JPH05178767A - Composition containing halogenated hydrocarbon - Google Patents

Abstract

PURPOSE:To obtain a detergent, a draining and drying agent and a foaming agent composition substitutable for CFC-113 without destroying the ozonosphere. CONSTITUTION:The objective composition comprises 1,1-dichloro-1-fluoroethane, dichloromethane, methanol and/or ethanol.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to compositions containing halogenated hydrocarbons. In the present specification, "%"
The terms "parts" and "parts" shall mean "% by weight" and "parts by weight", respectively.

[0002]

2. Description of the Related Art Trichlorotrifluoroethane (hereinafter referred to as CFC-113), which is a chlorofluoroethane-based compound, is a non-flammable, low biotoxic substance that does not attack polymeric substances such as plastics and rubber, and Since it has excellent characteristics such as excellent selective solubility of dissolving grease, wax, etc., it has been conventionally used alone or in the form of a mixture or azeotropic composition with another organic solvent. Widely used as a solvent, cleaning agent, etc.

[0003]

Recently, CFC-113 is used.
Use of chlorofluorocarbon-based compounds has become a problem because chlorofluorocarbon-based compounds in which all hydrogen in hydrocarbons such as chlorine is replaced by chlorine and fluorine destroys the ozone layer that surrounds the earth. It is an urgent task to gradually reduce the amount and eventually abolish it. However, C used alone or as an azeotropic or azeotrope-like mixture with other organic solvents
No useful material has been found yet that can replace FC-113 and does not destroy the ozone layer.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies conducted by the present inventor in view of the current state of the art as described above, a composition containing 1,1-dichloro-1-fluoroethane and dichloromethane was The inventors have found that the requirements of (1) are almost satisfied, and have completed the present invention. That is, the present invention provides the following composition: "1,1-dichloro-1-fluoroethane (hereinafter referred to as HCFC-141b).
And a composition containing dichloromethane. The present invention also provides the following composition: "HCFC
-141b, dichloromethane, methanol and /
Alternatively, a composition containing ethanol. The following compositions are mentioned as a preferable composition of this invention. (A) A composition comprising 30 to 70% of HCFC-141b and 70 to 30% of dichloromethane. (B) A composition containing 30 to 70% of HCFC-141b, 69 to 24% of dichloromethane, and 1 to 6% by weight of methanol and / or ethanol. In the present invention, a more preferable composition is an azeotrope-like composition having the following composition. (1) An azeotrope-like composition containing 40 to 60% of HCFC-141b, 56 to 36% of dichloromethane, and 1 to 6% of methanol. (2) An azeotrope-like composition containing 40 to 60% of HCFC-141b, 58 to 38% of dichloromethane, and 1 to 4% of methanol. These azeotrope-like compositions are excellent in properties such as cleaning ability and flammability, and have little composition variation.

H used as a component of the composition of the present invention
The physical properties of CFC-141b are as shown in Table 1 below.

The composition according to the invention exhibits a high stability compared to CFC-113-based mixtures, although stabilizers may be added if desired. As the stabilizer, those which are co-distilled by the distillation operation or those which form an azeotrope-like mixture are desirable. Specific examples of such stabilizers include nitro compounds such as nitromethane, nitroethane, nitropropane, nitrobenzene and nitrostyrene; 3-methyl-
1-butyn-3-ol, 3-methyl-1-pentyne-
Acetylene alcohols such as 3-ol; epoxides such as glycidol, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 1,2-butylene oxide, cyclohexene oxide, epichlorohydrin; dimethoxymethane, 1,2-dimethoxyethane, 1 , 4-dioxane, 1,3,5-trioxane and other ethers; hexene, heptene, octene, 2,4,4-trimethyl-1-pentene, pentadiene, octadiene, cyclohexene, cyclopentene and other unsaturated hydrocarbons; Allyl alcohol, 1-
Olefinic alcohols such as buten-3-ol and 3-methyl-1-buten-3-ol; acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate and vinyl methacrylate, and the like.
Preferred stabilizers include nitromethane as described below. These stabilizers may be used alone or in combination of two or more kinds. The preferable amount of nitromethane added is 0.1 to 5%, and when the amount of nitromethane added is within this range, a high stabilizing effect is obtained and the composition as a whole becomes azeotropic, which is preferable. Furthermore, by using the above stabilizer in combination with the following stabilizers, a synergistically improved stabilizing effect is achieved. Such stabilizers include phenols such as phenol, trimethylphenol, thymol, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole and isoeugenol; dipropylamine, diisopropylamine, diisobutylamine. ,
Triethylamine, tributylamine, pyridine, N-
Amines such as ethylmorpholine, 2,2,6,6-tetramethylpiperidine, N, N'-diallyl-p-phenylenediamine; benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole And triazoles such as chlorobenzotriazole. The amount of the stabilizer used varies depending on the kind of the stabilizer, etc., but should be such that the azeotropic property is not hindered. The amount used is usually 0.01 to 10 of the composition weight of the present invention.
%, And more preferably about 0.1 to 5%.

