JPH01268650A - Tetrachlorodifluoroethane-based solvent composition - Google Patents

Abstract

PURPOSE:To provide a composition containing tetrachlorodifluoroethane as a main component, hydrocarbons, alcohols, etc., as arbitrary components and nitro compounds and epoxides, phenols, etc., as stabilizers and having excellent effect to suppress the corrosion of metals. CONSTITUTION:The objective composition is composed of tetrachlorodifluo-ro ethane and optionally hydrocarbons, alcohols, etc., and contains 100ppm-3% of a stabilizer consisting of nitro compounds (preferably nitromethane) and at least one kind of compound selected from epoxides (preferably 1,2-butylene oxide) and phenols. The composition has excellent effect to suppress the corro sion of metals and gives high thermal stabilization effect. Especially, the composi tion can be used in the cleaning of electronic parts, electric parts, etc., without causing the corrosion of the metal and, accordingly, the problems of contact fault, etc. The stabilizer may further contain amines, ethers, organic phosphites, furans, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a stabilized tetrachlorodifluoroethane solvent composition.

[Prior art and problems to be solved by the invention] Tetrachlorodifluoroethane or a solvent composition consisting of it and hydrocarbons or alcohols can be used for IC parts, precision machinery parts,
It is suitable for steam cleaning of various other articles and is not widely used, but its thermal stability is not necessarily sufficient.

[Means for Solving the Problems] The present invention has been made to improve the above-mentioned stability, and contains tetrachlorodifluoroethane as a main component, at least one selected from epoxides and phenols as a stabilizer, and nitrofluoroethylene as a stabilizer. This relates to a tetrachlorodifluoroethane solvent containing compounds, and an it1 product.

The solvent composition may contain at least one selected from hydrocarbons and alcohols.

In addition, as stabilizers, amines, ethers, amicins,
At least one selected from esters, organic phosphites, furans, ketones, and triazoles may be added in combination.

Tetrachlorodifluoroethane in the present invention includes tetrachloro-1,2-difluoroethane (n-112)
and tetrachloro-1,1-difluoroethane (R-1
Isomers of 12a) are known, and since these have similar physical properties, they can be used alone or in combination. R-112 has a boiling point of 92.8℃, R
-112a has a boiling point of 91.5°C, a KB value of about 70, and low toxicity with an allowable concentration of 500pp, making it extremely excellent as a cleaning solvent.

The composition of the solvent stabilized according to the invention is as follows.

() Composition weight% Tetrachlorodifluoroethane/hydrocarbons (99/1
~5/95) Tetrachlorodifluoroethane/Alcohols (9971~5/95) Can the above solvent composition be used as a solvent for various purposes? When used as a detergent for dry cleaning, etc., steam cleaning may be performed, and it is necessary to stabilize it thermally.

In particular, if the object to be cleaned or the material of the cleaning device is made of metal (iron, zinc, aluminum, copper, brass, various alloys, etc.), the effects of this metal will make it even more unstable.

Hydrocarbons used in the stabilized solvent composition of the present invention include pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-hebutane, 2-methylhexane, 3-
Methylhexane, 2.3-dimethylpentane, 2.4-
dimethylpentane, n-octane, isooctane, 2,
2.3- Trimethylpentane, nonane, 2.2.5-
Trimethylhexane, decane, dodecane, 1-pentene, 2-pentene, l-hexene, l-octene, 2-
Nonene, 1-decene, 3-ethylpentane, 3-methylpentane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,2,3-trimethylbutane, 4-methylhebutane, 2,4-dimethyl hexane, cyclopentane, cyclohexane, methylcyclopentane, 1,1
-dimethylcyclopentane, benzene, preferably n-hebutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 4-methylhebutane, cyclohexane, 1,1-dimethylcyclo It has an azeotropic composition with tetrachlorodifluoroethane, such as pentane and benzene. More preferred is n-hebutane.

Alcohols include methanol, ethanol, 1-propanol, 2-propanol, l-butanol, 2-butanol, iso-butyl alcohol, terL-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-propanol, -Methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, l-hexanol, 2-methyl-1-pentanol, 4-methyl-2-pentanol, 2-ethyl-1-butanol, l
-heptatool, 2-heptatool, 3-heptatool, l-octatool, 2-octatool, 2-ethyl-
1-hexanol, l-nonanol, L5,5-)limethyl-1-hexanol, 1-decanol, l-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, l-methylcyclohexanol, 2 - Methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol selected from 2α-terpineol, avinitinol 1, more preferably 1-propanol, 2-butanol, etc. having an azeotropic composition with tetrachlorodifluoroethane It is something you have.

