JPH0368401A - Defoaming agent - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is aimed at solving various troubles associated with foaming in various industrial processes that handle surfactants, water-soluble polymer compounds, etc. This invention relates to useful new antifoaming agents.

In particular, it prevents foaming in the valve stock solution and paper manufacturing wastewater in each process of the paper mill, improving the operability of the paper mill, the quality of paper, etc.
It can be used as an antifoaming agent to solve problems related to environmental pollution caused by wastewater.

[Prior Art] In the pulp and paper manufacturing process, contaminants mixed in from pulp raw materials and various processing chemicals tend to cause problems due to foaming in various processes. Foaming during the cleaning process increases the amount of clean water used and reduces processing capacity, significantly reducing cleaning efficiency. Foaming in the papermaking process also causes pinholes and
This not only causes deterioration in paper quality, such as a decrease in formation, but also deteriorates productivity, such as a decrease in water quality and an increase in the outflow of raw materials. Furthermore, foaming during the treatment process of paper manufacturing wastewater causes a decrease in treatment capacity due to poor sedimentation and causes environmental pollution.

Therefore, various antifoaming agents have been used to prevent various troubles caused by foaming in paper mills. Conventionally used antifoaming agents include, for example, mineral oil-based, oil-based, fatty acid-based, fatty acid ester-based, alcohol-based, silicone-based, polyalkylene glycol-based, and arbitrary mixtures thereof.

However, these antifoaming agents have various drawbacks when used in each process of a paper mill.For example, mineral oil-based and fatty acid ester-based antifoaming agents are insoluble in water, so they contaminate blankets and wires, In addition, oil spots were generated on the surface of the paper, leading to a decline in the quality of the paper. Furthermore, when silicone-based materials are added to the foaming liquid, they generate insoluble scum, which stains machinery and equipment, and also adheres to the surface of papermaking, lowering the value of the paper and causing uneven printing and dyeing. It caused this. Furthermore, it has been pointed out that polyalkylene glycol-based foams have drawbacks such as the inability to obtain a practical defoaming effect.

[Problem to be solved by the invention] In recent years, paper manufacturing chemicals used in each process of the paper manufacturing industry have become increasingly diverse, and with the use of these new chemicals, foaming problems that are difficult to deal with with conventional antifoaming agents have arisen. occurs frequently. The papermaking chemicals that cause these foaming problems include paper strength enhancers such as polyacrylamide-based and modified starch-based agents, yield strength agents such as cationic polymer compounds such as polyamide amine-based, and water-resistance improvers: various anions. Deinking agents and pitch dispersants that are mainly composed of aqueous or nonionic surfactants include rosin-based, cationic-based, or reactive-type sizing agents.

Valve stock solutions or paper manufacturing wastewater containing these chemicals often cause various foaming problems due to the foaming properties of these chemicals themselves and their synergistic effects with other additives. It was difficult to solve this problem using antifoaming agents for paper manufacturing.

Furthermore, regulations on factory wastewater have been tightened, and in line with this, closed water systems have become widespread in paper mills in order to reduce the amount of wastewater and water usage. As a result, the concentration of chemicals in papermaking white water has increased, foaming substances have become concentrated, and the temperature of whitewater in papermaking systems has also increased. For this reason, conventional antifoaming agents are no longer able to provide sufficient antifoaming effects, and the sustainability of the antifoaming effects is also lost. I have to do it. As a result, the types and amounts of antifoaming agents used in paper mills have increased, causing increases in paper manufacturing costs and deterioration in quality.

Under these circumstances, there is a strong demand in the paper industry for the development of a new antifoaming agent that has excellent antifoaming effects and long-lasting effects even when a small amount of chemicals are added.

[Means for Solving the Problems] The present invention solves the above-mentioned problems, has excellent antifoaming power even when added in a small amount, and has excellent sustainability that tends to extend its effect over a wide range of papermaking processes. Another purpose is to provide a new antifoaming agent for use in paper mills.

That is, the present invention has the following formula: Represents one unit of a 3-4 oxyalkylene chain, n is 1-30, and m is an integer of 1-3.

where, X represents a mono- to trivalent carboxylic acid residue having 1 to 6 carbon atoms, and when the carboxylic acid is a polyvalent carboxylic acid, the residue is a free carboxyl group, a salt thereof, or an ester thereof. ) The present invention provides an antifoaming agent containing a compound represented by:

The compound represented by the general formula (I) is a linear or branched saturated or unsaturated higher alcohol having 8 to 18 carbon atoms, or an alkylphenyl group having 8 to 18 carbon atoms and/or butylene oxide, Alternatively, tetrahydrofuran is added in a ratio of 1 to 30 moles in the presence of an acid or alkali catalyst by a conventional method, and then this adduct is added with a carbon number of 1 to 6.
It can be synthesized from mono- to trivalent carboxylic acid, carboxylic acid anhydride, or carboxylic acid ester by esterification reaction or transesterification reaction. Examples of higher alcohols include alcohols obtained from natural oils and fats such as coconut oil alcohol, macaw whale oil alcohol, and beef tallow alcohol; synthetic primary alcohols such as oxo alcohol and Ziegler alcohol; and synthetic secondary alcohols obtained by paraffin oxidation. Alcohols and the like may be used, and a mixture of two or more of these may be used.

