JPS6086B2 - Antifoaming agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antifoaming agent containing a fluorosurfactant.

In many industrial fields such as the textile industry, paint industry, pulp and paper industry, synthetic rubber latex industry, food industry, and fermentation industry, many troubles such as decreased production capacity and quality deterioration are occurring due to inconvenient foaming. How to prevent bubbles from forming or how to quickly eliminate the generated bubbles is an extremely important problem.

To address these problems, various foaming agents have been used.

For example, pot oil, natural oils, higher fatty acids, fatty acid esters,
Hydrocarbon antifoaming agents such as higher alcohols, metal soaps, phosphate esters, polyoxyalkylenes, and polyoxyalkylene derivatives are known. These antifoaming agents are often used because they are inexpensive, but they have a serious drawback of weak antifoaming properties.

Even if a large amount is added, the defoaming property is not improved, and on the contrary, it has the undesirable property of promoting foaming. In addition to these, silicone antifoaming agents are also known.

Although their antifoaming properties are superior to those of the hydrocarbon type, they still have various defects specific to silicone types. For example, it is easy to form a silicone oil film on the foaming solution, which can lead to a decrease in product quality. Particularly when used as an antifoaming agent for paints, silicone foaming agents act as scale agents, making it impossible to apply multiple coats. Otherwise, problems such as cratering may occur. In addition, there is no antifoaming agent that is effective against oily foams such as lubricants and crude oil, and the industry that handles these oily substances is strongly demanding the development of antifoaming agents that can eliminate the various troubles caused by oily foams. It is in a required situation.

From this point of view, the present inventors have conducted extensive studies and have discovered that a compound containing a fluorinated aliphatic group and a long-chain aliphatic group in the same molecule has a remarkable defoaming effect. Furthermore, they discovered that the silicone-based silicone-based silicone material does not cause any repelling phenomenon, thereby completing the present invention.

That is, the present invention provides a fluorinated aliphatic group Rf having 3 to 20 carbon atoms.
and a fluorine-containing compound (A) containing a higher aliphatic group R having 10 or more carbon atoms, preferably 12 to 36 carbon atoms, in the same molecule. Ru.

Preferred examples of the fluorinated aliphatic group Rf include a barfluoroalkyl group or a perfluoroalkenyl group, which may be linear, branched, cyclic (for example, a group such as cyclohexyl), or a combination thereof. Often, there are also oxygen or nitrogen atoms interposed in the main chain, such as (CF3)2CFOCF2CF2-, (
C3F, 7)2NCF2CF2-, etc. may be used.

As a preferable example of the higher aliphatic group R, 3 is an alkyl group or an alkenyl group, which may be linear, branched, cyclic, or a combination thereof.

The intramolecular connection method between the R★ group and the R group is not particularly limited, but
Preferred examples include [where X is -SQ-, -CO]
-, 10S02-, 1010-CO-, 1(CZ)nCO-, (however, n represents an integer from 1 to 12).

]. It is essential that at least one Rf group and one R group each be contained in the molecule, and a plurality of Rf groups and R groups can also be contained by introducing them into the polymer compound as repeating units. Specific examples of the fluorine-containing compound (A) according to the present invention include the following.

(However, p is an integer of 1 to 20) (However, p is an integer of 1 to 50) 3. The fluorine-containing compound (A) according to the present invention can be prepared by a method well known in the art (for example, see US Pat. No. 2,803,656).
It can be easily manufactured by

In the antifoaming agent of the present invention, the fluorine-containing compound (A) can be used alone, but the hydrocarbon antifoaming agent 3 (for example, mineral oil, natural fat, higher fatty acid, fatty acid ester, higher alcohol, metal stone) It can also be used in combination with silicone antifoaming agents, phosphoric acid esters, polyoxyalkylenes, polyoxyalkylene derivatives, etc.), or silicone antifoaming agents.
When used in combination, a fluorine-containing compound (A
) must be added in an amount of 0.1% by weight or more in the active ingredients.
When the amount is less than this, the fluorine-containing compound exhibits less defoaming properties.