In the present invention, a solvent composition containing tetrachlorodifluoroethane as an active ingredient can be well stabilized by adding at least one kind selected from epoxides and phenols and a stabilizer consisting of a nitro compound. . When the usage conditions of the solvent composition to be stabilized are severe and a high stabilizing effect is required, amines, ethers, amicins, esters, organic phosphites, and furans may be added to the above stabilizers. It is effective to add at least one member selected from the group consisting of , ketones and triazoles.

The amount of stabilizer added is not particularly limited, but
lpp~10%, preferably 10pp~5%, more preferably 100p based on parts by weight based on the solvent composition
f) ■~3%. In particular, phenols are toopp■
~1% is preferred.

As the nitro compounds, those represented by the general 2R-No. It is selected from propane, 2-nitropropane, nitrobenzene, etc., and nitromethane is more preferred. As the phenols, those represented by the following general formula are preferable, (where R,
, R', , R"IIR"' is Of (or carbon number 1-6
A chain or cyclic hydrocarbon group having saturated or unsaturated bonds. ) Phenol, 0-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, ineugenol, 〇-methoxyphenol, 4,4°-dihydroxyphenyl-2,2- Propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2
．． It is selected from 6-di-t-butyl-p-cresol and the like. More preferred are phenol and 2,6-di-t-butyl-p-cresol.

The amines are preferably those represented by the following general formula: R2-N(R'2)2. (Rz)2-NCR't)*,
(Rz)t-NR'2゜(Rz)J-R'z-N-(R
"2) 2, nz-R't-Ni1-R"2゜R2-CIIN(R'2)2-R"2-N-(R"t)
*.

(Rz)J-R'*-NH-R"z-N-(R"z)z
.

(I+2)J-(R'JI+)4-R'',,R2-NH
-R',.

(llz)2-N-OR', - (where R,, R',, R''2. hydrocarbon groups,) 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, cyphthylamine, tributylamine,
Dibenzylamine, 1-libentylamine, 2-ethylhexylamine, aniline, N,N-dimethylaniline, N,N-diethylaniline, ethylenecyamine, propylene diamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzyl Amine, diphenylamine, diethylhydroxylamine, N-phenyl-1-naphthylamine, dioctylamine, N-
It is selected from methylpencylamine and the like. More preferably diisopropylamine, diallylamine,
It is diphenylamine.

The ethers are preferably those represented by the following general formula: +10-R, -0-11', 110-R, -0-
It':l-0-R'', HO-R,-011゜(
Here, R,, R',, R'' are chain or cyclic hydrocarbon groups having 1 to 10 carbon atoms and having a saturated or unsaturated bond.) 1.4-dioxane, 1.2-butanediol .

Isopropyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether,
Diethylene glycol monoethyl ether, dibropylene gelicol methyl ether, ethyl isobutyl ether, ethyl isopropyl ether, ethyl isopentyl ether, ethyl naphthyl ether, ethyl vinyl ether, ethyl phenyl ether, anisole, anethole, ethyl propargyl 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 monobutyl 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, dimethyl ether, diethyl ether, di-normal propyl ether, dibutyl ether, and the like. More preferred are 1,2-butanediol and 1,4-dioxane.

Preferred amines are α-amylene.

β-amylene, γ-amylene, α-isoamylene, β-
Among them, β-amylene is more preferable.

Preferably, the esters are those represented by the following general formulas: OR', -GOOR'',

(Here, R,, R',, R''4 are hydrogen atoms or chain or cyclic hydrocarbon groups having 1 to 6 carbon atoms and having a saturated or unsaturated bond.) Methyl acetate, ethyl acetate, propyl acetate, Normal butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, ethyl carbamate, methyl carbamate, methyl salicylate Among them, methyl acetate is more preferable.

As the organic phosphites, those represented by the following general formula are preferable, (IlsO):+P, (Rs-R'5-
0)zP, (R50)zPOR's.

