JPH0820553A - Mixed liquid composition - Google Patents

Abstract

PURPOSE:To obtain a mixed liquid solvent having high solvent power and low flammability by compounding a flammable organic solvent, a perfluoro polyether and a flon compound. CONSTITUTION:Flammable organic solvent, a perfluoro polyether of the formula and a flon compound of each 4-96wt.% are mixed. Example of the organic solvent includes an aliphatic saturated (or unsaturated) hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, a chlorine-containing hydrocarbon, an alcohol compound, a ketone compound, an ether compound and an ester compound. The mixed liquid composition is useful as a cleaning agent, an extraction solvent, a chemical reaction medium, etc. Further, it is useful for dissolving other effective components, such as a paint, a lubricant, a water proofing agent, an insecticide, etc., and it is useful for an industrial use, household use, automobile use, daily life use and public use. This mixed solvent can exclude flon which is worried about depleting ozone layer and a chlorine solvent which is suspicious of carcinogenicity. The mixed solvent can substitute flon.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solvent composition, which enables uniform mixing of a non-combustible perfluoropolyether, which has hitherto not been miscible with a combustible organic solvent. However, since the risk of disasters due to fire is reduced, the range of use is extremely wide regardless of the fields of home, industry and public industry.

[0002]

2. Description of the Related Art Conventionally, a low flammability solvent has been achieved by using a chlorine-containing organic solvent and a fluorocarbon solvent. Also with regard to aerosols, nonflammability was common using CFC propellants. However, due to global environmental problems such as ozone depletion, some of the CFCs and chlorine-containing solvents are subject to regulation, and in addition to carcinogenic substances, they are also listed as VOCs (volatile organic compounds). It is almost impossible to use. That is, at the 4th International Conference on Montreal, tricucloethane and CFC were frozen in 1996, and some HCFCs were gradually reduced, and by 2030 it was decided to abolish them.

Even if these circumstances are natural from an environmental point of view, if alternative solvents are sought, flammable solvents have to be adopted, so that the danger of flames is inevitable and a safety problem arises. In some cases, there is an urgent need for the development of alternative low-flammability solvents.

[0004]

In developing a low-flammability solvent, when a liquid compound having a low flammability is first searched for, a selection candidate can be given from CFC compounds that do not meet the regulations. The inventor of the present invention conducted an experiment on the several items for the ability to make the combustible substance incombustible when mixed with the combustible solvent. The experimental method is "isobutane" as a combustible gas according to "High-pressure gas control method / flammability measurement method for aerosol products".
And "Dimethyl ether" are used to mix each candidate CFC compound (CFC12 is subject to regulation but added for comparison) at each stage ratio, and the nozzle length is fixed and the flame length of the jet is measured. Then, the flame length was less than 5 cm to make it flame-retardant, and the incombustibility thereof was determined. The results are shown in Table 1.
Shown in

[0005]

[Table 1]

From these results, perfluoropolyether (hereinafter also referred to as PFPE) is the most promising.
Incidentally, it can be seen that HCFC141b has almost no incombustibility. HFC134a also has a non-combustible ability, but has a low boiling point (−26.3 ° C.), so that only PFPE can be used as a liquid at room temperature.

According to publicly known literatures, when using PFPE, the drawbacks of the product are as follows: (a) Incompatible with other solvents other than freon-based solvent. "Excluding fluorine-based solvent, organic solvent / fat / water It is insoluble in, and easily separates when mixed. " B) Do not dissolve the active ingredient for the purpose of use "Maximum dissolution of 4.0% in petroleum ether and perfluorooctane". C) Too heavy specific gravity "1.6-2.
1 ”. D) High economic prices.

The present inventor has found that PFPE and some solvents
Table 2 shows the results of the liquefied gas solubility.
It was confirmed that PE does not include any solute.

[0009]

[Table 2]

Therefore, in summary of the problems of the present invention,
It is to improve the above-mentioned drawbacks of PFPE and obtain a mixed liquid composition which is a homogeneous phase. If it is possible to make a mixed liquid of PFPE and other common organic solvents that is compatible with each other, it is expected that the combustibility of the organic solvent will be reduced and the dissolving power will be improved. The specific gravity should be light, and the economic price should be integrated to make it cheap.

