CS51391A2 - Azeotropic solvents' mixture - Google Patents

Description

Azeotropic solvent mixture Ό

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Technical field

The invention relates to an azeotropic solvent mixture comprising dichloropentafluoropropane (hereinafter referred to as HCFC-225) and a fluorinated alcohol.

Trichlorotrifluoroethane (hereafter referred to as CFC-113), one of the chlorofluoroethane compounds, is non-flammable, has low toxicity to living organisms, and has excellent solubility since it can dissolve fats and oils, fatty substances and waxes, etc., without would damage polymeric substances such as plastics and rubbers. For this reason, CFC-113 is used alone, or in the form of a mixture, or azeo-tropical mixture with another organic solvent, such as solvent, cleaning solvent, and the like.

Recently, the problem of environmental pollution has arisen worldwide, with chlorofluoroethane compounds in which all hydrogen atoms are ethane substituted with chlorine atoms and fluorine atoms (hereafter referred to as perhalogenes), such as CFC-113, destroying the Earth's ozone layer. . For this reason, there is an urgent search for a way to reduce the use of such perhalogenethanes or to exclude their use at all.

Background Art

One way to reduce the use of perhaloethane is to use a mixed solvent containing CFC-113 in a mixture with an organic solvent that is different from the halo-ethane. However, in this process, the amount of CFC used can only be reduced to a certain extent, whereas the mixed solvent has a reduced performance.

When using CFC-113 in the form of a mixed solvent, it is also desirable to be able to easily control the composition thereof, further to allow the solvent to be easily regenerated and reused, and in addition it is desirable to use a solvent for the solvent. steam purification. To meet these requirements, the mixed solvent needs to form an azeotropic mixture. Finding such mixtures is not easy. For these reasons, no suitable substitute has been found to date.

A suitable substitute has not been found even among solvents that do not contain any perhalogenethanes, although many attempts have been made. Although mixed solvents formed by halogenated organic solvent and fluorinated alcohol have been described in Japanese Patent Publication No. 12,864 / 1971, the azeotropic mixtures of HCFC-225 and fluorinated alcohol have not been described therein. Also, mixed solvents consisting of halogenated organic solvent in particular, the fluorocarbon solvent and the hydrocarbon chain alcohol are already well known. However, these mixed solvents have the disadvantage of releasing an acid, such as hydrochloric acid, in the presence of moisture, which causes metal corrosion. Therefore, using such mixed solvents, it is necessary to remove moisture, or to use different types of materials to be washed and various conditions limited. SUMMARY OF THE INVENTION It is an object of the present invention to provide an azeotropic solvent composition which does not contain any CFC-113, which improves the cleaning performance of the "Rogin Flux" flux, which is also ozone-damaging and non-flammable.

SUMMARY OF THE INVENTION The present invention provides an azeotropic solvent composition comprising dichloropentafluoropropane and a fluorinated alcohol. Surprisingly, the composition of the invention does not corrode metals even in the presence of moisture and is stable. The KCFC-225 used in the present invention has isomers such as 1,1-dichloro-2,2,3,3,3-pentafluropropane (boiling point 51C), 1,2-dichloro-1,2,3,3,3- pentafluoropropane (boiling point 56 ° C), 1,3-dichloro-1,2,2,3,3-pentafluoropropane (boiling point 56 ° C), 2,2-dichloro-1,3,3,3,3-pentafluoropropane (boiling point 54 ° C), 2,3-dichloro-1,2,2,3,3-pentafluoropropane (boiling point 56 ° C), 3,3-dichloro-1,2,2,2,3-pentaftaoropropane (boiling point 58 ° C), 1,1-dichloro-1,2,3,3,3-pentafluoropropane (boiling point 49 ° C), 1,3, dichloro-1,1,2,3,3-pentafluoropropane (temperature boiling point 48 ° C), α1,2, -dichloro-1,1,3,3,3 - pentafluoropropane (boiling point 50 ° C) HCFC-225 is non-flammable, has low toxicity to living organisms, is chemically stable and has selective solubility in the sense that it can wash fats and oils, or remove stains caused by these substances, with no effect on plastics, rubbers, metals, etc. Outside, HCFC-225 damages the ozone layer less than CFC-113.

Specific examples of fluorinated alcohols which may be used in the present invention include compounds containing at least 2 fluorine atoms and not less than 2 carbon atoms per molecule. Specifically, they are fluorinated alcohols having a composition corresponding to the following formulas.

