JPH05220304A - Antifoaming agent - Google Patents

Abstract

PURPOSE:To provide an extremely high antiforming property by incorporating a fluoroalkyl group-contg. organosilicon compd. shown by the specified general formula as an effective component. CONSTITUTION:This antifoaming agent contains a fluoroalkyl group-contg. organosilicon compd. shown by formula I as the effective component. In formula I, R is a 1-10C alkyl, alkoxy or alkoxycarbonyloxy group, RF is (CF2)n1 or shown by formula II, wherein X is hydrogen, fluorine or chlorine atom, n1 is an integer of 1 to 10, n2 is an integer of 0 to 8, (a) and (b) are 0 or 1 and a+bnot equal to 0. The organosilicon compd. is produced by allowing a specified difluoroalkanoyl peroxide to reach with a specified phenyl group-contg. organosilicon compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a defoaming agent containing a novel fluoroalkyl group-containing organosilicon compound as an active ingredient.

[0002]

2. Description of the Related Art Organic compounds containing a fluoroalkyl group have been attracting attention as compounds having useful properties such as light resistance, water and oil repellency, and physiological activity.
In particular, a fluoroalkyl group-containing organosilicon compound in which a fluoroalkyl group is introduced into an organosilicon compound has low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, and mold release. In various fields, for example, pharmaceuticals, because of its excellent properties such as anti-foaming property, defoaming property and chemical resistance.
Surface treatment for imparting water and oil repellency and stain resistance to the surface of synthetic intermediates such as pesticides, adhesion improvers such as resists in the production process of semiconductor devices, optical lenses, eyeglass lenses, glassware, etc. It is widely used in the field of agents, and materials that impart releasability. As the above-mentioned fluoroalkyl group-containing organosilicon compound, JP-A-2-219829 and JP-A-2-219830 each disclose a compound in which a fluoroalkyl group is introduced into polysiloxane. On the other hand, an antifoaming agent containing such a silicon compound as an active ingredient is also known. However, in reality, it is desired to develop an active ingredient exhibiting excellent defoaming property by adding a small amount of the compound as compared with a silicon compound conventionally used as a defoaming agent. Further, a fluoroalkyl group-containing organosilicon compound itself obtained by introducing a fluoroalkyl group into the organosilicon compound as shown in the present invention is not known.

[0003]

The object of the present invention is to provide an antifoaming agent containing a novel fluoroalkyl group-containing organosilicon compound as an active ingredient, which has a low surface tension property and exhibits an excellent defoaming property. To do.

[0004]

According to the present invention, there is provided an antifoaming agent containing a fluoroalkyl group-containing organosilicon compound represented by the following general formula 2 (hereinafter referred to as organosilicon compound 1) as an active ingredient. To be done.

[0005]

[Chemical 2]

The present invention will be described in more detail below.

The defoaming agent of the present invention contains the organosilicon compound 1 represented by the general formula 2 as an active ingredient.
In the organosilicon compound 1, R has 11 carbon atoms.
In the case of the above alkyl group, alkoxy group or alkylcarbonyloxy group, it is difficult to produce, and n
_{When 1} exceeds 10, or n ₂ exceeds 8, the solubility in a solvent decreases, and therefore it cannot be used.

In the organosilicon compound 1, the applicable RF, namely,-(CF ₂ ) n ₁ X or the following general formula 3 is specifically listed. F ₃ C--, F (CF ₂ ) _2- , F (CF ₂ ) ₃ −, F
(CF ₂ ) ₄ −, F (CF ₂ ) ₅ −, F (CF ₂ ) ₆ −, F
(CF ₂ ) ₇ −, F (CF ₂ ) ₈ −, F (CF ₂ ) ₉ −, F
(CF ₂ ) ₁₀ −, HCF ₂ −, H (CF ₂ ) ₂ −, H (CF
_{2) 3 -, H (CF} 2) 4 -, H (CF 2) 5 -, H (C
F ₂ ) ₆ −, H (CF ₂ ) ₇ −, H (CF ₂ ) ₈ −, H (CF
_{2) 9 -, H (CF} 2) 10 -, ClCF 2 -, Cl (C
_{F 2) 2 -, Cl (} CF 2) 3 -, Cl (CF 2) 4 -, Cl
(CF ₂ ) ₅ −, Cl (CF ₂ ) ₆ −, Cl (CF ₂ ) ₇ −,
_{Cl (CF 2) 8 -,} Cl (CF 2) 9 -, Cl (CF 2)
_10- , the following chemical formulas are chemical formula 4, chemical formula 5, chemical formula 6, chemical formula 7, chemical formula 8, chemical formula 9, chemical formula ₁₀ , chemical formula 11, and chemical formula 12.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical 12]

