JPH02185596A - Fluorinated hydrocarbon mixture composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can be used as a chlorofluorocarbon substitute, has excellent characteristics as solvent, and has an azeotropic point by mixing 1,1,2-trichlorotrifluoroethane with cis-1,2- dichloroethylene. CONSTITUTION:The title composition consists of 1,1,2-trichlorotrifluoroethane preferably in an amount of 81-99wt.% and cis-1,2-dichloroethylene preferably in an amount of 1-19wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel fluorinated hydrocarbon mixed composition that can be used as a fluorocarbon substitute and has excellent properties as a solvent and the like.

[Conventional technology] Fluorinated hydrocarbon compounds (hereinafter simply referred to as fluorocarbons) have low toxicity (many are nonflammable and chemically stable, and various fluorocarbons with different standard boiling points are available, so it is important to take advantage of these characteristics. Various fluorocarbons are used as solvents, blowing agents, propellants, refrigerants, etc.For example, 1,1.2-)Rechloroethane (R113) is used as a blowing agent. Trichloromonofluoromethane (R11) is used as a propellant, and dichlorodifluoromethane (R12) is used as a propellant or refrigerant.

[Problem to be solved by the invention] R11, R12, and R113, which are particularly stable chemically, have a long life in the troposphere and diffuse into the stratosphere, where they are decomposed by sunlight and the generated chlorine radicals become ozone. There is a movement to restrict the use of these conventional fluorocarbons because they are said to cause a chain reaction and destroy the ozone layer. Therefore, in place of these conventional fluorocarbons, there is active search for alternative fluorocarbons that do not destroy the ozone layer.

An object of the present invention is to provide a new fluorocarbon composition that can be used as a fluorocarbon substitute while reducing the amount of conventional fluorocarbons used and satisfying the excellent properties of the fluorocarbons. .

[Means for solving the problems] The present invention provides 1,1,2-trichlorofluoroethane (R1
13) and a fluorinated hydrocarbon mixed composition comprising halogenated hydrocarbons. The mixture of the present invention is nonflammable or flame retardant, has an azeotropic composition, and has higher detergency as a cleaning solvent than conventional R113 alone, so it is extremely useful as a substitute for R113.

The mixing ratio of the composition of the present invention is R113/CiS-1,2
-Dichloroethylene = 81 to 99% by weight/1 to 19% by weight, preferably 85 to 95% by weight, 15 to 15% by weight, more preferably 90% by weight/10% by weight for an azeotropic composition
It is. The azeotropic composition ratio is R113 and CiS-1,2-
It can vary by about ±0.5 to 1% by weight depending on the purity of dichloroethylene.

When it is necessary to stabilize the fluorinated hydrocarbon mixed composition of the present invention, stabilizers such as nitro compounds, phenols, amines, ethers, amicins, esters, organic phosphites, At least one member selected from the group of epoxides, furans, alcohols, ketones, and triazoles can be added. The amount added is not particularly limited, but is 1 ppm to 10%, preferably 10 ppm to 5%, based on the mixed solvent composition.
, more preferably l100pp to 3%.

As nitro compounds, those represented by the general formula R-NO□ (R: a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms and having a saturated or unsaturated bond) are preferred, including nitromethane,
It is selected from nitroethane, l-nitropropane, 2-nitropropane, nitrobenzene, etc., and nitromethane is more preferred. As the phenols, those represented by the following general formula are preferred, and are selected from 2,6-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: Rz-N(R' 2) 2. (R2) 1-N(R'
2) z, (R2)2-NR"2゜R' (Here, R,, R',, R",, R"' have OH or a saturated or unsaturated bond having 1 to 6 carbon atoms. Chain or cyclic hydrocarbon group) Phenol, O-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butylcatechol, catechol, isoeugenol, 0-methoxyphenol, 4,4 '-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methi salicylate (R2
)2N-R'2-N-(R'2)2. R2-R'2
-NH-R'2゜R2-CHN (R' 2) 2-R
'm-N-(R"' z)z.

(R2)2N-R'2-NH-R'2-N-(R"'
2)! .

(R2)2N-(R'2NH)4-R'2. R2-
NH-R'2゜(R2)2-N-OR'2 (here, R2, R'2. R"2. R"' x is a hydrogen atom or a saturated or unsaturated bond with 1 to 1O carbon atoms (chain or cyclic hydrocarbon group) pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-normal brobylamine,
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,
From N,N-diethylaniline, ethylenediamine, propylenediamine, diethylenetriamine, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, diethylhydroxylamine, N-phenyl-1-naphthylamine, dioctylamine, N-methylbenzylamine, etc. It is chosen. More preferred are diisopropylamine, diallylamine, and diphenylamine.

The ethers are preferably those represented by the following general formula, HO-R, -0-R'3. HO-R3-0-R', -0
-R'3. HO-R3-OH.

(Here, R3, R'3. R1+ is a carbon number of 1 to 10
A chain or cyclic hydrocarbon group having saturated or unsaturated bonds. ) 1.4-dioxane, 1.2-butanediol, 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 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, diiso Pentyl ether, diallyl ether, butyl glycidyl ether, allyl glycidyl ether, dipropyl ether,
It is selected from ethyl glycidyl ether, vinyl glycidyl ether, dimethyl ether, diethyl ether, di-normal propyl ether, dibutyl ether, 1,2-dimethoxyethane, trimethoxyethane, triethoxyethane and the like. More preferred are 1,2-butanediol, 1,4-dioxane, and 1,2-dimethoxyethane.

