JP2774765B2 - Solvent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composition of a solvent containing an organosilicon compound having a fluoroalkoxy group, and to the organosilicon compound.

[0002]

2. Description of the Related Art Halogenated hydrocarbons are conventionally known as solvents for cleaning plastics, rubber products, electronic parts, etc., and are characterized as a chlorine atom or a hydrocarbon group having a chlorine atom and a fluorine atom. have. These halogenated hydrocarbons are widely used in various industrial fields because they are nonflammable, stable, and can dissolve waxes 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. Etc. are widely used because they do not erode the surface. However, halogenated hydrocarbons having such excellent characteristics have been shown to destroy the ozone layer surrounding the earth by using a chlorine atom as one of the constituent elements as a catalyst. , 1,1-Trichloroethane has been internationally decided to be abolished.

To cope with such problems, it is essential to develop new cleaning solvents to replace them. For example, although various substances in place of CFC113, which is a cleaning solvent, have been specifically studied, they are still effective. No alternative has been found. For example, US Pat.
No. 33 describes that dimethyl bis (nonafluoro-t-butoxy) silane is useful as a solvent. However, since the compound has as many as 6 trifluoromethyl groups in the molecule, its solubility is significantly reduced. Further, in this example, nonafluoro-t-butyl alcohol, which is a raw material and a decomposition product of the compound, is an extremely toxic compound, and when this compound is used as a cleaning agent, there is a danger of harm to workers. There is.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and eliminates the disadvantage that a conventional cleaning solvent such as CFC113 causes destruction of the ozone layer. The present invention is to provide a novel cleaning solvent composition excellent in water resistance.

[0006]

SUMMARY OF THE INVENTION The present invention has been made by conducting intensive studies in view of the state of the prior art, and as a result, an organosilicon compound having a specific structure, that is, a fluorine atom on a carbon atom adjacent to an oxygen atom. A composition comprising an organosilicon compound of the following general formula I having a fluoroalkoxy group not having,
Since there is no chlorine in the molecule, there is no danger of destroying the ozone layer, and it has an excellent cleaning effect on oils and fats, dust, etc., and has the same appropriate dissolving power as CFC113, which has been conventionally used. The present invention has been found to be selectively dissolved and removed, and not to attack composite parts made of metal, plastic, elastomer and the like, and have completed the present invention. That is, the present invention includes one or more organosilicon compounds having a fluoroalkoxy group, represented by the following general formula I, wherein the number of trifluoromethyl groups contained in the molecule is 5 or less. A solvent composition.

The general formula I

[0008]

Embedded image

In the general formula I presented in the present invention,
Examples of the fluoroalkyl group represented by R ¹ , R ² and R ³ having a straight or branched chain of 2 to 8 carbon atoms having no fluorine atom on the carbon atom adjacent to the oxygen atom include 2- Fluoroethyl group, 2,2-difluoroethyl 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, 1,1,1,3,3,3-hexafluoroisopropyl Group, 1,1,3,3-tetrafluoroisopropyl 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-nona Fluoropentyl group, 2,2,3,3,4,4,5,5
6,6,6-undecafluorohexyl group and the like. Among these groups, a linear or branched fluoroalkyl group having 2 or more fluorine atoms and 2 to 4 carbon atoms is preferred, and a compound having a fluoroalkyl group having 5 or more fluorine atoms is preferably hydrolyzed. It is more preferable because it is difficult to perform.

In the present invention, the alkyl group of R ⁴ and R ⁵ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group and a t-group.
-Butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Among them, R ⁴ and R ⁵ are preferably a straight-chain or branched alkyl group having 1 to 4 carbon atoms, since the organosilicon compound has an appropriate boiling point range. Among the organosilicon compounds having a fluoroalkoxy group, compounds having four fluoroalkoxy groups, or among the organosilicon compounds having a fluoroalkoxy group represented by the above general formula I, the trifluoromethyl group contained in the molecule Compounds with a number of 6 or more have poor solubility, which is a property required as a detergent, or are easily decomposed by moisture to form a non-volatile substance. Therefore, the number of trifluoromethyl groups contained in the molecule needs to be 5 or less, and more preferably 4 or less.

