JPH05228306A - Antifoaming agent - Google Patents

Abstract

PURPOSE:To obtain an antifoaming agent having a low surface tension and exhibiting an excellent antifoaming property with a minute amt. by incorporating a fluoroalkyl group-contg. silicon compd. having a specified structural formula into the agent as the effective component. CONSTITUTION:A fluoroalkyl group-contg. silicon compd. shown by formula I is incorporated into an antifoaming agent as the effective component. In formula I, R is 1-10C alkyl, alkoxy or alkylcarbonyloxy groups, RF is (CF2)n1X or the group shown by formula II (where X is H, F or Cl, n, is an integer of 1 to 10, and n2 is an integer of 0 to 8) and (n) is an integer of 1 to 10, m1 is an integer of 0 to 50, m2 is an integer of 1 to 3, m3 is an integer of 0 to 2, and m2+m3=3. The agent has a low surface tension and is resistant to heat, oil, etc., and chemically inert, and hence the agent does not react with foaming material even under various unfavorable conditions and is stable.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antifoaming agent containing a specific fluoroalkyl group-containing silicon 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, there has been a problem that a silicon compound conventionally used as a defoaming agent has an extremely weak foam suppressing effect on an organic solvent system. In addition, Japanese Patent Publication 35-1256
4, JP-A-62-71506, JP-A-62.
-71507, Japanese Patent Application Laid-Open No. 2-52007, and Japanese Patent Application Laid-Open No. 2-131105 disclose antifoaming agents containing a fluoroalkyl group-containing silicon compound as an active ingredient, but a sufficient foam suppressing effect is obtained. However, the fact is that the development of an active ingredient that exhibits excellent defoaming properties by adding a smaller amount is desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an antifoaming agent having a low surface tension property and exhibiting an excellent defoaming property even in a trace amount.

[0004]

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

[0005]

[Chemical 2]

The present invention will be described in more detail below.

The defoaming agent of the present invention contains the fluorosilicone compound 1 represented by the general formula 2 as an active ingredient. In the fluorosilicon compound 1, R
Is an alkyl group, an alkoxy group or an alkylcarbonyloxy group having 11 or more carbon atoms, n is more than 10, m ₁ is more than 50, the production is difficult, and n ₁ is more than 10. Alternatively, when n ₂ exceeds 8, the solubility in the solvent decreases.

In the fluorosilicon compound 1, the applicable RF, that is,-(CF ₂ ) n ₁ X or the following general formula 3 is specifically listed. F ₃ C-, F (C
_{F 2) 2 -, F (} CF 2) 3 -, F (CF 2) 4 -, F (CF
₂ ) ₅ −, F (CF ₂ ) ₆ −, F (CF ₂ ) ₇ −, F (C
_{F 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 (CF 2) 6 -, H (CF 2) 7
_{-, H (CF 2) 8} -, H (CF 2) 9 -, H (CF 2) 10
_{-, ClCF 2 -, Cl (} CF 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 formula 4 to
It is a 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]

The molecular weight of the fluorosilicon compound 1 is preferably 500 to 50,000. As the fluorosilicon compound 1, specifically, for example, the following general formulas 13 to 42 can be preferably mentioned (wherein, n is an integer of 1 to 10 and m ₁ is an integer of 0 to 50). Indicates).

[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]

In the present invention, the fluorosilicon compound 1 used as an active ingredient can be prepared by a method of reacting a specific difluoroalkanoyl peroxide with a specific vinyl group-containing organic silicon compound.

Preferred examples of the specific difluoroalkanoyl peroxide include difluoroalkanoyl peroxide represented by the following general formula 43.

[0052]

[Chemical 43]

In the above difluoroalkanoyl peroxide, when n ₁ is 11 or more or n ₂ is 9 or more,
It is not preferable because the solubility decreases when the reaction is carried out in the presence of a solvent.

The RF in the difluoroalkanoyl peroxide is the same as the RF specifically enumerated in the fluorosilicon compound 1, and the difluoroalkanoyl peroxide is specifically, for example, diperfluoro-2 peroxide. -Methyl-3-oxahexanoyl, diperfluoro-2,5-dimethyl-3,6-dioxanonanoyl peroxide, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like can be preferably mentioned.

As the specific vinyl group-containing organic silicon compound, a vinyl group-containing organic silicon compound represented by the following general formula 44 can be preferably mentioned.

