JP2660313B2 - Solvent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solvent composition comprising an organosilicon compound having a fluoroalkoxy group.

[0002]

2. Description of the Related Art Conventionally, halogenated hydrocarbons have been known as solvents for cleaning plastics, rubber products, electronic parts and the like, and these are chlorine atoms or hydrocarbons having chlorine and fluorine atoms. It has the characteristics as a group. These halogenated hydrocarbons are widely used in various industrial fields because they are nonflammable, stable, and can dissolve waxes and oils.

For example, trichloroethylene and tetrachloroethylene are known as having the chlorine atom, and trifluorotrichloroethane (hereinafter referred to as CFC113) is known as having a chlorine atom and a fluorine atom (hereinafter referred to as CFC). And especially the latter C
FC113 is widely used because it has low toxicity and does not erode the surface of plastic or rubber.

[0004]

However, halogenated hydrocarbons having such excellent characteristics are characterized in that chlorine atoms, one of the constituent elements, act as catalysts and destroy the ozone layer surrounding the earth. It has been decided internationally to abolish it.

[0005] In order to address such a problem, for example, various substances in place of CFC113, which is a cleaning solvent, have been specifically studied, but an effective alternative has not been found yet. Since it has been internationally determined that CFC113 and 1,1,1-trichloroethane will be totally abolished, the development of a new cleaning solvent to replace them is indispensable.

The present invention has been made in view of the above situation, and eliminates the drawback that the conventional cleaning solvent comprising CFC113 or the like causes destruction of the ozone layer. Another object of the present invention is to provide a novel cleaning solvent composition having excellent cleaning action.

[0007]

The present inventor has made extensive studies in view of the above-mentioned state of the art, and as a result, has found that an organosilicon compound having a specific structure, that is, a fluorine atom on a carbon atom adjacent to an oxygen atom An organosilicon compound of the following general formula (1) having a fluoroalkoxy group having no
1) Since there is no chlorine in the molecule, there is no danger of destruction of the ozone layer. 2) Excellent cleaning effect of oils and fats, dust, etc. and excellent thermal stability. 3) CFC1 conventionally used.
As a result, the present invention has been found to have a suitable dissolving power similar to that of No. 13 and to selectively dissolve and remove only various stains and not to attack composite parts made of metals, plastics, elastomers and the like, thereby completing the present invention.

Namely, the present invention is to provide a solvent composition such as the following 1 to 10: 1 formula ^{(1): R 1 O-} SiR 2 R 3 R 4 (1) [ In the formula, R ¹ Represents a linear or branched fluoroalkyl group having 2 to 8 carbon atoms having no fluorine atom on the carbon atom adjacent to the oxygen atom, and all of R ² , R ³ and R ⁴ are the same or different It represents a hydrogen atom, a fluorine atom or a monovalent organic group. A solvent composition comprising an organosilicon compound having a fluoroalkoxy group represented by the formula:

2. The solvent composition according to 1 , wherein 2 R ¹ represents a group in which all carbon atoms that are not adjacent to an oxygen atom are substituted with fluorine atoms.

3 R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom, a fluorine atom or a carbon atom
2. The solvent composition according to 1 , which is an alkyl group or an alkoxy group having from 4 to 4 linear or branched groups.

4. The solvent composition according to 3 , wherein R ² , R ³ and R ⁴ are the same and are a methyl group, an ethyl group, an n-propyl group or an isopropyl group.

( 5 ) The solvent further contains a hydrocarbon compound,
One or more selected from the group consisting of an organosilicon compound, an alcohol compound, a ketone compound and an ester compound may be used in an amount of 1 to 50% by weight of the organosilicon compound having a fluoroalkoxy group represented by the general formula (1). %. The solvent composition according to any one of 1 to 4 , wherein

A cleaning composition comprising the solvent composition according to any one of 6 to 5.

A water removing agent composition comprising the solvent composition according to any one of 7 to 5.