Further, as the organosilicon compound 1, specifically, for example, the following general formulas 13, 14, and 15
Chemical formula 16, Chemical formula 17, Chemical formula 18, Chemical formula 19, Chemical formula 20, Chemical formula 21, Chemical formula 22, Chemical formula 23, Chemical formula 24, Chemical formula 25, Chemical formula 26, Chemical formula 27, Chemical formula 2
8, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 33, Chemical 3
4, Chemical 35, Chemical 36, Chemical 37, Chemical 38, Chemical 39, Chemical 4
0, Chemical formula 41, Chemical formula 42 and the like can be mentioned (wherein, the position of the RF group bonded to the benzene ring is any of ortho, meta and para).

[0020]

[Chemical 13]

[0021]

[Chemical 14]

[0022]

[Chemical 15]

[0023]

[Chemical 16]

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Chemical 20]

[0028]

[Chemical 21]

[0029]

[Chemical formula 22]

[0030]

[Chemical formula 23]

[0031]

[Chemical formula 24]

[0032]

[Chemical 25]

[0033]

[Chemical formula 26]

[0034]

[Chemical 27]

[0035]

[Chemical 28]

[0036]

[Chemical 29]

[0037]

[Chemical 30]

[0038]

[Chemical 31]

[0039]

[Chemical 32]

[0040]

[Chemical 33]

[0041]

[Chemical 34]

[0042]

[Chemical 35]

[0043]

[Chemical 36]

[0044]

[Chemical 37]

[0045]

[Chemical 38]

[0046]

[Chemical Formula 39]

[0047]

[Chemical 40]

[0048]

[Chemical 41]

[0049]

[Chemical 42]

The organosilicon compound 1 can be produced by reacting a specific difluoroalkanoyl peroxide with a specific phenyl group-containing organosilicon compound.

The specific difluoroalkanoyl peroxide preferably includes difluoroalkanoyl peroxide represented by the following general formula 43 (hereinafter referred to as difluoroalkanoyl 2). In the above difluoroalkanoyl 2, when n ₁ is 11 or more or n ₂ is 9 or more, the solubility of the difluoroalkanoyl 2 is lowered when the reaction is performed in the presence of a solvent, which is not preferable.

[0052]

[Chemical 43]

In addition, R in the difluoroalkanoyl 2 is
F is the same as RF specifically listed in the organosilicon compound 1, and the difluoroalkanoyl 2 is specifically, for example, diperfluoro-2-peroxide.
Methyl-3-oxahexanoyl, diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide,
Preferable examples include diperfluorobutyryl peroxide and diperfluoroheptanoyl peroxide.

As the specific phenyl group-containing organosilicon compound, a phenyl group-containing organosilicon compound represented by the following general formula 44 (hereinafter referred to as organosilicon compound 3) can be preferably mentioned. In the organosilicon compound 3, R is an alkyl group having 11 or more carbon atoms,
In the case of an alkoxy group or an alkylcarbonyloxy group, it is difficult to manufacture and it is not preferable.

[0055]

[Chemical 44]

Specific examples of the organosilicon compound 3 include 3,3-diphenylhexamethyltrisiloxane, 3,3-diphenylhexaethyltrisiloxane, 3,3-diphenylhexapropyltrisiloxane and 3,3. -Diphenylhexabutyltrisiloxane,
3,3-diphenylhexamethoxytrisiloxane,
3,3-diphenylhexaethoxytrisiloxane,
3,3-diphenylhexapropoxytrisiloxane,
Preferred examples include 3,3-diphenylhexabutoxytrisiloxane and the like.