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F (CF 2 CF 2 -h-CH 2 CH 2 CH 2 OH CF.

Wherein each of a, c, e, g, and i is an integer from 1 to 5, and b, d, f, h, and j are each an integer from 1 to 3. Of these, trifluoroethanol (boiling point 77 ° C), tetrafluoropropanol (boiling point: 107 ° C) and pentafluoropropanol (hereinafter referred to as "5FP", boiling point: 81 ° C) are preferred. Even more preferred is 5FP because it is non-flammable. Fluorinated alcohols can be used alone or in bulk.

The composition of the invention comprises HCFC-225 having the listed properties and a fluorinated alcohol. Since it is an oazeotropic mixture, the composition of the liquid solvent can be readily controlled. Also, the regeneration and reuse of the mixed solvent of the present invention is easy so that it can be used for steam cleaning. In addition, the composition according to the invention is very much like a flux, because it has a significant effect on the efficient electrical and electronic industry, a cleaning solvent for the removal of flux, and the bonding of printed circuit boards. According to the invention, the composition is permanently stable, particularly remarkably stable in wetness and metal. It has a selective solubility, can wash and remove stains only, without bad plastics, rubbers, metals and the like. In addition, the blend damages the ozone layer rather than CFC-113 and is

A mixture of HCFC-225 and a fluorinated alcohol forms an azeotropic mixture or azeotrope-like mixture in an HCFC-225 to fluorinated alcohol ratio of 99.5 to 91.0 / 0.5 to 9.0, preferably 99.5 to 88.0. 0.5 to 12. The azeotropic mixture has a boiling point of the azeotrope from 47.5 to 57.5 ° C. Examples of such azeotropic and similar mixtures are the azeotropic boiling point 49.8 ° C, which contains 93.5% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane (boiling point 51 ° C) and 6.5% by weight of pentafluoropropane (5FP boiling point 81 ° C), azeotropic mixture (carbon black temperature 54.5 ° C) 92.2% by weight of 1,3-dichloro-1,2,2,3,3-pentafluoropropane (boiling point 56.1 ° C) and 7.8% by weight 5FP (boiling point 81 ° C), azeotrope-like mixture containing 93.5 to 92.2% by weight of a mixture of 1.1-dichloro-2.2, 3-3 , 3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane, at a weight ratio of 1,1-dichloro-2,2,3,3,3-pentafluoropropane to 1 3-dichloro-1,2,2,3,3-pentafluoropropane 0.5 to 99.5 / 99.5 to 0.5 preferably 5 to 60/95 to 40, preferably 20 to 50/80 to 50, and 6 5 to 7.8% by weight of 5FP, and the like.

The composition comprising predominantly HCFC-225 of the present invention is suitable not only for use as a cleaning solvent for removing rogin flux which is used in printed circuit boards and which is poorly removed using a single component solvent, but also for various uses, typically CFC-113 is used, for example as a degreasing solvent for removing paraffin, animal and vegetable oils, processing oils, as a cleaning solvent for removing the separating agents used in the forming and processing of plastics, as a cleaning solvent for removing waxes used to temporarily fix silicone layers (wafers) ) for semiconductors and further for use in the processing of crystal glass and ceramics, such as in cutting, some polishing. Furthermore, the composition of the invention may be used in the manufacture of pressure sensitive adhesive strips, paints, inks and the like and as a dispersing medium for ceramic or metal powders, such as solids, dehydrating agents and desiccants, as solvent-based cleaning agents and the like. a composition according to the invention chemically stable with solvents that contain an aliphatic addition of a stabilizer.

Ixono. It is preferred that the stabilizers distillate together with the azeotropic composition of the invention, or that the stabilizer / azeotropic mixture forms a further azeotropic mixture, except that the stabilizers should have a strong stabilizing effect of the mixture.

Examples of the above-mentioned stabilizers are aliphatic nitro compounds such as nitromethane, nitroethane and nitropropane; acetylene alcohols such as 3-methyl-1-butin-3-ol and 3-methyl-1-pentin-3-ol; epoxides such as glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 1,2-butylene oxide, cyclohexene oxide and epichlorohydrin; ethers such as dimethoxymethane, 1,2-dimethoxyethane, 1,4-dioxane and 1,3,5-trioxane; unsaturated hydrocarbons such as hexene, heptene, octene, 2,4,4-trimethyl-1-pentene, pentadiene, octadiene, cyclohexene and cyclopentene; olefinic alcohols such as allyl alcohol, 1-butene-3-ol and 3-methyl-1-buten-3-ol; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; etc. The stabilizers can be used alone or in mixtures.