[0015]8 The solvent composition according to any one of 1 to 5,
A cleaning solvent composition comprising: 9 A paint comprising the solvent composition according to any one of 1 to 5.
Solvent composition.

[0016] An extraction solvent composition comprising the solvent composition according to any one of 10 to 5.

In the present invention, examples of the linear or branched fluoroalkyl group having 2 to 8 carbon atoms and having no fluorine atom on the carbon atom adjacent to the oxygen atom represented by R ¹ include 2- Fluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3,3
-Difluoropropyl group, 3,3,3-trifluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group,
2-trifluoromethyl-3,3,3-trifluoropropyl group, 2,2,3,4,4,4-hexafluorobutyl group, nonafluoro-t-butyl group, 2,2,3
3,4,4,4-heptafluorobutyl group, 2,2
3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 1-H And a fluoroalkyl group such as a hexafluoroisopropyl group.
Among these groups, a straight-chain or branched group having 1 to 4 carbon atoms in which all carbon atoms not adjacent to an oxygen atom are substituted with fluorine atoms is preferred.

In the present invention, R ² , R ³ and R ⁴ are
Examples include a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isobutoxy group. Among them, R ² , R ³ and R ⁴ are the same or different and are preferably hydrogen atom, fluorine atom, methyl group, ethyl group, propyl group, methoxy group, ethoxy group and the like. In particular, when used as a solvent composition, R ¹ is a straight-chain or branched group having 1 to 4 carbon atoms in which all carbon atoms that are not adjacent to an oxygen atom are substituted with fluorine atoms, and R ² , R ^{2 When 3} and R ⁴ are the same and are a methyl group, an ethyl group, an n-propyl group or an isopropyl group, they have good detergency and thermal stability, selectively dissolve and remove only various stains, and can be used for materials, especially plastics. This is preferable since it has no effect and the boiling point is in an appropriate range.

Specific examples of the organosilicon compound having a fluoroalkoxy group represented by the above general formula of the present invention include: * (3,3,3-trifluoropropyl) dimethoxymethylsilane, * (1,1 , 1,3,3,3-hexafluoroisopropoxy) trimethylsilane, * (2-fluoroethoxy) trimethylsilane, * trimethyl (2,
2,3,3,3-pentafluoropropoxy) silane,
* Trimethyl (2,2,3,3-tetrafluoropropoxy) silane, * trimethoxy (3,3,3-trifluoropropyl) silane, * methoxydimethyl (3,3
3- (trifluoropropyl) silane, * (3,3-difluoropropyl) trimethoxysilane, * (3-fluoropropyl) trimethoxysilane, * (2,2,2-trifluoroethoxy) trimethylsilane, * (2 , 2,
3,3,4,4,4-heptafluorobutoxy) trimethylsilane, * (2,2,3,3,4,4,5,5,5
-Nonafluoropentoxy) trimethylsilane, *
(2,2,3,3,3-pentafluoropropoxy) triethylsilane, * (2,2,3,3,3-pentafluoropropoxy) dimethylethylsilane, * (perfluoro-t-butoxy) trimethylsilane, * [1,1-
Bis (trifluoromethyl) ethoxy] trimethylsilane, * (2,2,3,3-tetrafluoropropoxy)
Trimethylsilane, * (2,2,3,4,4,4-hexafluorobutoxy) trimethylsilane and the like.

These organosilicon compounds having a fluoroalkoxy group can be produced by a known method. For example, a fluorine-containing alcohol (for example, R ¹ O
H: R ¹ is the same as described above, and is easily obtained by reacting with silazane or chlorosilane (for example, P.YKMA
N. et al. Org. Chem. , 116 , 153-15
9 (1976)). These compounds can be further mixed with other components according to the application. For example,
In the cleaning composition, one or more of a hydrocarbon compound, an organosilicon compound, an alcohol compound, a ketone compound, and an ester compound are replaced with an organosilicon compound having a fluoroalkoxy group represented by the general formula (1). You may contain 1-50% of weight. Specific examples of the hydrocarbon compound include aliphatic and aromatic alkyl groups having 1 to 8 carbon atoms such as pentane, hexane, heptane, octane, cyclohexane, benzene, and toluene. Specific examples of the organosilicon compound include tetramethylsilane, tetraethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylsilane, dimethylethoxysilane, and ethyltrimethylsilane. Examples of the alcohol compound include alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, and butanol.
Examples of the ketone compound include propanone, butanone, 2-pentanone, and 3-pentanone. Examples of the ester compound include carboxylic acid esters such as formic acid esters and acetic acid esters.