[0011]

The means for solving the problems of the present inventor is to add a chlorofluorocarbon solvent as a component C to the system, so that the ternary mixture is compatible and uniformly mixed. However, it has been found that it has a dissolving ability and the flammability is reduced.

This demonstration will be described with reference to Table 3. First, component A and component B (“GALDENHT”: used by Montecatini) are mixed at a ratio of 1: 1 (this mixture is * m
, And mixed to see compatibility, only low molecular weight hydrocarbons and ethers were compatible <○>
It was confirmed that many other solvent substances were incompatible <x>. This is put in a pressure resistant glass bottle and the C component (HFC13
4a) was press-fitted, and it was examined whether the three components were compatible with each other. The amount of the C component was 0.2 to 1.4 with respect to * m, but cyclohexanol and propylene glycol were excluded. Others were able to make a uniform compatible layer. The flame length was measured, and the amount of * c added was determined until the flame retardancy was reached, and the ratio was expressed as a ratio to * a. It was confirmed that the flame retardant can be reduced in the homogeneous ternary system, while the flame retardant is observed even in the incompatible system of A + B, while the flame retardant property is exhibited only in A alone.

Incidentally, when a C component having a low boiling point is used as in the above example, it can be applied as an aerosol.
The same applies to the A component. The boiling point thereof cannot be generally stated, but if it is 20 ° C. or lower, it can be classified as a propellant (in a pressurized filling container, it also acts as a solvent).

[0014]

[Table 3]

Next, the homogeneously compatible ternary mixture is
Examine the ability to dissolve other active ingredients. The solvents used in this experiment were A: dimethyl pentane + methyl isoptyl ketone, B: Fluorinert PC72 (trade name of 3M Company), and C Freon 141b with a mixing ratio of 10 + 20:
When it was set to 40:30, they were uniformly mixed, and this mixed solvent had a [specific gravity of 0.98 and a flash point of 21 ° C.]. When the dissolving power of the raw materials and the mixed solvent is obtained, it is as shown in Table 4, and it is confirmed that the mixed solvent has the dissolving power of the intended active ingredient necessary for "lubricants, polishes" and the like which PFPE does not have. It was

[0016]

[Table 4]

If they are not compatible, deviation of the solute occurs, the flammable solvent floats to the upper layer due to the difference in specific gravity, and the flame ignites. Therefore, it is necessary that the three components be in a completely homogeneous phase. . It cannot be said that the range of its components varies depending on the individual substances of the three components, and the limitation also depends on the degree of flammability required, but the physical properties change significantly when each component is 4 wt% or less. Because there is no, the upper limit is 96w
t% is determined.

The means for solving the above problems are summarized as "A
A homogeneous compatible mixed solvent composed of 4-96 wt% of a combustible organic solvent as a component, 4-96 wt% of PFPE as a B component, and 4-96 wt% of a CFC-based compound as a C component "
Achieving the purpose by the following, the mixed solvent has such applications as "cleaning liquid, solvent, solvent for chemical reaction" and the like, and also dissolves or disperses each effective component for the following purposes "paint, dye, Coating, polish, lubricant, rust preventive, adhesive,
Cleaning agents, polishing agents, waterproofing agents, flaw detection agents, mold release agents, antistatic agents, insecticides, bactericides, cosmetics or personal products can be manufactured, including aerosol products.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The component B used as the main component in the present invention, that is, perfluoropolyether, is a fluorinated alkane polyether represented by the chemical formula [I], and its permeation number m, n Although they have different physical properties, they are all colorless transparent liquids having a high specific gravity and are chemically extremely stable. It is obtained by oxidative polymerization of propylene hexafluoride. Trade names and their manufacturers currently on the market: a.
"Galden" Montecatini, b. "Fonburi" Montefluos, c. There is "Florinato" 3M Company, and according to their catalog there are about 10 species, boiling point 56-252 ° C, specific gravity 1.68-2.03, viscosity 0.4.
A wide range of brands with ~ 73 cSt are listed.

