JP2728198B2 - Fluorine solvent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorine-containing solvent containing a hydrogen-containing polyfluorotertiary amine, which does not destroy the ozone layer and has a small influence on global warming.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons are known as solvents for cleaning plastics, rubber products, electronic parts and the like. Particularly, a chlorine atom or a halogenated hydrocarbon group having a chlorine atom and a fluorine atom is widely used in various industrial fields because it is nonflammable and stable and can dissolve waxes and fats and oils.

For example, those having a chlorine atom include:
1,1,1-trichloroethane, trichloroethylene,
As tetrachloroethylene having a chlorine atom and a fluorine atom (hereinafter referred to as “CFC”), trifluorotrichloroethane (hereinafter referred to as “CFC113”) and the like are known. Since it is toxic and does not erode the surface of plastic or rubber, it is widely used for various purposes.

[0004]

However, halogenated hydrocarbons have such excellent characteristics,
"Specific CFCs" such as CFC113 and 1,1,1-trichloroethane are completely abolished, as it has been shown that chlorine atoms, one of the constituent elements, act as catalysts and destroy the ozone layer surrounding the earth. That was negotiated internationally.

To cope with such a problem, it is essential to develop a new solvent in place of these solvents. Actually, although various substances in place of CFC113 have been specifically studied as cleaning solvents, they are still effective. At present, no alternative has been found.

[0006] In recent years, in addition to protection of the ozone layer, consideration has been particularly required for preventing global warming.
As one of the performances required for the alternative solvent compound, it is also an important requirement that the effect on global warming is small. The evaluation of the effect on global warming is considered to be based on the values of the global warming potential (GWP or HGWP) and the lifetime in the atmosphere. That is, considering the global warming problem,
It is said that it is desirable that a candidate compound for alternative CFCs in the future is a compound having a global warming potential as small as possible and having an atmospheric lifetime of 2 to 3 years or less.

On the other hand, in 1991 Du Pon
HFC-43, a hydrofluorocarbon developed by t
-10mee (CF ₃ CFHCFHCF ₂ CF ₃ )
Although it has some properties as an alternative solvent that does not destroy the ozone layer, it has been announced that HWGP is 0.25 and its lifetime in the atmosphere is 20.8 years, which means that it has a relatively long lifetime.

In the case of amine compounds, 3M has
As a drainer and a rinsing agent for an organic solvent in the VD ^™ cleaning system, a perfluorocarbon liquid PF-5052 (perfluoro-N-
Methylmorpholine) was launched several years ago, but the atmospheric lifetime of the compound is estimated to be hundreds to thousands of years.

As the hydrogen-containing polyfluorotertiary amine, for example, a monohydropolyfluorotertiary amine having one hydrogen atom in the molecule, which is described in JP-A-5-132451, is known. However, the compound has a remarkably low dissolving power and is unsuitable as a cleaning solvent.

The present invention has been made in view of the above circumstances, and eliminates the drawback that a conventional cleaning solvent such as CFC113 causes destruction of the ozone layer.
An object of the present invention is to provide a novel fluorine-based solvent having an excellent cleaning effect while taking into account new environmental problems such as global warming.

[0011]

The fluorinated solvent of claim 1 comprises one or more of hydrogen-containing polyfluorotertiary amines represented by the following general formula (I), or comprises It is characterized by containing one or more hydrogen polyfluoro tertiary amines.

[0012]

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The fluorinated solvent according to claim 2 is a hydrogen-containing polyfluorotertiary amine represented by the following general formula (II):
Or one or more of the hydrogen-containing polyfluorotertiary amines.

[0014]

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The fluorinated solvent according to claim 3 is the fluorinated solvent according to claim 1 or 2, further comprising a hydrocarbon compound, an alcohol compound, an ether compound, a ketone compound, an ester compound, an organic nitrogen compound, an organic nitrogen compound. 1 selected from the group consisting of sulfur compounds and organosilicon compounds
And the content of the second component is 1 to 50% by weight based on the weight of the hydrogen-containing polyfluorotertiary amine.

The fluorine-based solvent according to a fourth aspect is the fluorine-based solvent according to any one of the first to third aspects, characterized in that it is a cleaning agent.