The compound of the present invention has good thermal stability in ordinary use, but may use a stabilizer if necessary. Examples of the stabilizer include nitro compounds, unsaturated hydrocarbons, epoxy compounds, phenol compounds, alkenylamines, cyclic nitrogen compounds, and unsaturated alcohols. In addition, a surfactant may be added.

The compounds of the present invention may be used as a solvent composition, but also as a foaming agent, a propellant, a refrigerant, and the like.
Since it has the same dissolving power as that described above, it is preferable to use it as a solvent composition. Specific uses of the solvent composition include a detergent composition, a water removing agent composition, a dry cleaning solvent composition, a solvent composition for paint, and an extractant composition. The cleaning composition comprises flux, grease, oil,
It is used to remove wax, ink, and the like from the surface of glass, ceramics, plastics, rubber, various metallic articles, particularly IC parts, electric equipment, precision instruments, optical lenses, and the like. The water removing agent composition is used for removing 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.

The above-mentioned organosilicon compound of the present invention has good detergency and heat stability, selectively dissolves only various stains,
It has little effect on materials, especially plastics. Further, since it has no chlorine atom, there is no problem of depletion of the ozone layer. Further, since the thermal decomposition temperature is high, it can be applied to gas-phase soldering applications where thermal stability is particularly required.

The production examples of the compounds used in the present invention and the examples of the present invention are shown below.

[0025]

[Production Example 1] * Production of 2,2,2-trifluoroethoxytrimethylsilane 60.0 g of 2,2,2-trifluoroethanol (0.
6 mol) and 48.4 g of hexamethyldisilazane (0.3
Mol) were mixed at room temperature, heated gradually, and further heated to reflux for 11 hours. The reaction solution was distilled by attaching a rectification tube to obtain the title compound. 82.5 g (80% yield). Boiling point 81
８81.5 ° C.

[0026]

[Production Example 2] * Production of 2,2,3,3,3-pentafluoropropoxytrimethylsilane 2,2,3,3,3-pentafluoropropanol 6
0.0 g (0.4 mol) of hexamethyldisilazane 3
2.3 g (0.2 mol) are mixed at room temperature and gradually heated,
The mixture was further refluxed for 11 hours. After the reaction solution was distilled, the mixture was further distilled by attaching a rectification tube to obtain the title compound. Yield 54.
0 g (61% yield). Boiling point 96 ° C.

[0027]

[Production Example 3] * Production of 1-H-hexafluoroisopropoxytrimethylsilane 67.2 g (0.4 mol) of 1,1,1,3,3,3-hexafluoro-2-propanol and hexamethyldisilazane 32.3 g (0.2 mol) were mixed at room temperature, gradually heated, and further heated to reflux for 30 minutes. After distilling the reaction solution,
Further, a distillation column was attached and distillation was performed to obtain the title compound. Yield 79.1 g (82% yield). Boiling point 90 ° C

[0028]

Examples 1-3 and Comparative Examples 1-2 In air, temperature 50
Place the sample in a SUS-316 container heated at 0 ° C for 1 hour.
Inject 0 torr. Remove the container from room temperature to 50 over 2 hours.
The temperature was raised to 0 ° C., and the heat resistance of the sample was examined using the point where the pressure-temperature began to deviate from the straight line as the thermal decomposition starting temperature.

The results are collectively shown in Table 1.

