JPH07166199A - Mixed solvent composition - Google Patents

Abstract

PURPOSE:To obtain a composition, containing 1H-perfluorohexane and methanol in a specific proportion, excellent in incombustibility, low toxicity, stability and detergency without affecting the ozonosphere of the stratosphere and useful for removing, etc., foulings or water of electronic parts, etc. CONSTITUTION:This azeotropic mixed solvent composition is prepared by blending 89.2wt.% 1H-perfluorohexane with 10.8wt.% methanol or 91.1wt.% 1H- perfluorohexane with 8.9wt.% ethanol or this pseudoazeotropic mixed solvent composition is prepared by blending 80-99wt.% 1H-perfluorohexane with 1-20wt.% ethanol. Furthermore, this mixed solvent composition is obtained by blending an alcohol such as methanol or ethanol with 1H-perfluorohexane and a >=5C hydrocarbon at (1-25)/(50-98)/(1-25)wt.% ratio, etc. The resultant solvent composition, etc., are used to remove fluxes or oils sticking to articles such as electronic parts, precise mechanical parts or glass substrates and capable of washing the articles without affecting the ozonosphere of the stratosphere.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a printed wiring board, I
The present invention relates to a mixed solvent composition used for removing stains or moisture such as flux, oils and fats attached to articles such as electronic parts such as C, precision machine parts, glass substrates and the like.

[0002]

2. Description of the Related Art For removing flux, various kinds of oils and fats, or removing adhering water, it is excellent in nonflammability, low toxicity and stability.
1,2-trichloro-1,2,2-trifluoroethane
(Hereinafter, referred to as R113.) Or, a mixed solvent composition of this R113 and a solvent soluble in it is widely used. Since R113 has a characteristic that it selectively dissolves various stains without invading base materials such as metals, plastics, and elastomers, various precision machine parts and various electronic parts made of metals, plastics, elastomers, etc. It was ideal for cleaning printed wiring boards, precision machine parts, optical parts, etc. on which these electronic parts were mounted.

[0003]

[Problems to be Solved by the Invention]
Although 113 has various advantages, it has a long chemical life in the troposphere and diffuses into the stratosphere where it is decomposed by ultraviolet rays to generate chlorine radicals. Since chlorine radicals cause a chain reaction with stratospheric ozone and destroy the ozone layer, the production and consumption regulations thereof are being enforced.

Therefore, in place of the conventional R113, an alternative solvent that is less likely to destroy the ozone layer is being actively searched. This alternative solvent includes 2,2-dichloro-1,
1,1-trifluoroethane, 1,1-dichloro-1-
Fluoroethane, 3,3-dichloro-1,1,1,2,
2-pentafluoropropane, 1,3-dichloro-1,
1,2,2,3-pentafluoropropane and the like have been developed.

These alternative solvents have the same excellent cleaning properties as R113, and have a very small effect on the ozone layer. However, these alternative solvents have a slight influence on the ozone layer because they contain chlorine atoms. Therefore, it is desired to develop a more excellent alternative solvent that does not affect the ozone layer at all.

The present invention provides a novel azeotropic or pseudo-azeotropic composition which can be used as an alternative solvent which satisfies the excellent properties of conventional R113 but does not affect the ozone layer at all, and its use. The purpose is to do.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to achieve the above-mentioned object, and includes the following (1), (2),
(3) and (4) are selected from 1H- perfluorohexane _{(H (CF 2) 6 F} , 1,1,1,2,2,3,
Also referred to as 3,4,4,5,5,6,6-tridecafluorohexane, hereinafter referred to as R52-13p. ) Is a mixed solvent composition containing as a main component, and a method for removing dirt or moisture adhering to an article using the mixed solvent composition.

(1) An azeotropic mixed solvent composition comprising 89.2% by weight of R52-13p and 10.8% by weight of methanol.

(2) An azeotropic mixed solvent composition comprising 91.2% by weight of R52-13p and 8.9% by weight of ethanol.

(3) A pseudoazeotropic mixed solvent composition comprising 80 to 99% by weight of R52-13p and 1 to 20% by weight of ethanol.

(4) At least one selected from methanol and ethanol, R52-13p and carbon number 5
The above hydrocarbons are (at least one selected from methanol and ethanol) / (R52-13p) /
(Hydrocarbons having 5 or more carbon atoms) = 1 to 25/50 to 98
A mixed solvent composition containing 1 to 25% by weight.