Further, when the difluoroalkanoyl 2 and the organosilicon compound 3 are reacted, the charge molar ratio is preferably in the range of 1: 0.1 to 10.0, and particularly 1: 0. It is preferably in the range of 3 to 5.0. The molar ratio of the organosilicon compound 3 charged was 0.
When it is less than 1, a large amount of a product resulting from the self-decomposition of peroxide is produced, and when it is more than 10, the yield of the target fluoroalkyl group-containing organosilicon compound is lowered, which is preferable. Absent. When both a and b of the organosilicon compound 1 are set to 1, it is preferable that the charged molar ratio of the organosilicon compound 3 to the difluoroalkanoyl 2 is 2 or more. Furthermore, the reaction can be carried out at normal pressure, and the reaction temperature is preferably-
20 to + 150 ° C, particularly preferably 0 to 100 ° C. When the reaction temperature is lower than -20 ° C, the reaction takes a long time, and when it is higher than + 150 ° C, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Furthermore, the reaction time is preferably in the range of 30 minutes to 20 hours, and industrially particularly preferably in the range of 1 to 10 hours.

In the defoaming agent of the present invention, the content ratio of the organosilicon compound 1 can be variously selected according to the object, but is preferably 0.01 to 100% by weight, particularly preferably 0.1 to 50%. It is preferably set to wt%.

In the defoaming agent of the present invention, the organosilicon compound 1 can be used as it is as a defoaming agent. For example, when it is added to a non-aqueous solution, methyl ethyl ketone,
Ketone-based solvent such as methyl isobutyl ketone or 1,1,
It can also be prepared by dissolving the organosilicon compound 1 in a halogen-based organic solvent such as 2-trichlorotrifluoroethane. Further, the organosilicon compound 1 is emulsified in an aqueous solution by, for example, a homomixer or the like to prepare an emulsion. You can also The emulsion particle size is 0.1-100
The range of μm is preferable, and 1 to 10 μm is particularly preferable.
Further, in order to stabilize the emulsion, a known thickener such as polyvinyl alcohol may be contained. Furthermore, in the defoaming agent of the present invention, in order to facilitate entry into the foam film and exert a stronger defoaming effect,
If necessary, known antioxidants, fillers such as silica, alumina, titanium dioxide and the like can be contained.

When the defoaming agent of the present invention is used, an excellent effect can be obtained by adding it to a foaming aqueous solution or a non-aqueous solution. At this time, the addition amount of the defoaming agent of the present invention to the aqueous solution or the non-aqueous solution is preferably 0.01 ppm by weight based on the amount of the organosilicon compound 1.
It may be added in an amount of 1000 ppm, particularly preferably 0.1 ppm to 100 ppm. Addition amount is 0.01pp
When it is less than m, the decrease in the surface tension due to the organosilicon compound 1 is not sufficient, the solubility in an aqueous solution or a non-aqueous solution becomes large, the foam suppressing effect becomes insufficient, and the addition amount exceeds 1000 ppm. However, the dispersibility in an aqueous solution or a non-aqueous solution and the expandability to foams are lowered, and the defoaming effect, especially the defoaming property and the quick-acting property become insufficient, which is not preferable.

[0061]

The antifoaming agent of the present invention has low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency,
A fluoroalkyl group-containing organosilicon compound, which is a novel compound having properties such as releasability, defoaming property, and chemical resistance, is used as an active ingredient, so it is chemically inert and can be used under various adverse conditions. Stable without reacting with foaming substances. Therefore,
It can be used in a food manufacturing process or a dishwashing process, and further in wastewater treatment. In addition, to paints, inks, latexes, etc. for which known defoaming agents could not be used due to problems such as high-temperature dyeing process of fibers and decomposition gas desulfurization process of hydrocarbons and adhesion, paintability (paintability), and cissing Can be used and can be widely used in various industrial processes involving foaming.

[0062]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited thereto.

[0063]

Synthesis Example 1 3,3-Diphenylhexamethyltrisiloxane (10.9 g, 30 mmol) was added with diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide (24.8 g, 25 mmol). 300 g of a 1,1,2-trichlorotrifluoroethane solution containing it was added, and the reaction was carried out at 40 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solvent is removed, and then distillation is carried out to obtain the following chemical formula 4
A fluoroalkyl group-containing organosilicon compound represented by 5 was obtained with a yield of 91% (yield 22.8 g).

[0064]

[Chemical 45]

[0065]

[Synthesis Example 2] The reaction was performed in the same manner as in Synthesis Example 1 except that the charged amount of 3,3-diphenylhexamethyltrisiloxane was 12.5 mmol (4.5 g). An alkyl group-containing organosilicon compound was obtained with a yield of 63% (yield 9.9 g).