The fluorinated solvent according to claim 5 is the fluorinated solvent according to any one of claims 1 to 3, characterized in that it is a draining agent.

The fluorinated solvent according to claim 6 is the fluorinated solvent according to any one of claims 1 to 3, characterized in that it is a solvent for dry cleaning.

The fluorinated solvent according to claim 7 is the fluorinated solvent according to any one of claims 1 to 3, characterized in that it is a solvent for paint.

[0020] The fluorine-based solvent according to claim 8 is the solvent for extraction in the fluorine-based solvent according to any one of claims 1 to 3.

Hereinafter, the present invention will be described in detail.

The hydrogen-containing polyfluoro tertiary amine according to claim 1, wherein X is a trifluoromethyl group
In the case where R ¹ is a trifluoromethyl group, R ² has 1 carbon atom
Any polyfluoroalkyl group having or not having from 3 to 3 hydrogen atoms may be used. X is a trifluoromethyl group and R
^{When 1} is a pentafluoroethyl group , R ² may be a polyfluoroalkyl group having or not having a hydrogen atom having 1 or 2 carbon atoms, provided that the hydrogen-containing polyfluorotertiary amine has an appropriate boiling point range. This is preferable. Note that when X is R ¹ is H is a trifluoromethyl group or a peptidyl <br/> printer fluoroethyl group, R ² is or Lupo Li fluoroalkyl group having a hydrogen atom of 1 to 3 carbon atoms Perufuruo
Lopropyl group.

The hydrogen-containing polyfluoro tertiary amine according to claim 2 of the present invention,
Since oro tertiary amines have a suitable boiling point range, R
If ¹ is trifluoromethyl group, R ³ is Ri ethyl group or propyl group der, when R ¹ is a pentafluoroethyl group, R ³ is methyl group, ethyl group or propyl group.

The method for producing the hydrogen-containing polyfluorotertiary amine used in the first aspect of the present invention is described in Japanese Patent Application No. Hei.
No. 76769, namely the general formula CF
A perfluoroazaalkene represented by ₃ N = CFY (where Y is F or a trifluoromethyl group), for example, perfluoro-2-aza-2-propene (CF ₃ N = CF
₂ ), perfluoro-2-aza-2-butene (CF ₃ N
= CFCF ₃ ) and the like, acetonitrile, N, N-dimethylformamide, diglyme, dimethylsulfoxide, N
-Reaction with an alkali metal fluoride such as potassium fluoride and / or cesium fluoride and a sulfonic acid ester represented by the following general formula (III) in an aprotic polar solvent such as methylpyrrolidone and sulfolane Thereby, it can be easily obtained.

EZ ¹ ... (III) (where E is a perfluoroalkyl group having 1 to 4 carbon atoms, preferably a trifluoromethyl group.
Z ¹ is a sulfonic acid ester represented by the following formula wherein the ester portion (Z ¹ ) is an alkyl group having 2 to 5 carbon atoms. Z ¹ = —SO ₂ OCHXR ⁴ (where R ⁴ represents a polyfluoroalkyl group having or not having a hydrogen atom having 1 to 3 carbon atoms, and X represents H or a trifluoromethyl group)) sulfonic acid Specific examples of the ester include the following, which are selected and used depending on the intended hydrogen-containing polyfluorotertiary amine.

CF ₃ SO ₂ OCH ₂ CF ₂ H , CF ₃ SO ₂ OCH ₂ CF ₂ CF ₂ H , CF ₃ SO ₂ OCH (CF ₃ ) ₂ , CF ₃ SO ₂ OCH (CF ₃ ) CF ₂ CF ₃ , _{CF 3 SO 2 OCH (CF 3} ) CF 2 CF 2 CF 3, CF 3 SO 2 OCH 2 CF 2 CFHCF 3, CF 3 SO 2 OCH 2 CF 2 CF 2 CF 3 hydrogen-containing poly used in the invention of claim 2 In the case of producing a fluorotertiary amine, in the above method, the perfluoroalkylsulfonic acid ester used for producing the hydrogen-containing polyfluorotertiary amine according to claim 1 can be used as the sulfonic acid ester. In addition, p-
The ester moiety (Z ² ) of various sulfonic acid esters such as toluenesulfonic acid ester, alkyl sulfuric acid, and methanesulfonic acid ester, which has a carbon number of 1 as represented by the following formula:
Sulfonates which are alkyl groups of 3 to 3 can be used.