According to the findings of the present inventors, it has been found that there are cases where the antifoaming properties are synergistically improved by mixing the antifoaming agent, and furthermore, the added amount of the mixed antifoaming agent is equivalent to or better than when used alone. It was found that the sex is expressed.

Such a mixed system can reduce the amount of expensive fluorine-containing compounds used, resulting in an antifoaming agent that is more advantageous in terms of performance and economy. The antifoaming agent of the present invention exhibits both antifoaming properties, such as easily extinguishing foam when added to a foaming liquid, and antifoaming properties that suppress foaming when added to a liquid in advance. do.

The antifoaming agent of the present invention can be used in a suitable solvent (for example, water, lower aliphatic hydrocarbons, lower alcohols, lower ketones, lower esters,
It can be used as a diluted solution by dissolving it in lower ethers, halogenated hydrocarbons, aromatic hydrocarbons, etc.
Alternatively, it can be dispersed or emulsified in water, a suitable organic solvent, or a mixed solvent thereof, and if necessary, solid fine particles such as silica may be added thereto, and used as an emulsion type or a paste type.

In order to use the defoaming agent of the present invention efficiently, it is usually first dispersed or dissolved in the liquid to be defoamed to make a dilute solution, and adding this will improve the dispersibility of the defoaming agent and make it more effective. Can remove bubbles.

When a large amount of foam is generated in a short period of time, or when you want to eliminate temporarily generated foam, it is also effective to spray the foam using a spray gun or the like.

In addition, if the foam is applied to a wire mesh or gauze placed on the surface of the foaming liquid, or to the greenery of the container, even if the foam rises, the foam will be extinguished when it touches the antifoaming surface. The antifoaming agent of the present invention is used in various applications where foaming is a problem (e.g., paint industry, synthetic rubber, latex industry, pulp and paper industry, textile industry, food industry, fermentation industry, chemical industry, petrochemical industry, oil refining industry, etc.) can be widened, and in some cases even par*
*Additional properties (levelling properties, frictional resistance reduction properties, etc.) due to the low surface energy properties of the fluoroalkyl group can also be imparted at the same time, making it possible to improve the quality of products to which welding is applied.

Next, the present invention will be explained in more detail with reference to Examples.

All percentages in the examples are by weight. Example A 1% ethanol solution of a fluorine-containing compound (A-1) represented by the following formula was prepared and used as an antifoaming agent.

Add this to a 0.1% aqueous solution of sodium lauryl sulfate,
The foam suppression property was examined by the Ross-Miles method (25°). The results are shown in Table-1. Table 1 Example 2 Fluorine-containing compound (A-2) C8F,7S○2 (CH2CH20>,

An ethanol solution containing 10% of n-CI6day 37PPG-4000 was prepared and used as an antifoaming agent.

This was added to a 0.1% aqueous solution of sodium dodecylbenzenesulfonate, and its foam-inhibiting properties were examined by the Ross-Mills method. The results are shown in Table-2. Table-2 PPG-4000 as a comparative example
Table 3 shows the foam suppression properties of (10% ethanol solution).

(The foaming agent was the same 0.1% aqueous solution of sodium dodecylbenzenesulfonate as in Example 2). Table 3 Example 3 The antifoaming properties of the antifoaming agent of Example 2 were evaluated using a cationic superfoaming agent (0.1% aqueous solution of lauryltrimethylammonium chloride).
The table below shows the results of investigations on nonionic foaming agents (polyoxyethylene lauryl ether 0.1% aqueous solution) and amphoteric foaming agents (lauryl betaine 0.1% aqueous solution).
4.

Table 4 Example 4 A 10% toluene solution of a 1:1 copolymer (A-3) of fluorine-containing acrylate and PPG acrylate was used as an antifoaming agent.

Add this to the lubricating oil (hydraulic oil AIMOL) and use the JISK
According to the -251 loss test method, air was blown in using a diffuser stone and the amount of foaming was measured (25°C).

The results are shown in Table-5.

Table-5 Example 5 H Day C9F 7S02N (CH2) 6NCM, 8 days 3 1%
An ethanol solution containing 5% PPG-4000 was prepared and used as an antifoaming agent.

An ethanol solution containing 1% of Example 6 and 5% of sorbitan trioleate was prepared and used as an antifoaming agent.