The mixed composition ratio of the azeotropic composition consisting of R52-13p and methanol is R52-13p / methanol =
89.2% by weight / 10.8% by weight, the boiling point of this azeotropic composition is 52.4 ° C. at 1010 hPa.

The mixed composition ratio of the azeotropic composition consisting of R52-13p and ethanol is R52-13p / ethanol =
91.1% by weight / 8.9% by weight, and the boiling point of this azeotropic composition is 60.0 ° C. at 1004 hPa.

In Japanese Patent Laid-Open No. 5-194992, R5
Although an azeotrope-like composition containing 2-13 p / methanol = 91 to 95/5 to 9% by weight is described, the present invention has an azeotropic composition outside the composition range of this azeotrope-like composition. That is what I found. The azeotropic composition composed of R52-13p and methanol of the present invention shows no composition change of the composition even when the composition is repeatedly used, as compared with the conventional azeotropic composition composed of R52-13p and methanol. , Has the advantage of maintaining extremely stable performance.

Japanese Unexamined Patent Publication No. 5-186796 discloses R5.
2-13p / 2-propanol = 88 to 92/8 to 12
An azeotrope-like composition is described which comprises weight percent. Further, in Japanese Patent Application Laid-Open No. 3-252500, R52-13p / 2
A flux detergent consisting of propanol = 80/20% by weight is described. However, since none of these compositions is an azeotropic composition, there is a drawback that the composition may change when the composition is repeatedly used and stable performance cannot be maintained.

R52-13p and ethanol are R52-1
3p / ethanol = 80-99% by weight / 1-20% by weight
A pseudo-azeotropic composition is produced within the range.

The hydrocarbons having 5 or more carbon atoms used in the present invention include aliphatic hydrocarbons having 5 to 9 carbon atoms, alicyclic hydrocarbons having 5 to 9 carbon atoms and 6 to 12 carbon atoms. At least one selected from aromatic hydrocarbons is preferable. Particularly preferable hydrocarbons having 5 or more carbon atoms are aliphatic saturated hydrocarbons having 5 to 9 carbon atoms and alicyclic saturated hydrocarbons having 5 to 9 carbon atoms. More preferable hydrocarbons having 5 or more carbon atoms include the following.

N-pentane, 2-methylbutane, 2,2
-Dimethylpropane, n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,
2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, n-octane, 2,
Aliphatic hydrocarbons having 5 to 8 carbon atoms such as 2,3-trimethylpentane and 2,2,4-trimethylpentane, and alicyclic groups having 5 to 8 carbon atoms such as cyclopentane, cyclohexane, methylcyclohexane and ethylcyclohexane At least one selected from hydrocarbons.

The mixing ratio of R52-13p, methanol and hydrocarbons having 5 or more carbon atoms in the mixed solvent composition is R.
52-13p / methanol / hydrocarbons having 5 or more carbon atoms = 50 to 98/1 to 25/1 to 25% by weight, especially R52
-13p / methanol / hydrocarbons having 5 or more carbon atoms = 6
0 to 98/1 to 20/1 to 20% by weight is preferable.

The mixing ratio of R52-13p, ethanol and hydrocarbons having 5 or more carbon atoms in the mixed solvent composition is R
52-13p / ethanol / hydrocarbons having 5 or more carbon atoms = 50 to 98/1 to 25/1 to 25% by weight, especially R52
-13p / ethanol / hydrocarbons having 5 or more carbon atoms = 6
0 to 98/1 to 20/1 to 20% by weight is preferable.

Methanol and ethanol in these mixed solvent compositions may be used in combination. The total amount of methanol and ethanol is preferably contained in the mixed solvent composition in the range of 1 to 25% by weight, particularly 1 to 20% by weight. The ratio of methanol and ethanol in the total amount of methanol and ethanol used together is methanol / ethanol = 1 to
It can be selected from a wide range of 99/99 to 1% by weight.

The mixed solvent composition containing these hydrocarbons has improved solubility in various stains, as compared with those containing no hydrocarbons. In this respect, hydrocarbons are superior to esters and the like. In addition, hydrocarbons are preferable because they do not easily attack the base materials such as plastics and elastomers. In this respect, hydrocarbons are superior to ketones and the like.