Z ² = —SO ₂ OC _n H _{2n + 1} (where n is 1, 2 or 3) Specific examples thereof include the following, and the intended hydrogen-containing It is selectively used depending on the polyfluorotertiary amine. In the following, C ₆ H ₄ is a phenylene group.

CF ₃ SO ₂ OCH ₃ , C ₂ F ₅ SO ₂ OCH ₃ , C ₃ F ₇ SO ₂ OCH ₃ , C ₄ F ₉ SO ₂ OCH ₃ , CF ₃ SO ₂ OCH ₂ CH ₃ , CF ₃ SO _{2 OC 3 F 7, CH 3 C} 6 H 4 SO 2 OCH 3, CH 3 C 6 H 4 SO 2 OCH 2 CH 3, CH 3 C 6 H 4 SO 2 OC 3 F 7, CH 3 OSO 2 OCH 3, CH ₃ CH ₂ OSO ₂ OCH ₂ CH ₃ , C ₃ H ₇ OSO ₂ OC ₃ H ₇ , CH ₃ SO ₂ OCH ₃ , CH ₃ SO ₂ OCH ₂ CH ₃ , CH ₃ SO ₂ OC ₃ H ₇ The sulfonic acid ester used is an alkylating agent for introducing an alkyl group or a polyfluoroalkyl group, and the substituent derived from the sulfonic acid ester is
The substituent CHX in the general formula (I) is bonded to the nitrogen atom of the hydrogen-containing polyfluorotertiary amine to be synthesized.
Since R ² or the substituent R ³ in the general formula (II) is constituted, the above-mentioned sulfonic acid is an alkyl ester having 1 to 3 carbon atoms or a polyfluoroalkyl having 2 to 5 carbon atoms. Esters are used.

The synthesis yield also differs depending on the type of sulfonic acid ester used. In the case of synthesizing the compound according to the first aspect, the synthesis yield is generally higher if other conditions are the same. , Trifluoromethanesulfonic acid ester is the highest and, therefore, is most preferably used. Next, the yield decreases in the order of methanesulfonic acid ester, alkyl sulfate, and p-toluenesulfonic acid ester. In the case of synthesizing the compound described in claim 2, alkyl sulfuric acid and trifluoromethanesulfonic acid ester are most preferably used.

The composition of the reaction system, the reaction temperature, and the reaction time vary depending on the type of the drug to be used and the target product, but in the usual case, it is preferable to employ the following conditions.

The amount of the sulfonic acid ester used is 0.5 to 1 mol per mol of perfluoroazaalkene as a starting material.
It is suitable to use 2.0 times mol, preferably 1.05 to 1.25 times mol. Use of too much sulfonic acid ester does not improve the yield, and is uneconomical.

The amount of the alkali metal fluoride to be used is 0.5 to 1 mol per mol of perfluoroazaalkene as a starting material.
A 10-fold molar amount, preferably 1.5- to 8-fold molar amount, is appropriate. Use of such an excess amount improves the yield. However, even if it is used in an excessively large amount, the yield reaches a peak and the production efficiency is reduced.

The ratio of the aprotic polar solvent and the starting material perfluoroazaalkene is such that the aprotic polar solvent is used in an amount of 500 to 2 per mole of perfluoroazaalkene.
Preferably, it is used in the range of 000 ml. When the aprotic polar solvent is used in a large amount, the reaction time can be shortened. However, when the aprotic polar solvent is used in an excessively large amount, the production efficiency per batch is reduced, which is uneconomical.

The reaction temperature and the reaction time are preferably 0 to 100 ° C. and 6 to 80 hours, more preferably 20 to 80 ° C. and 12 to 65 hours, respectively.

Examples of the hydrogen-containing polyfluorotertiary amine according to the present invention thus produced include the following.