[0056]

[Chemical 44]

In the vinyl group-containing organosilicon compound, when R is an alkyl group having 11 or more carbon atoms, an alkoxy group or an alkylcarbonyloxy group, m ₁ is 5
If it exceeds 0, the production is difficult.

As the vinyl group-containing organic silicon compound, specifically, for example, the following general formulas 45 to 56 can be preferably mentioned (where m ₁ is 0 to 0).
Indicates an integer of 50).

[0059]

[Chemical 45]

[0060]

[Chemical 46]

[0061]

[Chemical 47]

[0062]

[Chemical 48]

[0063]

[Chemical 49]

[0064]

[Chemical 50]

[0065]

[Chemical 51]

[0066]

[Chemical 52]

[0067]

[Chemical 53]

[0068]

[Chemical 54]

[0069]

[Chemical 55]

[0070]

[Chemical 56]

When the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound are reacted, the molar ratio of the charge is preferably in the range of 1: 0.1 to 10.0, and particularly 1: 0. It is preferably in the range of 0.5 to 5.0. When the charged molar ratio of the vinyl group-containing organosilicon compound is less than 0.1, a large amount of product is generated due to the self-decomposition of peroxide, and when it exceeds 10, the target fluorocarbon is produced. It is not preferable because the yield of the alkyl group-containing organosilicon compound is lowered.
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. The reaction temperature is −20 ° C.
If it is less than 1, the reaction takes a long time, and if it exceeds + 150 ° C., the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Furthermore, the reaction time is 30 minutes to 2
It is preferably in the range of 0 hours, and industrially particularly preferably in the range of 3 to 10 hours.

In the defoaming agent of the present invention, the content ratio of the fluorosilicon compound 1 can be variously selected depending on the object, but is preferably 0.01 to 100% by weight.

The antifoaming agent of the present invention can be used by adding the fluorosilicone compound 1 to an aqueous solution or an organic solvent-based aqueous solution. When added to an organic solvent-based aqueous solution, it is prepared by dissolving fluorosilicon compound 1 in a ketone-based solvent such as methyl ethyl ketone or methyl isobutyl ketone or a halogen-based organic solvent such as 1,1,2-trichlorotrifluoroethane. Alternatively, the fluorosilicone compound 1 can be prepared by emulsifying the fluorosilicone compound 1 in an aqueous solution with, for example, a homomixer. The emulsion particle size is preferably 1 to 10 μm. Further, in order to stabilize the emulsion, a known thickener such as polyvinyl alcohol may be contained. Furthermore, the defoaming agent of the present invention may contain, if necessary, antioxidants such as commercially available tocophenol and fumed in order to facilitate penetration into the foam film and exert a stronger defoaming effect. Fillers such as silica, alumina, titanium dioxide and the like may 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 an organic solvent-based aqueous solution. At this time, the addition amount of the antifoaming agent of the present invention to the aqueous solution or the organic solvent-based aqueous solution is
It may be added in a weight ratio of 0.01 ppm to 5000 ppm based on the amount of the fluorosilicon compound 1. When the addition amount is less than 0.01 ppm, the decrease in surface tension due to the fluorosilicon compound 1 is not sufficient, the solubility in an aqueous solution or an organic solvent-based aqueous solution becomes large, and the foam suppressing effect becomes insufficient. It is not preferable. On the other hand, if the amount added exceeds 5000 ppm, dispersibility in an aqueous solution or an aqueous solution of an organic solvent system and expandability to foam are deteriorated, and the defoaming effect, especially the defoaming property and the rapid-acting property are insufficient, which is not preferable.

[0075]

The antifoaming agent of the present invention is effective for a specific fluoroalkyl group-containing organosilicon compound having properties such as low surface tension, heat resistance, cold resistance, oil resistance, antifoaming property and chemical resistance. Since it is used as a component, it is chemically inert and stable even under various adverse conditions without reacting with the foamed substance. Therefore, it can be used in a food manufacturing process or a dishwashing process, and further in wastewater treatment and the like. 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.

[0076]

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.