In order to further enhance the solubility, for example, at least one selected from the following compounds is 0.01 to 50% by weight, preferably 0.01 to 30% by weight, more preferably 0.1 to 20% by weight. It may be contained in the mixed solvent composition containing the hydrocarbon of the present invention in the range of weight%.

Dichloromethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene,
Chlorinated hydrocarbons such as trichlorethylene and tetrachloroethylene, 1-propanol, 2-propanol,
1-butanol, 2-butanol, isobutanol, t
Alcohols such as butanol.

Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and methyl isobutyl ketone,
Ethers such as diethyl ether, methyl cellosolve, tetrahydrofuran and 1,4-dioxane.

2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane,
3,3-dichloro-1,1,1,2,2-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-
Chlorinated fluorinated hydrocarbons such as pentafluoropropane and esters such as ethyl acetate, propyl acetate and butyl acetate.

Alkyl polyoxyethylene ether, alkylaryl polyoxyethylene ether, alkylaryl formaldehyde condensed polyoxyethylene ether, block polymer of polyoxyethylene and polyoxypropylene having polyoxypropylene as a lipophilic group, alkylthiopolyoxyethylene Ether-type surfactants such as ethers, propylene glycol ester polyoxyethylene ethers, glycerin ester polyoxyethylene ethers, sorbitan ester polyoxyethylene ethers, polyoxyethylene fatty acid ester and other ether ester type surfactants, glycerin ester , Sorbitan ester and other ester type surfactants or fatty acid alkanolamides, polyoxyethylene fatty acid amides Nonionic surface active agents such as any nitrogen-containing type surfactants.

In order to improve the stability mainly, for example, at least one stabilizer selected from the compounds shown below is used in the range of 0.001 to 10% by weight, preferably 0.01 to 5% by weight. It may be contained in a mixed solvent composition containing hydrogen.

Nitro compounds such as nitromethane, nitroethane, nitropropane and nitrobenzene, amines such as diethylamine, triethylamine, i-propylamine, butylamine and i-butylamine.

Phenol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, t-butylcatechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxydiphenyl-2, 2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate, 2,
Phenols such as 6-di-t-butyl-p-cresol.

2- (2'-hydroxy-5'-methyl-
Phenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-
Chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N, N-bis-2-ethylhexyl)
Aminomethyl] benzotriazole and other triazoles.

The mixed solvent composition of the present invention is the same as the conventional R11.
It can be suitably used for various uses similar to those of the 3 type composition. Such specific applications include applications such as detergents for removing articles with dirt or moisture, paint solvents or extractants. In particular, it is used for cleaning articles in which the performance of the articles may be deteriorated due to the adhered dirt and moisture.

Examples of the material of the article to be washed include glass, ceramics, plastics, elastomers, rubbers and metals. As a concrete example of the article,
Examples include electronic / electrical devices, precision machines / instruments, optical articles, and the like, which are printed wiring boards, ICs, micromotors, relays, optical lenses, glass substrates, and the like.

The dirt attached to the article includes dirt that is used in manufacturing the article or parts constituting the article and must be finally removed or that is attached when the article is used. Examples of the substance that forms stains include greases, mineral oils, oils and fats, waxes, oils such as oil-based inks, and fluxes.
Examples of the water include water remaining on the article after washing the article with water or an aqueous detergent.

The azeotropic or pseudo-azeotropic composition of the present invention is particularly effective when used in a method for removing fluxes or moisture adhering to an article. The mixed solvent composition containing hydrocarbons of the present invention is particularly effective when used in a method for removing oils or fluxes.

As a concrete means for removing the dirt and water, for example, hand-wiping, dipping, spraying, shaking, ultrasonic cleaning, steam cleaning or a combination thereof can be adopted.

[0037]

【Example】

[Example 1] 1000 g of a composition consisting of 90% by weight of R52-13p (boiling point 70.8 ° C) and 10% by weight of methanol (boiling point 64.5 ° C) was placed in a distillation flask and attached to a rectification column having 5 theoretical plates. It was Next, the composition was heated and totally refluxed for 2 hours to reach an equilibrium state, after which a fraction was collected with time and analyzed by gas chromatography. The results are shown in Table 1 (upper row).

Example 2 A mixed solvent composition containing 90% by weight of R52-13p and 10% by weight of ethanol (boiling point 78.3 ° C.) was analyzed in the same manner as in Example 1. The results are shown in Table 1 (bottom row).