(Here, R,, R',, R''5. R'''5 is a hydrogen atom or a chain or cyclic hydrocarbon group having 1 to 18 carbon atoms and having a saturated or unsaturated bond.) Triphenyl phosphite, 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)
One selected from pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, etc. It is. More preferred is triphenyl phosphite.

The epoxides are preferably those represented by the following general formula: R,0,XR,0 (where R6 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,
) It is selected from 1.2-butylene oxide, epichlorohydrin, propylene oxide, 2.3-butylene oxide, styrene oxide, etc., and 1.2-butylene oxide is more preferable.

As the furans, those represented by the following general formula are preferable (where R?, R'?, and R"7 are hydrocarbon groups having 1 to 2 carbon atoms and having saturated and/or unsaturated bonds.) It is selected from tetrahydrofuran, N-methylvirol, 2-methylvirol, 3-methylvirol, etc., and N-methylvirol is more preferred.

As the ketones, those represented by the following general formula are preferable, (R11)2GO,RI5-(:0-R'A, (R
aN(:O)2゜R5-C0N-(R'a)z,
(Ra)JCON(R'a)z.

(Here, R8, R', R", RIll. are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms and having saturated or unsaturated bonds.) Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, maleic acid. Hydrazide, hydrazine phthalate, formamide, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylpropionamide, 2-pyrrolidone, N,N,N',N'-tetramethylurea , N
-Methylpyrrolidone and the like, more preferably methylethylketone.

Preferred triazoles are those represented by the following general formula: 9-N--R's, Rs-N:+-R'
9-OH2 old・9 OH X-Rs-L-R's-R"s+ R9-N5-R'
9-N-R"9■ R"9 (here, R9, R'9.R"9.R"°9 is a hydrogen atom or a chain or cyclic chain having a saturated or unsaturated bond having 1 to 16 carbon atoms) Hydrocarbon group. 5-
Chloro-benzotriazole, 1,2. : 1-benzotriazole, 1-[(N,N-bis-2-ethylhexyl)aminomethyl]benzotriazole, etc., and 1,2.3-benzotriazole is more preferable.

[Example 1 Examples 1 to 60 A first test was conducted for the purpose of confirming the stabilizing effect of the tetrachlorodifluoroethane solvent composition of the present invention.
Tetrachlorodifluoroethane in the present invention is R11
Although either R112a or R112a can be used, R112 will be shown here.

In accordance with JIS-KIEioo, mild steel pieces were placed in each of the liquid phase and gas phase parts of the stabilized/A composition shown in Tables 1 to 8 below, and the corrosion status of the mild steel pieces after heating for 48 hours was observed.

The results are shown in Tables 1 to 8.

Here, A-0 in the table indicates the following substance.

(A) Nitromethane, (B) Phenol.

(C) 2.8-di-t-butyl-p-cresol, (
D) Isopropylamine, (E) Diallylamine, (F
) diphenylamine, (G) 1,2-butanediol, (H) 1. ．． 4-dioxane, (Dβ-amidino,
(J) Methyl acetate, (K) triphenylphosphite,
(L) 1,2-butylene oxide, (M) tetrahydrofuran, (N) methyl ethyl ketone, (0) 1,2
．． 3-benzotriazole.

Table 1 Δ: Slight corrosion, ×: Considerable corrosion, Table 2 Δ: Slight corrosion, ×: Considerable corrosion, Table 3 Δ: Slight corrosion,
Table Δ: Slightly corroded, ×: Significantly corroded, Table 5, Table 6, Table 7 Δ: Slightly corroded, G, C Effects of the Invention] As is clear from the examples, the tetrachlorodifluoroethane solvent composition of the present invention has an excellent effect of suppressing metal corrosion,
A high stabilizing effect can be obtained. In particular, when corrosion occurs during cleaning of electronic parts, electrical parts, etc., the problem of contact failure occurs, and the tetrachlorodifluoroethane solvent composition of the present invention is effective as a countermeasure against this problem.

Claims (3)

[Claims] (1) A tetrachlorodifluoroethane solvent composition containing tetrachlorodifluoroethane as a main component and at least one kind selected from epoxides and phenols as a stabilizer and a nitro compound. (2) The solvent composition according to claim 1, wherein the solvent composition contains at least one selected from hydrocarbons and alcohols. (3) The stabilizer further contains at least one member selected from the group of amines, ethers, amylenes, esters, organic phosphites, furans, ketones, and triazoles. solvent composition.