For comparison, a compound having a fluorine atom on a carbon atom adjacent to an oxygen atom and CFC113
The thermal decomposition onset temperature is also shown. In the table, Me represents a methyl group.

[0031]

[Table 1]

From the results shown in Table 1, the compound of the present invention having no fluorine atom on the carbon atom adjacent to the oxygen atom was compared with the compound having a fluorine atom on the carbon atom of Comparative Example 1 and the CFC113 of Comparative Example 2. It is clear that they have excellent thermal stability.

[0033]

Examples 4 to 10 and Comparative Example 3 A test piece of SUS-304 was immersed in machine oil (CQ-30 manufactured by Nippon Oil) and then immersed in various cleaning compositions of the present invention at 25 ° C. for 5 minutes. did. The extent to which the machine oil was removed was visually observed.

The results are collectively shown in Table 2. For comparison, a case where CFC113 which is a conventional cleaning agent for machine oil was used as a solvent is also shown.

[0035]

[Table 2]

However, in Table 2, “は” indicates that there is no washing residue visible to the naked eye.

"X" indicates that there is a wash residue that is visible to the naked eye.

From the results shown in Table 2, the solvent composition of the present invention was
It has been found that it has a detergency equivalent to that of the conventionally used CFC113.

[0039]

The organosilicon compound having a fluoroalkoxy group of the present invention has good detergency and thermal stability as a solvent composition, does not adversely affect materials, especially plastics, and has no chlorine atom. It does not cause the ozone layer depletion problem, can be used in the same manner as the conventional CFC-based solvent, does not require a significant change in existing equipment, and can be applied as it is, and is extremely valuable.

[0040]

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref., Institute of Chemical Technology, Industrial Technology Institute (72) Inventor Tsutomu Kobayashi Hongo Wakai Building 2-40-17 Hongo, Bunkyo-ku, Tokyo Within the Institute for Global Environmental Technology Research (72) Inventor Nobuto Hoshi 2-40-17 Hongo, Bungo-ku, Tokyo Hongo Wakai Building Examiner, Satoshi Moriyasu, Institute for Global Environmental Technology Research (56) References JP Akira 63-77886 (JP, A) JP-A-61-263986 (JP, A) JP-A-6-108095 (JP, A) CHEMICAL ABSTRACT 90: 175467 CHEMICAL ABSTRACT 85: 103123

Claims (5)

(57) [Claims] 1. A compound represented by the general formula (1): R ¹ O—SiR ² R ³ R ⁴ (1) [wherein R ¹ has 2 to 2 carbon atoms having no fluorine atom on a carbon atom adjacent to an oxygen atom. shows a fluoroalkyl group having a straight-chain or branched 8, R ^2, R ³ and R ⁴ are both the same or different hydrogen atom, a fluorine atom or a carbonitride
Straight-chain or branched alkyl groups having 1 to 4 atoms
Or an alkoxy group . ] The cleaning solvent composition containing the organosilicon compound which has a fluoroalkoxy group represented by these. 2. The cleaning solvent composition according to claim 1, wherein R ¹ represents a group in which all carbon atoms that are not adjacent to an oxygen atom are substituted with fluorine atoms. 3. R ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom, a fluorine atom , a methyl group, an ethyl group, a
Propyl group, isopropyl group, butyl group, isobutyl group,
Methoxy, ethoxy, propoxy, butoxy
The cleaning solvent composition according to claim 1, which is an isobutoxy group . 4. The cleaning solvent composition according to claim 3, wherein R ² , R ³ and R ⁴ are the same and are a methyl group, an ethyl group, an n-propyl group or an isopropyl group. 5. The solvent further comprises one or more selected from the group consisting of hydrocarbon compounds, organosilicon compounds, alcohol compounds, ketone compounds and ester compounds represented by the general formula (1). The cleaning solvent composition according to any one of claims 1 to 4, comprising 1 to 50% by weight of the organosilicon compound having a fluoroalkoxy group.