JPH08253799A - Use of hydrofluoroalkene as detergent and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent which does not disrupt ozonosphere and is usable as a substitute for F113 and F114b by using a specific hydrofluoroalkene in a detergent for the surface of a solid.

SOLUTION: A hydrofluoroalkene represented by the formula: R_f-(CH₂-CF₂)_n- CH=CF₂ (wherein (n) is 1 or 2 and R_f is a 1-3C linear or branched perfluoroalkyl), preferably 1,1,3,3,5,5,6,6,6-nonafluoror-1-hexene, is used in a detergent for the surface of a solid. The detergent preferably comprises a mixture of this hydrofluoroalkene with at least one organic solvent liquid at room temp. and preferably selected among alcohols, ketones, esters, hydrocarbons, and chlorohydrocarbons (e.g. methanol).

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to the field of fluorohydrocarbons, and more specifically to the use of hydrofluoroalkenes as detergents on solid surfaces.

[0002]

BACKGROUND OF THE INVENTION 1,1,2-Trichloro-1,2,2-
Trifluoroethane (known in the art by the name F113) is a solid of very diverse nature due to its physicochemical properties, especially non-flammability, high wettability powder, low solvent power and low boiling point. It is still widely used industrially for cleaning and degreasing surfaces (metals, glass, plastics or composite solids). In the electronics field, F1
13 has been found to be particularly useful in flux removal and low temperature cleaning of printed circuits. Other uses of F113 include degreasing of high quality and precision metal parts such as gyroscopes and military, aviation or medical equipment, and delicate fiber and skin cleaning.

1,1-dichloro-1 instead of F113
In these various applications using fluoroethane (known under the name F141b), these solvents do not undergo phase separation with other organic solvents (eg methanol), especially when used under reflux. Even in the vapor phase, they are often mixed in the form of an azeotropic or pseudo-azeotropic mixture having substantially the same composition as the liquid phase.

[0004]

Unfortunately, F113, which belongs to a fully halogenated chlorofluorocarbon, is now banned because it is suspected of attacking or destroying ozone in the stratosphere. , F141b belonging to chlorofluorohydrocarbon has already been strictly regulated. Therefore, it does not have a destructive effect on ozone, and is used in various applications such as F113 and F14.
There is a need for a product that can replace 1b.

[0005]

[Means for Solving the Problems]

Formula _{(I): R f - (} CH 2 -CF 2) n -CH = CF 2 (I) [wherein, n equals 1 or 2, R _f, line containing 1-3 carbon atoms Representing a cyclic or branched perfluoroalkyl group] are hydrofluoroalkenes F113 and F
It has been found to have the same physicochemical properties as 141b, but without the potential for depleting ozone in the stratosphere.

Accordingly, the subject of the present invention is the F113 or F
An alternative to 141b is the use of hydrofluoroalkenes of formula (I) for various applications. Detergent compositions based on hydrofluoroalkenes also form part of the invention.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of formula (I) is a known compound [for example, the specifications of US Pat. Nos. 3,106,589 and 3,116,337; Am. Che
m. Soc. 82, 2868-71 (1960); Te
trahedron 1964, Volume 20, 497-5
See page 06]. The compound can be prepared in a manner known per se, eg substantially: in the presence of a copper-based catalyst and ethanolamine,
Adding 1,1-difluoroethylene to the corresponding perfluoroalkyl iodide R _f I, and-deiodating the resulting iodide R _f- (CH ₂ CF ₂ ) _{n + 1} -I in the presence of potassium alcohol. It can be industrially obtained by a multi-step method including a step of hydrogenating.

Among the compounds of formula (I) of the present invention, 1,
1,3,3,5,5,6,6,6-nonafluoro-1-
Particularly preferably hexene _{CF 3 CF 2 -CH 2 CF 2} -CH = CF 2, the compound as shown in the following table, except ozone depletion potential (ODP) is perforated comparable properties and F113 are doing.

[0009]

[Table 1]

Cleaning technology using F113 or F141b and F113 or F141 used for these purposes
Various compositions based on b are well known to the person skilled in the art and are described in the literature. Therefore, in the practice of the present invention, those skilled in the art will recognize that F113 or F141b is equivalent to a hydrofluoroalkene of formula (I), preferably 1,1,1.
All that is required is to replace it with 3,3,5,5,6,6,6-nonafluoro-1-hexene.

As in the case of F113 or F141b,
The hydrofluoroalkene of the formula (I) may be a single compound, a mixture of the compounds, or another organic solvent which is liquid at room temperature with the compound, for example, alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, Esters such as methyl acetate, ethyl acetate and ethyl formate, as well as methylene chloride, 2-methylpentane,
It can also be used as a mixture with chlorinated or non-chlorinated hydrocarbons such as 2,3-dimethylbutane, n-hexane and 1-hexene.