The organosilicon compound having a fluoroalkoxy group of the present invention represented by the above general formula I and having no more than 5 trifluoromethyl groups in the molecule is specifically exemplified by dimethyl Bis (2,2,2-trifluoroethoxy) silane, methyltris (2,2,2
-Trifluoroethoxy) silane, ethyltris (2,
2,2-trifluoroethoxy) silane, propyltris (2,2,2-trifluoroethoxy) silane, diethylbis (2,2,2-trifluoroethoxy) silane, dimethylbis (1,1,1,3,3) 3,3-hexafluoroisopropoxy) silane, diethyl bis (1,
1,1,3,3,3-hexafluoroisopropoxy)
Silane, methyltris (2,2,3,3-tetrafluoropropoxy) silane, dimethylbis (1,1,3,3
-Tetrafluoropropoxy) silane, dimethylbis (2,2,3,4,4,4-hexafluorobutoxy)
Silane, dimethyl bis (2,2,3,3,4,4,4-
Heptafluorobutoxy) silane, dimethyl (1,1,
1,3,3,3-hexafluoropropoxy) (2
2,2-trifluoroethoxy) silane and the like.

[0012]

These organosilicon compounds having a fluoroalkoxy group can be produced by a known method. For example, a fluorinated alcohol (for example, ROH:
R can be obtained very easily only by reacting R ¹ , R ² or R ³ with dichlorosilane or trichlorosilane (for example, J. Pola et al., Collec).
t. Czech. Chem. Commun. , 44 volumes,
750-755, 1979). A method of synthesizing by photoreaction between dimethylsilane and hexafluoroacetone, such as dimethylbis (1,1,1,3,3,3-hexafluoroisopropoxy) silane, is also known (A.F. Janzen et al., Can. J. Che.
m. 43, 3063-3068, 1965
Year).

These compounds can be further mixed with other components, if necessary. For example, one 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
1 or 50% by weight of the organosilicon compound having a fluoroalkoxy group represented by the general formula I
May be contained. 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. As ether compounds, diethyl ether, diisopropyl ether, dibutyl ether, dioxane,
Examples include 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 tetramethylsilane, tetraethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, hexamethyldisiloxane, octamethylcyclotetrasiloxane, and the like. In the solvent composition of the present invention, a stabilizer may be used if necessary. 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 added.

The composition of the present invention is nonflammable or flame-retardant because it contains a compound having a large number of fluorine atoms in the molecule, has excellent surface permeability due to low surface tension, and has low latent heat of vaporization. Excellent drying properties from conventional CFCs
Since it has the same dissolving power as 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. The cleaning agent is used to remove flux, grease, oil, wax, ink, and the like from the surface of various articles made of glass, ceramics, plastic, rubber, and metal, particularly, IC parts, electric equipment, precision instruments, optical lenses, and the like. A drainer is used to remove water from the surface after washing the article with water. Cleaning methods include hand wiping, dipping, spraying,
Oscillation, ultrasonic cleaning, steam cleaning, or the like may be employed. The composition containing the above-mentioned organosilicon compound of the present invention has good cleaning properties, selectively dissolves only various stains, and has little effect on materials, especially plastics. Further, since there is no chlorine atom, there is no problem of destruction of the ozone layer.

[0016]

The present invention will now be described by way of examples, which should not be construed as limiting the invention. Reference Example 1 Synthesis of dimethylbis (2,2,3,3,3-pentafluoropropoxy) silane In 60 g (0.4 mol) of 2,2,3,3,3-pentafluoropropanol, 26 g of dichlorodimethylsilane ( 0.2 mol) was added dropwise at 0 ° C. Gradually raise the temperature, 100 ° C for 13 hours, 1 more
Stirred at 40 ° C. for 2 days. The reaction solution was distilled by attaching a rectification tube to obtain the title compound. The structure of the product is NMR, IR
Confirmed by spectrum and mass spectrum. Yield 5
5.1 g (77.4% yield). Boiling point 140 ° C.

