole, 1,2.3-benzotriazole, l-[(N,
N-bis-2-ethylhexyl)aminomethyl 1-benzotriazole, etc., and 1,2.3-benzotriazole is more preferred.

[Example] For the purpose of confirming the effects of the method for stabilizing azeotrope and azeotrope-like compositions of the present invention, the following tests were conducted on the compositions shown in Table 1.

In accordance with JIS-1600, metal pieces were placed in each of the n&phase and gas phase parts of the stabilizing compositions shown in Tables 2 to 19 below, and the corrosion status of the metal pieces was observed after 48 hours had elapsed.

The results are shown in Tables 2 to 19 along with comparative examples (Table 20).

The symbols in the table are as follows.

0: No corrosion, ○: No corrosion △: Slight corrosion, X: Corrosion Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 [Effects of the invention] Stabilization of azeotropic and azeotrope-like compositions of the present invention As is clear from the examples, the method is excellent in suppressing metal corrosion and provides a high stabilizing effect.

In particular, when corrosion occurs during cleaning of electronic parts, electrical parts, etc. using these azeotrope and azeotrope-like compositions, the problem of contact failure occurs, but this is a very effective countermeasure against such problems.

Claims (1)

[Claims] 1. Azeotropic and azeotrope-like compositions containing trichlorodifluoroethane as a main ingredient and one or more of hydrocarbons, alcohols, ketones, ethers, esters, and halogenated hydrocarbons, Addition of at least one stabilizer selected from the group of compounds, phenols, amines, ethers, amylenes, esters, organic phosphites, epoxides, furans, alcohols, ketones, and triazoles. A method for stabilizing azeotropic and azeotrope-like compositions.