In addition, other compounds may also be used. If the stabilizer is used in combination with other compounds, synergistic effects can be achieved. Examples of such compounds include phenols such as phenol, trimethylphenol, cyclohexylphenol, thymol, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole and isoeugenol; amines such as hexylamine, pentylamine, dipropylamine, diisopropylamine, diisobutylamine, triethylamine, tributylamine, pyridine, N-methylmorpholine, cyclohexvlamine, 2,2,6, β-tetramethylpiperidine and Ν, Ν'-diallyl-β-phenenyl-diamine; triazoles such as benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benztriazole and chlorobenztriazole; and so on.

The amount of stabilizer depends on its kind and is determined accordingly. Typically, the amount is from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight. based on the azeotropic mixture. When nitromethane is used in this case, the amount of nitromethane is usually from 0.1 to 1.0% by weight, based on the azeotropic mixture. Nitromethane is usually preferred as a stabilizer.

The stabilizers are used in an amount such that the azeotropic mixture is not disturbed. Since the stabilizer is usually used in small amounts, such as less than 1% by weight, the addition of an azeotropic stabilizer does not affect the mixture much.

The composition of the invention has the same or better CFC-113 properties in terms of cleaning performance in the case of flux removal, non-flammability, chemical stability, and the like. The invention has selective dissolution capabilities, with virtually no effect on plastics, rubbers, and especially metals. The azeotropic solvent composition of the present invention also contains the major component of HCFC-225, which depletes the ozone layer of less than CFC-113, has an excellent fluxing capacity of roginflux, i.e., can remove it, which is capable of retaining various excellent solvent levels. properties of HCFC-225. In addition, the composition of the invention has the excellent properties required for an azeotropic solvent mixture, i.e., has a low boiling point, high solubility, readily reacts with the liquid phase composition, and simply seregenerates and reuses.

In particular, when the mixture according to the invention is used in the presence of moisture, it does not undergo metal corrosion, although the corrosion of metals in the presence of water could not be prevented when combined with alcohol as usual. Consequently, the compositions according to the invention can be used under different conditions of use and in combination with different types of materials to be washed.

The invention is better described in the following examples. The examples are more particularly limiting and do not limit the scope of the invention in any way. All% are% by weight unless indicated by weight. DETAILED DESCRIPTION OF THE INVENTION Example 1. Also the parts are parts 1 and 1

To a distillation flask, add 200 g of a mixture of 1,1-dichloro-2,2,3,3,3-pentafluoropropane (225 µl boiling point 51 ° C and pentafluoropropaole (5FP) boiling point 81 ° C, in a weight ratio of 225φ: 5FP) = 50: 50. The mixture is distilled under a normal pressure in a rectification column with a theoretical number of 30, a distillate having a azeotropic temperature of 49.8 ° C, which is below the boiling point of both solvents used.

Gas chromatography analysis indicated that the desilate was 93.5% 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 6.5% pentafluoropropanol.

Using this azeotropic mixture, as a solvent, the flux cleaning performance, plasticity and stability effects are tested. The following test is used:

Flux removal cleansing test

The Rogin Flux flux, which is commercially available under Kabushiki Kaisna Tamura Seisakushose MH-32OV, is applied to the printed circuit board (10 x 10 cm) and preheated to 110 ° C. Then the printed circuit board is soldered (63 Sn) at temperature 2c0 C, for 5 seconds. Thereafter, using the solvent described in Table 1, the plate was cleaned by dipping for 1 minute and steamed for 1 minute.

The surface condition of the printed circuit board is determined by the naked eye. The plate also detects the ionic residue using the Omegameter 500, which is commercially available from Kenco Industries Inc. The results are shown in Table 1 as results of the flux removal purification test. Effect on plastics

To 100 g of the solvent shown in Table 1, the plastic test specimen described in Table 1 (5 x 50 x 2 mm) was urinated and allowed to stand in a 50 ° C thermostat for 5 minutes. The test sample is then removed from the solvent and its weight and volume are immediately measured. The change in weight and volume of the plastic sample is calculated and the effect on the plastics is estimated according to the following criteria. (3) ·% weight gain or volume ranging from 0 to less than 2%. Q:% increase in weight or volume is not less than 2% but is less than 5%. :% increase in weight or volume is not less than 5%. The plastic sample is dissolved in a solvent. The results are shown in Table 1 as an effect on plastics.