The hydrogen-containing polyfluoro tertiary amine according to the first aspect is characterized in that the hydrogen-containing polyfluoro tertiary amine has an α carbon atom in one of the three substituents bonded to the nitrogen atom represented by the general formula (I) It is a hydrogen-containing polyfluorotertiary amine having a structure having no fluorine atom, and preferable specific examples thereof are as follows.

[0037]

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[0038]

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The most suitable specific example is represented by the above general formula (I)
In, R ¹ is Ah trifluoromethyl group having one carbon atom
And specific examples thereof are as follows.

[0040]

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The hydrogen-containing polyfluoro tertiary amine according to claim 2 is a hydrogen-containing polyfluoro tertiary amine having an alkyl group represented by the general formula (II), and preferred specific examples thereof. Is as follows.

[0042]

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Further, more preferred specific examples are those represented by the general formula (I)
In I), R ¹ is a trifluoromethyl group having 1 carbon atom .
A Oh Ru compound, and specific examples are as follows.

[0044]

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When these hydrogen-containing polyfluorotertiary amines are used alone, the hydrogen-containing polyfluorotertiary amine has a function of selectively dissolving and removing dirt, compatibility with materials, and incombustibility. In addition, the effects such as flame retardancy, drying properties, and dirt removal properties of minute parts due to low surface tension are most effectively exhibited. However, depending on the object to be cleaned, the hydrogen-containing polyfluoro tertiary amine alone may not be used alone. In some cases, a sufficient cleaning effect cannot be obtained. Therefore,
In such a case, the hydrogen-containing polyfluorotertiary amine and, as a second component, a hydrocarbon compound, an alcohol compound, an ether compound, a ketone compound, an ester compound, an organic nitrogen compound, an organic sulfur compound and an organic silicon compound One or more selected from the group consisting of In this case, specific examples of the hydrocarbon compound include aliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Examples of the alcohol compound include methanol, ethanol, propanol, isopropanol, butanol, carbitol and the like.
Examples of the ether compound include diethyl ether, diisopropyl ether, dibutyl ether, dioxane, tetrahydrofuran, monoglyme, diglyme and the like. Examples of the ketone compound include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclopentanone, cyclohexanone and the like. Examples of the ester compound include carboxylate esters such as formate ester and acetate ester. Examples of the organic nitrogen compound include acetonitrile, nitrobenzene, dimethylformamide, N-methylpyrrolidone and the like. Examples of the organic sulfur compound include dimethyl sulfoxide, sulfolane and the like. Specific examples of the organosilicon compound include hexamethyldisiloxane, octamethylcyclotetrasiloxane, and the like. The hydrogen-containing polyfluoro tertiary amine according to the present invention exhibits good solubility in these second components at any ratio.

When the fluorine-based solvent of the present invention is used for applications requiring solubility such as a cleaning agent, these second solvents may be used.
If the use ratio of the component is too small, the effect of improving the dissolving power due to the use of the second component is not sufficiently obtained. Conversely, if the use ratio of the second component is too large, the hydrogen-containing poly according to the present invention is used. The use of the fluorinated tertiary amine impairs the effects of selectively dissolving and removing stains, compatibility with materials, nonflammability or flame retardancy, drying properties, and the ability to remove minute stains due to low surface tension. It is. Therefore, when the second component is used, the amount of the second component is preferably 1 to 50% by weight based on the weight of the hydrogen-containing polyfluorotertiary amine.

When the hydrogen-containing polyfluorotertiary amine according to the present invention is used as a draining agent, the hydrogen-containing polyfluorotertiary amine is generally used alone without using the second component. Alternatively, even when the second component is used, it is preferable that the ratio be lower than the above ratio.

The fluorine-based solvent of the present invention may further contain a stabilizer, if necessary. In this case, examples of the stabilizer include nitro compounds, unsaturated hydrocarbons, epoxy compounds, phenol compounds, alkenylamines, cyclic nitrogen compounds, unsaturated alcohols, and the like. In addition, various surfactants may be blended.

The solvent of the present invention is nonflammable or flame-retardant because it contains a hydrogen-containing polyfluorotertiary amine having a large number of fluorine atoms in the molecule, and has excellent drying properties because of its low surface tension. Since it has the same dissolving power as the conventional CFC 113, it can be suitably used as a solvent.