Example 3 20 kg of a mixed solvent composition consisting of 99% by weight of R52-13p and 1% by weight of ethanol was placed in a small single tank open type washing machine and operated for 6 hours per day for 3 days. The operating conditions were such that only the mixed solvent composition was charged into the cleaning tank, the composition was heated, evaporated and condensed, then introduced into the water separator, and the circulating amount per hour until returning to the cleaning tank was charged. The operating conditions were such that the amount of the composition was obtained. Table 2 (upper row) shows the results of gas chromatograph analysis by sampling from the cleaning tank and water separator over time.
Shown in.

Example 4 A mixed solvent composition of 80% by weight of R52-13p and 20% by weight of ethanol was also operated in the same manner as in Example 3. Table 2 (bottom row) shows the results of gas chromatograph analysis by sampling from the cleaning tank and water separator over time.

[Examples 5 to 12] Flux cleaning tests were conducted using the mixed solvent compositions shown in Table 3. That is, a printed circuit board (50 mm x
100 mm x 1.6 mm) Flux (Speedy Flux AGF-J-I: manufactured by Asahi Chemical Laboratory) was applied to the entire surface, and after soldering at a soldering temperature of 260 ° C using a wave soldering machine, the composition shown in Table 3 was used. It was immersed for 5 minutes and washed. The degree of flux removal was determined, and the results are shown in Table 3 as the degree of removal (A). ◎: Can be removed well,
△: Trace remains, ×: Remains considerably.

[Examples 13 to 16] The mixed solvent compositions shown in Table 4 were used to carry out a washing test of machine oil. That is, SU
S-304 test piece (25mm × 30mm × 2m
m) was immersed in machine oil (CQ-30 manufactured by Nippon Oil Co., Ltd.) and then immersed in the composition shown in Table 4 for 5 minutes. The degree of removal of the mechanical oil was judged, and the result is shown in Table 4 as the degree of removal (B). ⊚: Can be removed satisfactorily, △: Trace amount remains, ×: Remains considerably.

[Examples 17 to 23] Using the mixed solvent compositions shown in Table 5, a test for removing adhered water was conducted. That is, 30
After immersing a glass plate (mm × 18 mm × 5 mm) in pure water, it is immersed in the composition shown in Table 5 for 20 seconds to drain water, and the taken out glass plate is immersed in anhydrous methanol to adhere from the increased water content. The water removal status was judged. The removal degree of the adhered water is shown in Table 5 as the removal degree (C). ⊚: Can be removed satisfactorily, △: Trace amount remains, ×: Remains considerably.

In the table, MeOH is methanol, EtOH is ethanol, 2-PrOH is 2-propanol, n-C ₆ H ₁₄ is n-hexane, and cyclo-C.
₆ H ₁₂ represents cyclohexane.

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

[0049]

[Table 5]

[0050]

The composition of the present invention has the advantages that it satisfies the excellent characteristics of conventional R113 and does not affect the stratospheric ozone layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C11D 7:30 7:26) (72) Inventor Masaaki Tsuzaki 10 Goi Kaigan, Ichihara, Chiba Asahi Glass Co., Ltd. Company Chiba Plant (72) Inventor Kazuya Ohharu 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Central Research Laboratory, Asahi Glass Co., Ltd.

Claims (6)

[Claims] 1. An azeotropic solvent composition comprising 89.2% by weight of 1H-perfluorohexane and 10.8% by weight of methanol. 2. An azeotropic mixed solvent composition comprising 91.1% by weight of 1H-perfluorohexane and 8.9% by weight of ethanol. 3. A pseudoazeotropic mixed solvent composition comprising 80 to 99% by weight of 1H-perfluorohexane and 1 to 20% by weight of ethanol. 4. At least one selected from methanol and ethanol, 1H-perfluorohexane and hydrocarbons having 5 or more carbon atoms, (at least one selected from methanol and ethanol) / (1H-perfluorohexane) / ( Hydrocarbons having 5 or more carbon atoms) = 1
A mixed solvent composition containing 25/50 to 98/1 to 25% by weight. 5. A cleaning method for removing dirt or moisture adhered to an article from the article using the composition of claim 1, 2, 3 or 4. 6. The cleaning method according to claim 5, wherein the dirt attached to the article is flux or oil.