[0077]

Synthesis Example 1 CH ₂ = CHSiCH ₃ (O (Si (C
H ₃ ) ₂ O) m ₁ Si (CH ₃ ) ₃ ) ₂ (Mn = 1790, M
w / Mn = 1.27) and 17.9 g of a vinyl group-containing organosilicon compound, diperfluoro-2-peroxide
Methyl-3-oxahexanoyl 3.3 g (5.0 mmo
50 g of a 1,1,2-trichlorotrifluoroethane solution containing 1) was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed, and then distillation was carried out to obtain a colorless liquid fluoroalkyl group-containing silicon compound represented by the following chemical formula 57.
Obtained in 4 g. In the chemical formula 57, n is an integer of 2 to 5 and m ₁ is 2
It was an integer mixture of 10.

[0078]

[Chemical 57]

[0079]

[Synthesis Example 2] Diperfluoro-2-methyl-3-peroxide
Diperfluoro-peroxide instead of oxahexanoyl
The reaction was performed in the same manner as in Synthesis Example 1 except that 2,5-dimethyl-3,6-dioxanonanoyl was used, and the fluoroalkyl group-containing silicon compound represented by the following chemical formula 58 was obtained at a yield of 22.4 g. Obtained. In chemical formula 58, n is 2 to
The mixture was an integer of 5 and m ₁ was an integer of 2 to 10.

[0080]

[Chemical 58]

[0081]

[Synthesis Example 3] Diperfluoro-2-methyl-3-peroxide
Diperfluoro-peroxide instead of oxahexanoyl
The reaction was performed in the same manner as in Synthesis Example 1 except that 2,5,8-trimethyl-3,6,9-trioxadodecanoyl was used, and the fluoroalkyl group-containing silicon compound represented by the following chemical formula 59 was obtained in a yield of 24. Obtained in 0.0 g. Conversion 59
Was a mixture of n being an integer of 2 to 5 and m ₁ being an integer of 2 to 10.

[0082]

[Chemical 59]

[0083]

Synthesis Example 4 Diperfluoro-2-methyl-3-peroxide
A reaction was performed in the same manner as in Synthesis Example 1 except that diperfluorobutyryl peroxide was used instead of oxahexanoyl to obtain a fluoroalkyl group-containing silicon compound represented by the following chemical formula 60 in a yield of 18.9 g. Conversion 60
Was a mixture of n being an integer of 2 to 5 and m ₁ being an integer of 2 to 10.

[0084]

[Chemical 60]

[0085]

[Synthesis Example 5] Diperfluoro-2-methyl-3-peroxide
A reaction was performed in the same manner as in Synthesis Example 1 except that diperfluoroheptanoyl peroxide was used instead of oxahexanoyl, and a fluoroalkyl group-containing silicon compound represented by the following chemical formula 61 was obtained in a yield of 20.1 g. Conversion 61
Was a mixture of n being an integer of 2 to 5 and m ₁ being an integer of 2 to 10.

[0086]

[Chemical formula 61]

[0087]

[Example 1] An organic foaming liquid ("Modiper F-200" manufactured by NOF CORPORATION) (A-B type block polymer having a perfluoroalkyl group as one component), trade name, was placed in a 50 ml graduated test tube. 10 ml of a solution diluted 6-fold with 2-propanol) was added, and then 90 ppm of the fluoroalkyl group-containing silicon compound synthesized in Synthesis Example 1 was added to the organic foaming liquid, and then the mixture was placed in a 25 ° C. constant temperature bath. 2
After standing for 4 hours, foam was generated by shaking 50 times up and down. The foam volume after foam formation was measured until 1 minute, 3 minutes, 5 minutes, and 10 minutes as shown in Table 1. The results are shown in Table 1.

[0088]

Example 2 The foam volume was measured in the same manner as in Example 1 except that the fluoroalkyl group-containing silicon compound was 380 ppm. The results are shown in Table 1.

[0089]

Examples 3 to 6 Foam volumes were 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 5. The results are shown in Table 1.

[0090]

Comparative Example 1 The foam volume was measured in the same manner as in Example 1 except that the starting material used in Synthesis Example 1 was a vinyl group-containing organosilicon compound instead of the fluoroalkyl group-containing silicon compound. . The results are shown in Table 1.

[0091]

[Table 1]

From the results shown in Table 1, the antifoaming agent containing the fluoroalkyl group-containing silicon compound of the present invention as an active ingredient has a very high foam suppressing property as compared with a usual silicon compound due to the addition of a very small amount, and can be used for a very short time. It was found that it showed excellent defoaming property.

Claims (1)

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