Specific uses as a solvent are a detergent, a drainer, a solvent for dry cleaning, a solvent for paint, a solvent for extraction, and the like. Used as a cleaning agent to remove flux, grease, oil, wax, ink, etc. from the surface of glass, ceramics, plastics, rubber, various metallic articles, especially IC parts, electrical equipment, precision instruments, optical lenses, etc. Can be In addition, as a draining agent, it is used to remove water from the surface after washing the article with water. As a cleaning method, hand wiping, dipping, spraying, rocking, ultrasonic cleaning, steam cleaning, or the like may be employed.

[0051]

The present inventors have conducted intensive studies in view of the above-mentioned state of the art, and as a result, have found that an amine compound having a specific structure, that is, a solvent containing a hydrogen-containing polyfluoro tertiary amine, has an Since it does not contain chlorine, there is no danger of destroying the ozone layer, and it has an excellent cleaning effect on oils and fats, dust, etc., and also has an appropriate dissolving power like CFC113. Was selectively dissolved and removed, and it was found that it did not attack the composite parts made of metal, plastic, estramer and the like as the article to be cleaned.

Further, in consideration of the problem of global warming, it is desirable that the compound has a suitable balance between moderate stability and decomposability.
The contents and positions of introduction of fluorine atoms and hydrogen atoms are important factors that essentially determine the chemical and thermal stability of the compound itself, the degree of influence on the environment, and the like.

For example, in an amine fluorine compound,
In general, when a carbon atom adjacent to a nitrogen atom is surrounded by a fluorine atom, it is said that it is extremely stable and is not easily decomposed, and conversely, both a fluorine atom and a hydrogen atom are included in this carbon atom. When bound, it is said to be extremely unstable.

From this point of view, one of the three substituents bonded to the nitrogen atom is an alkyl group or a polyfluoro group in which a fluorine atom is not bonded to the α-position carbon atom. The inventors have found that a hydrogen-containing polyfluorotertiary amine which is an alkyl group is a compound to which appropriate stability and decomposability are imparted in a well-balanced manner, and have completed the present invention.

The hydrogen-containing polyfluorotertiary amines according to claims 1 and 2 of the present invention each have a fluorine atom at the α-carbon atom in one of the three substituents adjacent to the nitrogen atom. Is a compound having no structure, and its HGW
It is estimated that P is 0.1 or less and the life in the atmosphere is several years or less. Therefore, the aforementioned HFC-43-10mee and PF-
Compared to 5052 etc. and monohydropolyfluorotertiary amines, they have more appropriate chemical and thermal stability and decomposability, and are useful as alternative solvents in consideration of global warming.

Since the hydrogen-containing polyfluorotertiary amine according to the present invention does not contain chlorine in the molecule, there is no danger of destroying the ozone layer. Since it has an appropriate dissolving power, it does not affect the article to be cleaned, has little effect particularly on plastic, and can selectively dissolve and remove only dirt. Among the substituents bonded to the nitrogen atom, the structure has one substituent with no fluorine atom at the α carbon atom, so it has a good balance between moderate stability and decomposability, so the life in the atmosphere is also compared Short and effective in preventing global warming. It is nonflammable or flame retardant because it has many fluorine atoms in the molecule. In addition, since the surface tension is small and the latent heat of evaporation is small, it has excellent drying properties, and can be easily dried and removed after washing. In particular, due to the characteristic that the surface tension is small, even an article to be cleaned having a complicated shape can easily penetrate into very small cracks or holes and remove stains on the part. It can be used very effectively as a solvent.

Incidentally, the fluorinated solvent according to the present invention comprises:
When used alone, good solubility cannot be obtained,
The second component further contains one or more selected from the group consisting of hydrocarbon compounds, alcohol compounds, ether compounds, ketone compounds, ester compounds, organic nitrogen compounds, organic sulfur compounds and organic silicon compounds. When the content is 1 to 50% by weight based on the hydrogen polyfluorotertiary amine, a good cleaning effect can be obtained with excellent dissolving power.