*An ethanol solution containing 1% of Example 7 and 5% of a key oil-based antifoaming agent (commercial product A) was prepared and used as an antifoaming agent.
An ethanol solution containing 1% of Example 8 and a mineral oil antifoaming agent (commercial product B) was prepared and used as an antifoaming agent.

*An ethanol solution containing 1% of Example 9 and 5% of Span 85 was prepared and used as an antifoaming agent.

*An ethanol solution containing 1% of Example 10 and 5% of a natural oil-based antifoaming agent (commercial product C) was prepared and used as an antifoaming agent.

The foam suppressing performance and defoaming performance of the antifoaming agents obtained in Examples 5 to 10 are shown in Table 6 below.

In Table 6, the antifoaming performance is determined by adding 0.1% antifoaming agent in advance.
(21 pm as the added concentration of fluorine-containing compounds) including 0
．． The foamability of a 1% sodium lauryl sulfate aqueous solution was evaluated based on the foaming property (immediate foam height (sail)).

In addition, in Table 6, the antifoaming performance is determined by measuring 10% of a 0.1% sodium lauryl sulfate aqueous solution without adding an antifoaming agent in a test tube with 3 scales (inner capacity: 50', with a stopper), and testing it horizontally. 3
During the making process, it was shaken and foamed in 5 ratio water (foam volume 45±).
2').

0.1% of an antifoaming agent was added to this foam using a microsyringe, and the time (seconds) until all the foam disappeared was measured to evaluate the antifoaming performance. 3. The comparative examples in Table 6 are made of commercially available hydrocarbon antifoaming agents, all of which are 10% ethanol solutions, and the amount added is 0.1%, which is the same as Examples 5 to 10. Comparative Example 2 10% ethanol solution of PPG-4000 4″ 3 sorbitan trioleate 1
0% ethanol solution^ 4 Mineral oil-based antifoaming agent (commercial product A)
10% ethanol solution of r 5 10% ethanol solution of key oil-based antifoaming agent (commercial product B)'' 6 Span 85 of 10
% ethanol solution'' 7 Natural oil-based antifoaming agent (commercial product C
) 10% ethanol solution table [[ 6 Comparative Examples 8 to 15 Similarly to Example 1 of the present invention, a 1% ethanol solution of the fluorine surfactant shown in Table 7 was used as an antifoaming agent and sodium lauryl sulfate 0 A fluorine-containing compound was added to a 1% aqueous solution at a concentration of 5 pm, and the foaming state was examined using the Ross-Mills method.

The results are shown in Table-7. Comparative Examples 16 to 23 Similarly to Example 2 of the present invention, an ethanol solution of 1% of the fluorosurfactant shown in Table 7 and PPG-400010**% was used as an antifoaming agent, and a non-foaming agent was used as a foaming agent. A fluorine-containing compound was added to a 0.1% aqueous solution of ionic polyoxyethylene lauryl ether at a concentration of 1 pm, and the foaming state was examined by the Ross-Miles method.

The results are shown in Table-7.

Table-7.

Claims (1)

[Scope of Claims] 1 A fluorinated aliphatic group (Rf) having 3 to 20 carbon atoms and a higher aliphatic group (Rf) having 10 or more carbon atoms, preferably 12 to 36 carbon atoms
) and a fluorine-containing compound (A) in the same molecule. 2. The antifoaming agent according to claim 1, wherein Rc is a perfluoroalkyl group or a perfluoroalkenyl group. 3. The antifoaming agent according to claim 1 or 2, wherein R is an alkyl group or an alkenyl group. 4 The intramolecular connection method of Rf and R is ▲ mathematical formula, chemical formula, table, etc. ▼ [However, in the formula, X is -SO_2-, -CO-, -O▲ mathematical formula,
There are chemical formulas, tables, etc.▼(CH_2)n-SO_2-
, -(CH_2)nCO- (where n represents an integer from 1 to 12). ] The antifoaming agent according to claim 1, 2 or 3. 5 0.0% of the fluorine-containing compound (A) in the antifoaming agent active ingredients.
Claims 1, 2, and 3 containing 1 to 100% by weight
Or the antifoaming agent according to item 4.