¹ H-NMR spectrum; δ (CDC
l ₃ ): 0.24 ppm (s, 3H), 4.10 ppm
(T, J = 12.9 Hz, 2H). The spectrum is shown in FIG. ¹⁹ F-NMR spectrum; δ (CDCl ₃ ):-
83.87 ppm (s, 3F), -125.93 ppm
(T, J = 12.9 Hz, 2F). The spectrum is shown in FIG. IR spectrum; 1270, 1201, 114
8, 1100, 1031, 870, 813 cm ^-1 . The spectrum is shown in FIG. GC-MS (CI); (M + H)
+357 Reference Example 2 Synthesis of methyltris (2,2,3,3,3-pentafluoropropoxy) silane To 45 g (0.3 mol) of 2,2,3,3,3-pentafluoropropanol and 15 g of trichloromethylsilane (0.1 mol) was added dropwise at 0 ° C. After stirring at room temperature for 3 hours, the temperature was gradually increased to 14
The mixture was stirred at 0 ° C for 13 hours and further at 180 ° C for 2 hours. The reaction solution was distilled by attaching a rectification tube to obtain the title compound. The structure of the product was confirmed by NMR, IR spectrum and mass spectrum. Yield 39.4g (80.4% yield).
Boiling point 171 ° C.

¹ H-NMR spectrum; δ (CDC
l ₃ ): 0.31 ppm (s, 1H), 4.18 ppm
(T, J = 12.7 Hz, 2H). The spectrum is shown in FIG. ¹⁹ F-NMR spectrum; δ (CDCl ₃ ): -83.
61 ppm (s, 3F), -125.79 ppm (t,
J = 12.9 Hz, 2F). The spectrum is shown in FIG.

IR spectrum; 1279, 1206, 1
148, 1099, 1033, 870 cm ^-1 . The spectrum is shown in FIG. GC-MS (CI); (M + H) +491 Reference Example 3 Synthesis of dimethylbis (2,2,2-trifluoroethoxy) silane 2,2,2-trifluoroethanol 200
g (2.0 mol), 129 g of dichlorodimethylsilane
(1.0 mol) was added dropwise at 0 ° C. over 1 hour. After stirring at room temperature for 19 hours and at 50 ° C. for 6 hours, the mixture was heated under reflux for 1 hour. The reaction solution was distilled by attaching a rectification tube to obtain the title compound. Yield 228 g (89% yield). Boiling point 12
0.5-121.5 ° C.

Reference Example 4 Synthesis of methyltris (2,2,2-trifluoroethoxy) silane 2,2,2-trifluoroethanol 305
g (3.05 moles) with trichloromethylsilane 14
9.5 g (1.0 mol) was added dropwise at 0 ° C. over 4 hours. After further stirring at room temperature for 24 hours, the mixture was heated under reflux for 2 hours. The reaction solution was distilled by attaching a rectification tube to obtain the title compound. Yield 265 g (78% yield). Boiling point 146.5-
147.5 ° C.

Examples 1 to 7 and Comparative Example 1 A test piece of SUS-304 was used as a machine oil (C
Q-30) After immersion in various cleaning agents of the present invention,
Soak for minutes. The extent to which the machine oil was removed was visually observed. The results are collectively shown in Table 1. For comparison, a case where CFC113, which is a conventional cleaning agent for machine oil, was used as a solvent is also shown.

[0022]

[Table 1]

In Table 1, ○ indicates that there is no cleaning residue visible to the naked eye, and X indicates that there is cleaning residue visible to the naked eye. Examples 8 to 12 and Comparative Examples 2 to 3 Test pieces of each plastic were immersed in various cleaning agents of the present invention at 45 ° C. for 1 hour, and the weight change rate was left at room temperature for 2 hours, and the dimensional change rate was taken out. Measured immediately. For comparison, a similar test was performed for CFC113, 1,1,1-trichloroethane. The results are summarized in Table 2.