In addition, various surfactants can be added to the composition of the present invention, if necessary, in order to improve detergency, interfacial action and the like. As the surfactant, sorbitan monooleate, sorbitan trioleate and other sorbitan fatty acid esters; polyoxyethylene sorbit tetraoleate and other polyoxyethylene sorbit fatty acid esters; polyoxyethylene monolaurate and other polyethylene glycol fatty acids Esters; Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether; Polyoxyethylene polyoxypropylene alkyl ethers such as polyoxyethylene polyoxypropylene cetyl ether; Polyoxyethylene nonylphenyl ether Polyoxyethylene alkyl phenyl ethers; polyoxyethylene oleylamine, polyoxyethylene oleic acid One or two or more nonionic surfactants such as polyoxyethylene alkylamine fatty acid amides can be used, such as de. A cationic surfactant or an anionic surfactant may be used in combination with these nonionic surfactants. Cationic surfactants and anionic surfactants are difficult to dissolve in the composition of the present invention, but when used in combination with a nonionic surfactant, the solubility is improved,
Synergistically improves detergency and interfacial action. Although the amount of the surfactant used varies depending on the type of the surfactant, it is usually about 0.1 to 20% by weight of the composition of the present invention, and 0.3 to 5%.
It is more preferable to set the degree. Although the composition of the present invention can be widely used for known washing and drying applications, it can be preferably used as a draining desiccant, a flux detergent, a washing solvent, and a degreasing detergent. Incidentally, the draining desiccant is, for example, by removing various water adhered to the article by contacting various members such as electronic components and optical components after washing with the composition of the present invention to remove the water and facilitate drying. It is to be able to do. The composition of the present invention is also suitably used as a foaming agent for the production of polyurethane and thermoplastic resin foams. Well-known polyurethane and thermoplastic resins can be widely used as the foaming raw material. The amount of the foaming agent of the present invention used with respect to the foaming raw material is not different from that of the known foaming agent, and is appropriately determined depending on the type of the foaming raw material, the density of the desired foam, etc. The ratio of the foaming agent to the total is about 1 to 40%.
The production of polyurethane and thermoplastic resin foams using the foaming agent of the present invention may be carried out in the same manner as known methods. For example, a method of reacting an active hydrogen compound having two or more active hydrogen-containing groups such as a polyol with a polyisocyanate compound in the presence of a catalyst and a foaming agent is widely known in the production of polyurethane foams. It can also be produced by a known one-step method, a prepolymer method, a block foaming method or a double belt conveyor method. Known foam stabilizers, catalysts and the like can also be used. As the foam stabilizer, a silicone-based foam stabilizer,
Fluorine-containing foam stabilizers and the like are mentioned, and these are used in an amount of about 0.1 to 2% with respect to the foaming raw material. Examples of the catalyst include tertiary amine catalysts such as triethylenediamine and metal compound catalysts such as organic tin compounds, which are used in an amount of about 0.1 to 5% based on the foaming raw material. In the foaming agent of the present invention, other, water, a filler, and
Colorants, flame retardants and the like can be added.