[0058]

EXAMPLES The present invention will be specifically described below with reference to examples, comparative examples, reference examples and experimental examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. is not.

Examples 1 to 6 , Comparative Example 1, and Reference Examples 1 to 3 SUS-304 test pieces were machine oil (Nippon Oil Co., Ltd.)
After immersion in Q-30), it was immersed in various cleaning agents having the composition shown in Table 1 for 5 minutes, taken out, visually observed for the degree of removal of the mechanical oil, and the results are shown in Table 1.

[0060]

[Table 1]

From Table 1, it can be seen that the specific hydrogen-containing polyfluoro
The fluorinated solvent of the present invention containing a tertiary amine, especially a hydrogen-containing polyfluorotertiary amine, and a hydrogen-containing polyfluorotertiary amine
As long as the detergent contains a second component within a predetermined range with respect to the secondary amine, CFC113 which is a conventional detergent for machine oil is used.
It can be seen that a good cleaning effect equivalent to that of Example 1 can be obtained.

Experimental Example 1 Each test piece of each plastic was immersed in various cleaning agents shown in Table 2 at 20 ° C. for 24 hours, taken out, and measured immediately after taking out the dimensional change and weight change. Observation was made visually, and the results are shown in Table 2. Note that N
In o. 4 and 5 , the results of immersion at 45 ° C. for 1 hour were examined.

As shown in Table 2, the fluorinated solvent according to the present invention is:
It can be seen that there is almost no adverse effect on the plastic.

[0064]

[Table 2]

Experimental Example 2 Hydrogen-containing polyfluorotertiary amine compounds 50 shown in Table 3
Parts by weight and 0 to 50 parts by weight of n-hexane or 0 to 50 parts by weight of carbitol were mixed at room temperature, and the solubility was examined. The results are shown in Table 3.

[0066]

[Table 3]

Table 3 shows that the hydrogen-containing polyfluorotertiary amine according to the present invention can be dissolved at an arbitrary ratio with the second component such as n-hexane.

Experimental Example 3 The solubility of the hydrogen-containing polyfluorotertiary amine shown in Table 4 in water at room temperature was measured by a quantitative method using gas chromatography, and the results are shown in Table 4.

Table 4 shows that the hydrogen-containing polyfluorotertiary amine according to the present invention hardly dissolves in water, and is very useful as a draining agent.

[0070]

[Table 4]

[0071]

As described in detail above, the fluorinated solvent containing a hydrogen-containing polyfluorotertiary amine of the present invention has good cleaning properties, does not adversely affect materials, especially plastics, and has a chlorine atom. As a result, there is no problem of destruction of the ozone layer. In addition, it is effective in terms of the global warming problem, and can adopt the same usage mode as the conventional CFC-based solvent. Since it has advantages such as applicability, it is extremely valuable industrially.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Masami Iwasaki 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building 6F Examiner at the Institute for Global Environmental Technology, Motohiro Okubo (56) References Special Kaihei 6-72971 (JP, A)

Claims (8)

(57) [Claims] 1. A fluorine-based solvent containing one or more hydrogen-containing polyfluorotertiary amines represented by the following general formula (I). Embedded image 2. A fluorine-containing solvent containing one or more hydrogen-containing polyfluorotertiary amines represented by the following general formula (II). Embedded image 3. A hydrocarbon compound, an alcohol compound, an ether compound, a ketone compound, an ester compound, an organic nitrogen compound, or an organic compound, together with the hydrogen-containing polyfluorotertiary amine represented by the general formula (I) or (II). The method according to claim 1, wherein one or more kinds selected from the group consisting of a sulfur compound and an organosilicon compound are contained in an amount of 1 to 50% by weight based on the weight of the hydrogen-containing polyfluorotertiary amine. Fluorinated solvent. 4. The fluorine-based solvent according to claim 1, which is a cleaning agent. 5. The fluorine-based solvent according to claim 1, wherein the fluorine-based solvent is a drainer. 6. The fluorine-based solvent according to claim 1, which is a solvent for dry cleaning. 7. The fluorine-based solvent according to claim 1, which is a solvent for a paint. 8. The fluorine-based solvent according to claim 1, which is a solvent for extraction.