[0024]

[Table 2]

Examples 13 to 17 and Comparative Examples 4 to 5 The organosilicon compounds of various cleaning agents of the present invention were shaken with water for 1 hour at room temperature or 4 hours at 80 ° C.
The presence or absence of decomposition was determined by analysis. For comparison, tetrakis (2,2,2-trifluoroethoxy) silane, which is a compound having four fluoroalkoxy groups, and tris (1,1), which is a compound having six trifluoromethyl groups, are provided. A similar test was conducted for (1,1,3,3,3-hexafluoroisopropoxy) methylsilane.
The results are summarized in Table 3.

[0026]

[Table 3]

Examples 18 to 22 and Comparative Examples 6 to 7 50 parts by weight of an organosilicon compound of various detergents of the present invention and 50 parts by weight of n-hexane or 50 parts by weight of carbitol were mixed at room temperature. Was examined. The results are summarized in Table 4. For comparison, tetrakis (2, 2, 3, 3), which is a compound having 4 fluoroalkoxy groups,
A similar test was conducted for 3,3-pentafluoropropoxy) silane. However, two layers were separated from n-hexane, and the solubility was low (Comparative Example 6). Bis (nonafluoro-t-) which is a compound having 6 trifluoromethyl groups
The same test was carried out for butoxy) dimethylsilane, but it was separated into two layers from carbitol and the solubility was low (Comparative Example 7).

[0028]

[Table 4]

[0029]

As described above, the composition containing the organosilicon compound having a fluoroalkoxy group of the present invention has good detergency, does not affect materials, especially plastics, and has a chlorine atom. Therefore, it does not cause a problem of destruction of the ozone layer, can be used in the same manner as a conventional CFC-based solvent, does not require a significant change in existing equipment, and can be applied as it is.

[Brief description of the drawings]

¹ H-N in FIG. 1 of the compound obtained in Reference Example 1 of the present invention
It is an MR spectrum figure.

FIG. 2 shows ¹⁹ FN of the compound obtained in Reference Example 1 of the present invention.
It is an MR spectrum figure.

FIG. 3 is an IR spectrum of the compound obtained in Reference Example 1 of the present invention.

FIG. 4 shows ^1- NM of the compound obtained in Reference Example 2 of the present invention.
It is an R spectrum.

FIG. 5 shows ¹⁹ FN of the compound obtained in Reference Example 2 of the present invention.
It is an MR spectrum figure.

FIG. 6 is an IR spectrum of the compound obtained in Reference Example 2 of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (74) Attorney Hidetaka Komatsu (3 outside agents) (72) Inventor Akira Sekiya 1-1-1 Higashi, Tsukuba, Ibaraki Pref. (72) Inventor Nobuto Hoshi 2-40-17 Hongo Wakai Building, Bunkyo-ku, Tokyo Within the Institute for Global Environmental Technology Research (72) Inventor Tsutomu Kobayashi 2-40-17 Hongo, Bunkyo-ku, Tokyo Hongo Wakai Building Foundation Examiner at the Institute of Technology for Environmental Innovative Technology Ichiyoshi Karaki (56) Reference US Patent 2882859 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07F 7/12 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (3)

(57) [Claims] 1. A composition comprising one or more kinds of organosilicon compounds having a fluoroalkoxy group, represented by the following general formula I, wherein the number of trifluoromethyl groups contained in the molecule is 5 or less. Solvent composition. Formula (I) (R ¹ O) l (R ² O) m (R ³ O) nSiR ⁴ rR ⁵ s (wherein R ¹ , R ² and R ³ are on a carbon atom adjacent to an oxygen atom Represents a linear or branched fluoroalkyl group having 2 to 8 carbon atoms having no fluorine atom, R ⁴ and R ⁵ represent alkyl groups, and l, m, n = 0 to 3, l + m
+ N = 2-3, r, s = 0-2, r + s = 1-2, l +
m + n + r + s = 4) 2. The solvent composition according to claim 1, wherein R ⁴ and R ⁵ are the same or different and are linear or branched alkyl groups having 1 to 4 carbon atoms. 3. The solvent further comprises 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. The solvent composition according to any one of claims 1 to 2, comprising 1 to 50% by weight of the organosilicon compound having a fluoroalkoxy group represented by the general formula I.