[0008]

The composition of the present invention has the following remarkable effects. * Since the ozone depletion coefficient is smaller than that of CFC-113, the risk of ozone layer depletion can be reduced. * Excellent safety in use because it is non-flammable and has low toxicity. Since the compositions of claims 5 and 6 are azeotrope-like compositions, the composition hardly changes during use, and liquid management, recovery, and regeneration are easy. It can also be used for steam cleaning, which is essential for the final finishing of cleaning and drying. * By adding nitromethane, the composition of the present invention can be stabilized even under severe conditions. * Extremely excellent effect in drying articles wet with water. More specifically, wafers used for manufacturing semiconductors (IC, LSI, etc.), plated products, optical lenses, photolithography masks, liquid crystal display device parts, various metals, plastics, glass, ceramics and other parts, and It is useful for washing materials and for draining and drying after washing with water. * Furthermore, it is also suitable for cleaning solvents such as circuit boards and contacts, removal of cutting oil used during metal processing, and cleaning such as dry cleaning. * Since it is chemically stable, it can be washed and dried with almost no effect on metal, plastic, rubber, etc. * Suitable for producing urethane foams due to its good compatibility with polyols. * Polyurethane resin and thermoplastic resin foams obtained by using the foaming agent of the present invention are closed cells, and thus have heat insulating properties.
Excellent dimensional stability and compressive strength as well as appearance and uniformity.

EXAMPLES Examples will be shown below to further clarify the features of the present invention. It goes without saying that the invention is not limited to these examples. In the examples below, HCFC-141b is simply referred to as 141b.

[0009]

Example 1 * Distillation test (1) 141b (50.1%), dichloromethane (4
Mixture of 6.0%) and methanol (3.9%) 200
g was placed in a distillation flask and distilled with a distillation apparatus having 20 theoretical plates. Collect the fractionated liquid while monitoring the steam temperature,
It was analyzed by gas chromatography. The result is the second
Shown in the table. Table 2 Evaporation rate Ratio of each component of temperature composition (%) (%) (° C) 141b Dichloromethane Methanol 1 30.1 52.2 44.0 3.8 20 20 30.2 51.7 44.5 3. 8 40 30.2 51.4 44.8 3.8 60 30.2 50.6 45.5 3.9 80 30.3 49.6 46.5 3.9 (2) 141b (50.2%) , Dichloromethane (4
Mixture of 8.0%) and ethanol (1.8%) 200
g was placed in a distillation flask and distilled with a distillation apparatus having 20 theoretical plates. Collect the fractionated liquid while monitoring the steam temperature,
It was analyzed by gas chromatography. The result is the third
Shown in the table. Table 3 Evaporation rate Ratio of each component of temperature composition (%) (%) (° C) 141b Dichloromethane ethanol 1 32.0 51.8 46.5 1.7 20 20 32.1 51.1 47.1 1. 8 40 32.1 50.8 47.4 1.8 60 32.1 50.2 48.0 1.8 80 32.2 49.1 49.0 1.9 (3) 141b (50.0%) And dichloromethane (5
200 g of a mixture with 0.0%) into a distillation flask,
Distillation was performed using a distillation apparatus having 20 theoretical plates. Fractions were collected while monitoring the steam temperature and analyzed by gas chromatography. The results are shown in Table 4. Table 4 Amount of evaporation Ratio of each component of temperature composition (%) (%) (° C) 141b Dichloromethane 1 32.4 52.0 48.0 20 32.5 51.7 48.3 40 32.5 51. 2 48.8 60 32.7 50.5 49.5 80 32.9 49.8 50.2 From the results of Tables 2-4, the composition of the present invention does not cause a large composition change during evaporation, It became clear that it has azeotropic properties.

[Example 2 and Comparative Example 1] * Flux cleaning property Flux on a printed circuit board of 10 cm x 10 cm MH
After applying -820V (trade name, manufactured by Tamura Manufacturing Co., Ltd.) and preheating at 110 ° C, soldering was performed at 250 ° C for 5 seconds. Next, a flux cleaning test was conducted by carrying out immersion cleaning for 1 minute and steam cleaning for 1 minute using 1 liter of the solvent shown in Table 4. The printed board after washing was visually observed, and the ionic residue thereof was measured using an Omega meter 600SMD (manufactured by Nippon Alpha Metals Co., Ltd.). As Comparative Example 1, the same test was performed using 1 liter of a solvent containing no dichloromethane. The results are shown in Table 5. Table 5 Solvent Visual observation Residual oil content (μg NaCl / cm ² ) Example 141b (50%) Surface cleaning 0.6 2-1 Dichloromethane (46%) Methanol (4%) Example 141b (50%) Surface cleaning 0.8 2-2 Dichloromethane (48%) Ethanol (2%) Example 141b (50%) Surface cleaning 1.0 2-3 Dichloromethane (50%) Comparative example 141b (96%) Surface cleaning 1.2 1- 1 Methanol (4%) Comparative Example 141b (98%) White residue 2.8 1-2 Ethanol (2%)