[0020]

Embedded image

Next, the C component used in the present invention refers to a hydrocarbon in which a part or all of hydrogen is replaced by fluorine (which may contain a part of chlorine), and one or more kinds thereof are used. Is blended. Depending on its boiling point, it may also be used as a propellant for aerosol products. These are summarized in Table 5.

[0022]

[Table 5]

In the present invention, the combustible organic solvent as the component A is generally as shown below, but it refers to a wide range of commonly used ones.
Here, those representatives will be exemplified, and the others will be treated as equivalents. Selected 1 for use
One kind or two or more kinds are blended.

A) Aliphatic hydrocarbons: propane, butane, pentane, isopentane, isoprene, hexane,
Methyl pentane, dimethyl pentane, 2-methyl-1,
3-butadiene, heptane, octane, isooctane,
Isooctene, dodecene, diisobutylene, methylcyclopentane, cyclohexane, cyclohexene, squalene and the like. b) Aromatic hydrocarbons: toluene, xylene, ethylbenzene, decalin, diphenylethane, styrene, etc. c) Mixed hydrocarbons: gasoline, benzine, petroleum naphtha, hydrogenated naphtha, solvent naphtha, C ₅ cracked naphtha,
Mineral spirit, n-paraffin, etc. d) Turpentine hydrocarbons: Simene, pine oil, turpentine oil, etc. e) Halogenated hydrocarbons: methylene chloride, hexachlorobutadiene, chloro-n-butyl, 1,4-dichlorobutane, chlorocarbonic acid methyl ester oxalic acid dichloride, chlorotoluene, chloronitromethane and the like. f) Alcohols: ethanol, isopropyl alcohol, butyl alcohol, tert-butyl alcohol, pentazole, acetylene alcohol, diethylene glycol, benzyl alcohol and the like. g) ethers: dimethyl ether, ethyl ether,
Isopropyl ether, dibutyl ether, ethyl vinyl ether, methyl cellosolve, methylal, acetal, dioxane, methyldioxolane, methyl-ter
t-butyl ether, lauryl nonanoate and the like. h) Ketones: acetone, methacrolein, methyl isobutyl ketone, diethyl ketone, acetylacetone, cyclohexenone, 2,2-dimethoxypropane and the like. i) Esters: methyl formate, propyl acetate, ethyl isopropionate, cyclopentyl acetate, benzyl acetate,
Cellosolve acetate, methyl lactate, ethyl oxalate,
Methyl benzoate, ethylene carbonate, etc. j) Glycerides: trioleins glyceride, dilauric acid glyceride, myristic acid glycolide, linseed oil, jojoba oil and the like. h) Others: acetic anhydride, furfural, dimethyl sulfoxide, dimethylformamide, acrylic acid and its esters, n-methylpyrrolidone, methylal and the like.

Further, the solvent is not a single product as described above, but a mixed product (eg, Solver TT: Zeonsolve: Kyowasol; Nippon Steel SBP; Mitsubishi Petroleum HAWS; Solmix; Highsolve; AP solvent; Paint dilute solution). , Etc. are commercially available, and it may be more economical to use them, and the present invention naturally includes them.

[0026]

In the mixed liquid composition of the present invention, the vapor pressure of PFPE suppresses the evaporation of the combustible organic solvent and suppresses the combustion in the liquid phase in which it is uniformly compatible.
For this purpose, it is most effective to combine the boiling points of A, B, and C as close as possible.

It is important that the three-component mixed solvent used in the present invention is uniformly compatible. The range of compatible components of the three components differs depending on the compositional essence of A, B, C, and should be changed according to the quality standard required for the purpose of use. For example,
Regarding miscibility, it can be said that when A is a low molecular weight hydrocarbon, C can be extremely small or zero. Regarding the combustibility, when the C component is CFC 141b, it is inferior in the suppression ability, and therefore it is dealt with by reducing A or blending B in a large amount.