[0066]

[Chemical 46]

[0067]

Synthesis Example 3 Similar to Synthesis Example 1 except that diperfluoro-2-methyl-3-oxahexanoyl peroxide was used instead of diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide. To give a fluoroalkyl group-containing organosilicon compound represented by the following chemical formula 47 in a yield of 88% (yield 17.0 g).

[0068]

[Chemical 47]

[0069]

Synthesis Example 4 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was converted to diperfluoro-2-methyl-3-oxahexanoyl peroxide, and 3,3
The reaction was performed in the same manner as in Synthesis Example 1 except that the charged amount of 3-diphenylhexamethyltrisiloxane was set to 12.5 mmol (4.5 g), and a fluoroalkyl group-containing organosilicon compound represented by the following chemical formula 48 was obtained. Obtained in 67% (yield 7.8 g).

[0070]

[Chemical 48]

[0071]

[Synthesis Example 5] The reaction was performed in the same manner as in Synthesis Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was replaced with diperfluoroheptanoyl peroxide. The yield of the fluoroalkyl group-containing organosilicon compound represented by is 83% (yield 16.9).
Obtained in g).

[0072]

[Chemical 49]

[0073]

Synthesis Example 6 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was added to diperfluoroheptanoyl peroxide, and the amount of 3,3-diphenylhexamethyltrisiloxane was 12. 5 mmol (4.5
The reaction was performed in the same manner as in Synthesis Example 1 except that g) was used, and a fluoroalkyl group-containing organosilicon compound represented by the following chemical formula 50 was obtained with a yield of 60% (yield 7.5 g).

[0074]

[Chemical 50]

[0075]

[Synthesis Example 7] The reaction is performed in the same manner as in Synthesis Example 1 except that diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide is replaced with diperfluorobutyryl peroxide. The yield of the fluoroalkyl group-containing organosilicon compound represented by is 79% (yield 12.5 g).
Got with.

[0076]

[Chemical 51]

[0077]

Synthesis Example 8 Diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide was added to diperfluorobutyryl peroxide, and the amount of 3,3-diphenylhexamethyltrisiloxane was 12. The reaction was performed in the same manner as in Synthesis Example 1 except that the amount was 5 mmol (4.5 g) to obtain a fluoroalkyl group-containing organosilicon compound represented by the following chemical formula 52 in a yield of 55% (amount of 4.8 g).

[0078]

[Chemical 52]

[0079]

Example 1 Using a 0.01 mol / l sodium dodecylsulfate aqueous solution as a foaming liquid, the fluoroalkyl group-containing organosilicon compound 57 synthesized in Synthesis Example 1 was added to 100 ml of the aqueous solution.
After adding 0 ppm, the mixture was placed in a glass foam tube,
The amount of foaming when aerated at 25 ° C. at an air blowing rate of 300 ml / min was measured every 5 minutes from 5 minutes to 40 minutes, as shown in Table 1. The results are shown in Table 1.

[0080]

Example 2 The same procedure as in Example 1 was repeated except that the fluoroalkyl group-containing organosilicon compound was changed to 380 ppm.
The amount of foaming was measured. The results are shown in Table 1.

[0081]

Examples 3 to 9 The amount of foaming was measured in the same manner as in Example 1 except that the fluoroalkyl group-containing organosilicon compound was replaced with the compounds synthesized in Synthesis Examples 2 to 8. The results are shown in Table 1.
Shown in.

[0082]

Comparative Example 1 The amount of foaming was measured in the same manner as in Example 1 except that the fluoroalkyl group-containing organosilicon compound was replaced with 3,3-diphenylhexamethyltrisiloxane. The results are shown in Table 1.

[0083]

[Comparative Example 2] Fluoroalkyl group-containing organosilicon compound was used as 3,3-diphenylhexamethyltrisiloxane 28
The amount of foaming was measured in the same manner as in Example 1 except that the amount was changed to 50 ppm. The results are shown in Table 1.

[0084]

[Table 1]

As shown in the above Examples and Comparative Examples, the defoaming agent containing the fluoroalkyl group-containing organosilicon compound of the present invention as an active ingredient is extremely high in foam suppressing property as compared with ordinary silicon compounds. it is obvious.

Claims (1)

[Claims] 1. An antifoaming agent containing a fluoroalkyl group-containing organosilicon compound represented by the following general formula 1 as an active ingredient. [Chemical 1]