[0011]

Example 3 * Production of polyurethane foam (1) Tolylenediamine was reacted with propylene oxide.
Polyether polyol 100 having a hydroxyl value of 430
g, silicone type foam stabilizer 1 g, water 0.5 g, as a catalyst
N, N, N ', N'-tetramethylhexane-1,6-
2 g of diamine and the following composition (1) of the present invention,
35 g of each of (2) and (3) was mixed. The mixture is
It dissolved uniformly and did not separate. Composition (1): 141b / dichloromethane / ethanol
(50/48/2%) Composition (2): 141b / dichloromethane / methanol
(50/46/4%) Composition (3): 141b / dichloromethane (50/50)
%) This mixture is mixed with crude polymethylene polyphenylisocyanate.
Hard polyurethane with mixture of 148g
A foam was obtained. Foaming and physical data are shown in Table 6.
You Table 6Composition (1) Composition (2) Composition (3) Cream time (sec) 12 13 12 Gel time (sec) 75 78 74 Free total density (kg / m³) 26 27 26 Compressive strength (kg / cm²) 1.30 1.30 1.30 Dimensional stability −0.40 −0.45 −0.40 (−20 ° C., 24 hours (Δ%)) Thermal conductivity 0.0160 0.0163 0.0158 (Kcal / m ・ hour ・ ° C) From the above results, the composition of the present invention was found to be a detergent and a foaming agent.
It has become clear that

Example 4 and Comparative Example 2 * Stabilizing effect of nitromethane In a 100 ml pressure-resistant glass bottle, 50 g of any of the following compositions (A) of the present invention and compositions (B) and (C) as comparative examples was used. added. Composition (A): 141b / dichloromethane / methanol / nitromethane (50.0 / 45.8 / 3.9 / 0.3%) Composition (B): 141b / dichloromethane / methanol (50.0 / 46.1) /3.9%) Composition (C): 141b / methanol (96.0 / 4.
0%) Next, iron was added to this composition as a metal test piece and heated at 50 ° C. for 2 weeks to observe the corrosion state.
Copper or aluminum was added separately instead of iron, and the corrosion state was observed under the same conditions. The results are shown in Table 7. Table 7 Metal test piece composition Iron Copper Aluminum Example 4 (A) ○ ○ ○ Comparative Example 2-1 (B) △ ○ △ Comparative Example 2-2 (C) × △ × In Table 7, ○: Indicates no corrosion. Δ indicates that some corrosion was observed. X indicates corrosion. From the results in Table 7, it was revealed that nitromethane has a stabilizing effect on the composition of the present invention even under severe conditions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C11D 7/30 7/50 // C07C 31/04 6958-4H 31/08 6958-4H H05K 3 / 26 7511-4E

Claims (13)

[Claims] 1. A composition comprising 1,1-dichloro-1-fluoroethane and dichloromethane. 2. A composition comprising 1,1-dichloro-1-fluoroethane, dichloromethane, and methanol and / or ethanol. 3. 1,1-Dichloro-1-fluoroethane 3
The composition of claim 1 comprising 0-70% and dichloromethane 70-30%. 4. 1,1-Dichloro-1-fluoroethane 3
The composition of claim 2 comprising 0-70%, dichloromethane 69-24%, and methanol and / or ethanol 1-6%. 5. 1,1-Dichloro-1-fluoroethane 4
The azeotrope-like composition according to claim 4, comprising 0 to 60%, dichloromethane 56 to 36%, and methanol 1 to 6%. 6. 1,1-Dichloro-1-fluoroethane 4
The azeotrope-like composition according to claim 4, comprising 0 to 60%, dichloromethane 58 to 38%, and ethanol 1 to 4%. 7. Nitromethane 0.1 to 0.1 as a stabilizer.
The composition according to any one of claims 1 to 6, which comprises 5%. 8. A draining desiccant comprising the composition according to claim 1. 9. A flux cleaner comprising the composition according to claim 1. 10. A degreasing detergent comprising the composition according to any one of claims 1 to 7. 11. A cleaning solvent comprising the composition according to any one of claims 1 to 7. 12. A foaming agent for producing a polyurethane resin foam, which comprises the composition according to any one of claims 1 to 7. 13. A foaming agent for producing a thermoplastic resin foam, which comprises the composition according to any one of claims 1 to 7.