FIG. 1 shows A: ethanol, B: Galden F.
The three components of TX and C: HCFC-141b are mixed and the state is created as a ternary phase diagram. Here, the long diagonal line is the range in which the three components form a mixed phase homogeneous solution, and the dotted line range is the range in which the flammability can be reduced (flash point 22 ° C or higher = applicable to type 3 petroleums). You can understand it by looking at this figure,
This indicates that even if the blending ratio should originally be low, if the components are not compatible with each other, the component A in the upper layer will have a flash point and will not be improved.

FIG. 2 is a diagram in which three components of A: dimethylpentane, B: Galden FTX, and C: HCFC-134a are mixed and the combustion state thereof is prepared as a ternary phase diagram. In this system, since C has a boiling point of not higher than room temperature, it is sealed in a pressure resistant glass bottle and observed. However, C is uniformly compatible in any range. The flammability is shown by a dotted line range as a low combustion range with a flame length of 5 cm or less by an aerosol test method. Naturally, the flame length is slightly flammable (25 cm) and weakly flammable (4
A range of 5 cm) will extend this range.
Although only two examples are shown above as the ternary phase diagram, it goes without saying that each ternary state diagram may differ.

[0030]

【Example】

 Example 1. Remedy (parts by weight) No. Drug name # 1 # 2 # 3 A1 Ethyl alcohol 28 25-A2 Dimethylpentane--15 A3 Hexane 5--A4 Isopropyl ether-20-A5 Methyl isopropyl ketone--15 B1 Galden FTX 5745-B2 Fomblin Y25- -30 C1 HCFC141b 10 10-C2 HCFC225ca--40

According to the above formulation, each drug is taken and mixed,
100 parts by weight of each of # 1, # 2 and # 3 of the present invention was obtained.
None of them was separated in a uniform transparent layer even after being left for one month. # 1 This mixed liquid composition may be used as an extraction solvent because it has a flash point of 45 ° C., an explosion range of 5 to 9 and is highly safe against fire as compared with other solvents. In particular, it has the feature that it has a high dissolving power for animal and plant waxes, oils and fats, essential oils, and oil-soluble components. # 2 This mixed liquid composition also has low flammability and can be used in the same manner as in the above example, and also has applications as, for example, a urethane varnish diluting solution, a dry cleaning laundry solution, and an organic chemical reaction solvent. # 3 This mixed liquid composition is used as a cleaning solvent. Especially for electronic parts, in the finishing process, the attached dust and the oily component of the solder flux are washed off at the same time, but in the current situation where flammable solvents have to be used due to the regulations of CFC used in the past, By substituting the product of the present invention, it became possible to mitigate the risk of fire.

Example 2. Remedy (parts by weight) No. Drug name # 4 # 5 # 6 A6 Solver TT305 15 − − A7 Ligroin − 18 − A8 Dimethyl ether − − 48 A9 Liquefied petroleum gas 4 kg / cm ² G − 30 − B1 Galden FTX − 32 − B3 Fluorinert FC − 75 15 − 24 C3 HCF143a 50 20 28

According to the above formulation, 100 parts by weight of each of the solvents # 4, # 5, # 6 according to the present invention, which are compatible with each other by mixing the respective chemicals, were obtained. Each of the products of this example contains a component which is gasified at room temperature and atmospheric pressure and can be applied as an aerosol propellant. # 4 This formulation was directly filled in an aerosol pressure canister to give a nonflammable brake cleaner. It was a product with good dust and dirt oil washing and drying properties. # 5 This solvent is blended with a petroleum-based stock solution to form an aerosol. Example: Insecticide stock solution (DDVP in 3% kerosene solution) 65 g, # 5 mixed solution 115 g AE30
It was filled in a No. 0 aerosol can to obtain a space insecticide. This product was flame retardant. # 6 This solvent has a large ability to dissolve other organic substances, and can be applied to various aerosols as a propellant that doubles as a solvent. This product was slightly flammable. Example i: 0.8 g of methyl siloxane and 39.2 g of this solvent were filled in a 100 ml aluminum can, and an aerosol valve, a button and a cap were attached to make a waterproof spray. Example ii: (liquid paraffin 40
+ Kerosene 60) (4.4 g) and the present solvent (41.8 g) were similarly charged to produce a rust preventive lubricant spray. Example iii: 220 g of chassis stock solution (Gilsonite, brown pitch, etc. dissolved in solvent naphtha and neutralized with TEA (tetraethylammonium)) and 200 g of this solvent were filled in a tin plate 480 can for an aerosol, and an automobile chassis black spray was used. Was produced.