Particularly advantageous mixtures for the washing operation are, for example:
1,1, using linear or branched alcohols containing 1 to 8 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, pentanol, amyl alcohol or isoamyl alcohol. 3, 3, 5, 5,
It is an azeotropic or pseudoazeotropic composition formed from 6,6,6-nonafluoro-1-hexene.

If desired, a hydrofluoroalkene-based detergent composition according to the invention, such as in known detergent compositions based on F113 or F141b, is added to said composition, for example a nitroalkane. Conventional stabilizers such as (nitromethane, nitroethane, nitropropane etc.) or acetals may be added to stabilize against hydrolysis and / or radical attack which may occur during the washing process. The proportion of stabilizer may range from 0.01 to 5% of the total weight of the composition.

[0014]

The present invention will be described with reference to the following examples, but the present invention is not limited to these examples.

Example 1 : C ₂ F ₅ CH ₂ --CF ₂ --CH = C
F ₂ / methanol azeotrope (a) a compound of confirmation 100g of azeotropic mixture _{C 2 F 5 CH 2 -CF 2} -CH = CF 2 and methanol distillation column 100g (30 plates)
Introduce into boiling container. The mixture is then completely refluxed for 1 hour in order to equilibrate the system. About 40 g of a fraction is collected at a constant temperature (55.5 ° C.) and analyzed by gas chromatography.

Examination of the results shown in the table below shows the presence of a C ₂ F ₅ CH ₂ —CF ₂ —CH═CF ₂ / methanol azeotrope.

[0017]

[Table 2]

(B) Confirmation of azeotropic composition 200 g of a mixture consisting of 84.5% by weight of C ₂ F ₅ CH ₂ —CF ₂ —CH═CF ₂ and 15.5% by weight of methanol.
Is introduced into the boiling vessel of an adiabatic distillation column (30 plates). The mixture is then refluxed for 1 hour in order to equilibrate the system, then about 50 g of fractions are collected and the fractions and the distillation residue are analyzed by gas chromatography. The results shown in the table below indicate the presence of azeotropes.

[0019]

[Table 3]

When used for cleaning solder flux or degreasing metal parts, this azeotrope gives good results.

Examples 2-8 The process is carried out as in Example 1, except that other alcohols are used instead of methanol. The table below shows the boiling points and compositions of the azeotropes under standard pressure (1.013 bar).

[0022]

[Table 4]

Example 9 : Stabilizing composition 150 g of a mixture containing 93% by weight of C ₂ F ₅ CH ₂ —CF ₂ —CH═CF ₂ , 6% by weight of 2-butanol and 1% by weight of nitromethane as stabilizer. Is introduced into the ultrasonic cleaning tank. After refluxing the system for 1 hour, an aliquot of the vapor phase is collected. Analysis of the aliquot by gas chromatography shows the presence of nitromethane which suggests that the mixture is stabilized in the vapor phase.

[0024]

[Table 5]

Example 10 : Cleaning of Solder Flux 125 ml of the azeotropic composition of Example 1 is introduced into a small single-vessel experimental machine equipped with an ultrasonic generator and then the liquid is boiled.

Rosin-based solder flux (Alp
5 standard test circuits (IPC-B-25 model) which were coated with a flux F8 manufactured by Hametal Co., annealed at 230 ° C. for 30 seconds and recooled were immersed in a boiling liquid for 3 minutes under ultrasonic waves, Then rinse in the vapor phase for 3 minutes.

After air drying, the standardized procedure IPC-TM650 Nos. 2.3.25 and 2.3.26 and standard MIL.
-Evaluate the quality of the wash by measuring the amount of ionic residues according to STD-2000. The value obtained, 1.79 μg
eq. NaCl / cm ² is a threshold value allowed in the electronics field (2.5 μg.eq.NaCl / cm ² ).
Is far below.

Claims (8)

[Claims] 1. A formula _{(I): R f - (} CH 2 -CF 2) n -CH = CF 2 (I) [wherein, n equals 1 or 2, R _f is one to three Representing a linear or branched perfluoroalkyl group containing carbon atoms] as a cleaning agent for solid surfaces of hydrofluoroalkenes. 2. The hydrofluoroalkene is 1,1,3.
Application according to claim 1, which is 3,5,5,6,6,6-nonafluoro-1-hexene. 3. A solid surface cleaning composition comprising a mixture of the hydrofluoroalkene according to claim 1 or 2 and at least one organic solvent which is liquid at room temperature. 4. The composition according to claim 3, wherein the solvent is selected from alcohols, ketones, esters, hydrocarbons and chlorinated hydrocarbons. 5. 1,1,3,3,5,5,6,6,6-
A composition according to claim 4 consisting of nonafluoro-1-hexene and a linear or branched alcohol containing from 1 to 8 carbon atoms. 6. The composition according to claim 3, further comprising at least one stabilizer. 7. The composition according to claim 6, wherein the stabilizer is a nitroalkane or acetal. 8. The proportion of stabilizer is 0.1% of the total weight of the composition.
The composition according to claim 6 or 7, which is 01 to 5%.