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

The esters are preferably those represented by the following general formula, R40-R'4-C0OR"4" (where R4, R'4. Chain or cyclic hydrocarbon group having a saturated bond.) Methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, ethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate, acrylic It is selected from butyl acrylate, phenyl acrylate, allyl acrylate, caprolactam, ethyl carbamate, methyl carbamate, methyl salicylate, etc., and methyl acetate is more preferable.

As the organic phosphites, those represented by the following general formula are preferable, (R1,o)ip, (Rr+-R'5
-0)3P+ (RsO)aPOR'B.

(Here, R5, R's, R''B, R'''5 are hydrogen atoms or chain or cyclic hydrocarbon groups having 1 to 18 carbon atoms and having a saturated or unsaturated bond.) Triphenyl phosphite, tris (nonylphenyl)
Phosphite, tridecyl 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 dipropylene glycol pentaerythritol 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, O, 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, and those selected from the following are more preferable, and N-methylpyrrole is more preferable.

As the ketones, those represented by the following general formula are preferable, (Ra)2GO, Re-Go-R'a, (RaNCO
)2°R8-C0N-(R'[1) 2. (RQ) 2
NGON (R'8) 2゜ (R?, R'? here?
, Rt is a hydrocarbon group having 1 to 2 carbon atoms and having a saturated and/or unsaturated bond. ) Tetrahydrofuran, N-methylpyrrole, 2-methylvirol, 3-methylvirol, etc. (where R8, R'
8. R″8.R″’B is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms and having a saturated or unsaturated bond. ) Acetone, methyl ethyl ketone, methyl isobutyl ketone, azodicarbonamide, maleic hydrazide, phthalic hydrazine, formamide, N-methylformamide, N,N-dimethylpormamide, N,N-diethylformamide, N-methylpropionamide, 2-pyrrolidone, N, N, N', N'-tetramethylurea, N
-Methylpyrrolidone and the like, more preferably methylethylketone.

As triazoles, those represented by the following general formula are preferred, (where R,, R''9.R'',, R'' is a hydrogen atom or a saturated or unsaturated bond having 1 to 16 carbon atoms) Chain or cyclic hydrocarbon group. )-5-chloro-
benzotriazole, 1,2.3-benzotriazole, 1-[(N,N-bis-2-ethylhexyl)aminomethyl]benzotriazole, etc., more preferably 1,2.3-benzotriazole It is.

The fluorinated hydrocarbon mixed composition of the present invention can be used, for example, in various applications similar to conventional R113, and in particular R113
It is advantageous in that it has better dissolving power than that used alone.

The fluorinated hydrocarbon mixed composition of the present invention can be used in various applications such as refrigerants, blowing agents, propellants, and solvents, just like conventional fluorocarbons.

Specific uses of solvents include flux, grease, oil, wax, abrasives, ink removers, paint solvents,
Extractants, stain removers, solvents for cleaning and dry cleaning various products made of ceramics, plastics, rubber, metals, etc. In particular, cleaning agents and draining agents for IC parts, electrical equipment, precision machinery, optical lenses, etc. can be mentioned. can. As a cleaning method, hand wiping, dipping, spray shaking, ultrasonic cleaning, steam cleaning, etc. may be employed.

[Examples] Example 1 1000 g of a solvent mixture having the following composition was placed in a distillation flask and distilled under atmospheric pressure using a rectification column with 20 theoretical plates.

(Composition) (Weight %) R113 (boiling point 47.6°C) 95 CiS-1,2-dichloroethylene (boiling point 60.6°C)
5 As a result, 200 g of a fraction was obtained at 42°C. As a result of measuring this product with a gas chromatograph, it had the following composition.

(Composition) (% by weight) R11390 CiS-1,2-dichloroethylene 10
Example 2 A flux cleaning test was conducted using the composition of the present invention shown in Table 1.

Flux (Sparkle Flux PO-F-309, manufactured by Senju Metals) was applied to the entire surface of the printed circuit board (copper-clad laminate), and after firing for 1 minute in an electric furnace at 200°C, it was immersed in a mixed solvent composition for 3 minutes. Table 1 shows the degree of flux removal.

Table 1: 0: Can be removed well ○: Very good △: Trace amount remains It is possible to reduce the amount of fluorocarbon used while satisfying the characteristics, and since it has an azeotropic point, there is no change in composition during recycling.It can be used in the same way as conventional single fluorocarbons, and does not require major changes to conventional technology. There are advantages. In addition, R113 has better ability to dissolve and remove flux and oil than R113 alone, which is often used as a solvent.
It is suitable as a cleaning solvent in place of 113.

Claims (2)

[Claims] 1.1,1,2-trichlorotrifluoroethane and C
iS-A fluorinated hydrocarbon mixed composition consisting of 1,2-dichloroethylene. 2.1,1,2-trichlorotrifluoroethane 81~
99% by weight and CiS-1,2-dichloroethylene 1~
A fluorinated hydrocarbon mixed composition consisting of 19% by weight.