Chemical stability

In a 100 ml glass stoppered glass flask, add 100 g of the solvent listed in Table 1, 0.1% 10 of the water based on the solvent (in Comparative Example 1 or 4, below, 0.01% of the water based on the amount of water). 225 or 225 cb) and metal, aluminum or zinc, and the glass flask is closed. Place the glass flask in a thermostat at 50 ° C for 30 days. During the placement of the flask in the thermostat and for the next 30 days, the corrosion of the metal is monitored by viewing it with a primer. The results are shown in Table 1 as chemical stability.

Comparative Examples 1, 2, and 3 The cleaning power of flux removal, effected by plastics, and chemical stability were tested in the same manner as in Example 1 except that 225 cc alone was used as the solvent (Comparative Example 1, 5FP alone (comparative example) 2) or a mixture of 225ca and ethanol (225ca: ethanol = 97: 3) (Comparative Example 3) instead of the azeotropic mixture of 225 ca / 5FP.

A mixture of 1,3-dichloro-1,2,2,3,3-yentafluoropropane (225cb), b.p. 56.1 ° C and 5FP, bp 81 ° C, 50:50, is distilled in the same manner as Example 1, to produce a distillate with a 54.7 ° C azeotropic temperature, which is below the boiling point of each of the solvents used.

Gas chromatography shows that the distillate consists of 92.2% 1,3-dichloro-1,2,2,3,3-pentafluoropropane and 7,8% 5FP. 11 The cleaning ability of the obtained azeotropic flux remover, its effects on plastics and its stability is measured in the same manner as in Example 1. The results are shown in Table 1. Example

A mixture of 55% Y17-dichloro-2,2,3,3,3-pentafluoropropane boiling at 51 ° C and 45% 1,3-dichloro-1,2,2,3,3, pentafluoropropane, boiling point 56, 1 ° C and 5FP in a ratio of mixture to 5FP 50: 50 are distilled in the same manner as in Example 1 to form a distillate. The distillate has a constant boiling point in the narrow range of 50 to 54.9 ° C.

Analysis by gas chromatography showed that the distillate consisted of 93.4 to 92.4% of a mixture of 1.1% dichloro-2,2, 3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3, 3-pentafluoropropane (60: 4/40: 96) and 6.6 to 7.6% 5FP. The cleaning ability of the resulting mixture of the azeotropic mixture in flux removal, its effects on plastics and its stability is measured in the same manner as in Example 1. The results are shown in Table 1.

COMPARATIVE EXAMPLE 4 Flux removal performance, plastic effect and chemical stability were measured in the same manner as Example 1 except that 225 cb alone was used as solvent instead of 225 cc / 5FP azeotrope.

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Claims (8)

/ 5 16 PATENT ABOUT THE CLAIMS An azeotropic solvent composition comprising dichloropentafluoropropane and a fluorinated alcohol. 2. A composition according to claim 1 wherein the weight ratio of the dichloropenta fluoropropane to the fluorinated alcohol is 99.5 to 88.0 / 0.5 to 12.0. 3. Azeotropic solvent composition comprising an azeotropic mixture of dichloropentyl fluoropropane and fluorinated alcohol. 4. A composition according to claim 3 wherein the weight ratio of the dichloropenta fluoropropane to the fluorinated alcohol is 99.5 to 88.0 / 0.5 to 12.0. 5. A composition according to claim 3 comprising a mixture of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and pentafluoropropanol. 6. A composition according to claim 3 wherein the azeotropic mixture is a mixture of 93.5% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 6.5% by weight of pentafluoropropanol. 7. A composition according to claim 3 wherein the azeotropic mixture is a mixture of 1,3-dicloro-1,2,2,3,3-pentafluoropropane and pentafluoropropanol. 3. A composition according to claim 3, wherein the azeotropic mixture is a mixture of 92.2% by weight of 1,3-dichloro-1,2,2,3,3-pentafluoropropane and 7.3% by weight of pentafluoropropanol. 17 9. Azeotrope-like blend composition A) 93.5 to 92.2% by weight of a mixture of 0.5 to 99.5% by weight of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 99% by weight. 5 to 0.5% by weight of 1,3-dichloro-1,2,2,3,3-pentafluoropropane; and B) 6.5 to 7.8% by weight of pentafluoropropanol. MP-188-91-HO 9