Example 3. The metal flaw detection agent is used for the leak test of the equipment of the chemical plant equipment, and it is absolutely necessary that it is neither flammable nor explosive even from the environment of its use. The solvents used are required to have good permeability and low viscosity fluid resistance. c) Undiluted solution: Hexachlorobutadiene 28 parts by weight Methacrolein 12 〃 Dibutyl ether 12 〃 HCFC-225cb 30 〃 Galden HT110 16 〃 Oil red XO (pigment) 2 〃 Total 100 p) Propellant: HCFC-22 40 parts by weight HCFC -142b 60〃 Total 100

The stock solution is added with a dye, heated to about 60.degree. C. to dissolve the stock solution, and added with uniform stirring. Mixtures of propellants are commercially available. C) 55 parts by weight and p) 45 parts by weight were aerosol-filled by a conventional method to produce a flaw detection agent. According to the old aerosol test method,
[Explosion test * Explosion up to 20g, flame length test * 1-2
cm].

[0036]

EFFECTS OF THE INVENTION The present invention has PFPE (component B), which is originally nonflammable but does not dissolve other substances at all, and organic solvent (component A), which has a dissolving power for other substances but is flammable, Where the two have incompatible properties, by blending a CFC compound as the third medium (component C),
It has become possible to form a composition in which the three components A, B and C are uniformly compatible. The mixed liquid composition is low inflammability, has a dissolving power, has a specific gravity that is not particularly heavy around 1, is colorless and transparent, has no particular offensive odor, and has no toxicity to the human body. Be a fraction,
It has a superior performance. Therefore, this mixed liquid composition can be used as a cleaning agent, a solvent for extraction, a chemical reaction medium, etc., and further dissolves an active ingredient for other purposes to produce paints, lubricants, waterproofing agents, insecticides, etc. for industrial and household use. It is applied to pharmaceuticals in various fields such as commercial use, automobile use, daily use and public use.

[Brief description of drawings]

FIG. 1A, which constitutes an example of a mixed liquid composition of the present invention,
It is a figure which shows the ternary state of B, C three component.

FIG. 2 is a diagram showing a ternary state of A, B, and C ternary components constituting another example of the mixed liquid composition of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 7:24 7:26 7:28 7:30)

Claims (5)

[Claims] 1. A flammable organic solvent of 4 to 96 w as the component A.
t%, perfluoropolyether 4-96 as B component
A mixed liquid composition in which the composition is in a composition range of 4 wt% to 96 wt% of a CFC-based compound as a C component, and the components are uniformly compatible with each other. 2. A cleaning liquid, a solvent, or a solvent for a chemical reaction, which comprises the mixed liquid composition according to claim 1. 3. A paint, a dye, a coating, a brightening agent, a lubricant, a rust preventive, an adhesive, which is obtained by dissolving or dispersing the mixed liquid composition of claim 1 and the intended active ingredient therewith. ,
Cleaning agents, detergents, abrasives, waterproofing agents, flaw detection agents, release agents, antistatic agents, insecticides, bactericides, cosmetics or human body preparations. 4. The aerosol product according to claim 1, wherein one or more components A or C having a boiling point of −49 to + 20 ° C. is used as a propellant. 5. A component is an aliphatic saturated hydrocarbon, an aliphatic unsaturated hydrocarbon, a cyclic hydrocarbon, an aromatic hydrocarbon, a chlorine-containing hydrocarbon, an alcohol compound, a ketone compound, an ester compound, an ether compound, a terpene compound, The mixed liquid composition according to claim 1, which is one or more selected from glycolide compounds, glyceride compounds, furfurals and pyrrolidones.