Further, as the alkylphenol, for example, octylphenol, nonylphenol, dodecylphenol, etc. can be used.

To produce propylene oxide and/or butylene oxide or tetrahydrofuran adducts from such higher alcohols or alkylphenols, propylene oxide and/or butylene oxide, or tetrahydrofuran is added to the higher alcohols or alkylphenols, usually in the presence of an alkali catalyst or an acid catalyst. can be added by sequentially introducing. The number of moles added to 1 mole of higher alcohol or alkylphenol is 1 to 30 moles. When the number of moles of propylene oxide and/or butylene oxide or tetrahydrofuran added is less than 1, the antifoaming effect of the final product, that is, the compound of general formula (I) becomes poor.

If it exceeds 30, the defoaming effect will also deteriorate.

Next, propylene oxide and/or butylene oxide of the higher alcohol or alkylphenol obtained in this way,
Alternatively, when the tetrahydrofuran adduct is reacted with a mono- to trivalent carboxylic acid, the compound of general formula (I) in the present invention can be obtained, but the carboxylic acid must have 6 or less carbon atoms. This is because when the number of carbon atoms is 7 or more, the lipophilicity of the final product becomes strong, which may cause oil spots to occur in papermaking when this is used in the papermaking process.

Examples of such monovalent to trivalent carboxylic acids having 1 to 6 carbon atoms include formic acid, acetic acid, propionic acid, oxalic acid, maleic acid, succinic acid, lactic acid, malic acid, tartaric acid, and citric acid. Naturally, these carboxylic acids can also be used as anhydrides (eg, acetic anhydride, maleic anhydride, succinic anhydride, etc.) or carboxylic acid reactive derivatives such as acid chlorides.

As described above, the compound represented by the general formula (1) is composed of the above-mentioned higher alcohol or alkylphenol propylene oxide and/or butylene oxide, or the tetrahydrofuran adduct and the above-mentioned mono- to trivalent carbon atoms having 1 to 6 carbon atoms. Although it can be produced by an esterification reaction with an acid, in addition to such a direct esterification reaction, it can also be produced by, for example, a transesterification reaction between a lower alcohol ester of the above carboxylic acid and the above adduct. be.

The compound of general formula (I) may be a monoester when the carboxylic acid is a dibasic acid, or
It may be a diesterified product; in the case of a tribasic acid, it may be a monoesterified product, a diesterified product, or a triesterified product; a monoesterified product in the case of a dibasic acid; a monoesterified product in the case of a tribasic acid; In the esterified products and diesterified products, the free carboxyl groups may remain as they are, or the free carboxyl groups may be neutralized with an alkaline substance or esterified with alcohol.

As the antifoaming agent of the present invention, the compound of general formula (1) may be used as it is, or water or an organic solvent (for example, ethanol, toluene, glycol ethers, methyl acetate,
The antifoaming agent of the present invention may be used as a solution at an appropriate concentration by dissolving or emulsifying it in (n-hexane) etc. Furthermore, a small amount of other known antifoaming agents may be added to the solution of general formula (I) to prepare the antifoaming agent of the present invention. It is also possible to do this.

In addition, the compound of general formula (I) has an excellent antifoaming effect and its sustainability even when used alone, but it is also used in foaming systems (valve stock solutions in the acidic papermaking process using rosin sizing agents). In order to improve the dispersibility of the compound of general formula (I) in the foaming system, an anionic or nonionic emulsifier (surfactant) may be added in advance. This further improves the defoaming effect and its sustainability.

A preferred first embodiment of the antifoaming agent of the present invention is 0.1 to 10 parts by weight per 100 parts by weight of the compound of general formula (I).
The composition contains parts by weight of an anionic or nonionic emulsifier.

Examples of anionic or nonionic surfactants used as emulsifiers include higher fatty acid salts such as potassium laurate, sodium oleate, or ammonium stearate, higher alcohols with an alkyl moiety of 8 to 18 carbon atoms, or Sulfates of ethoxylates thereof, sulfates of ethoxylates of alkylphenols whose alkyl moiety has 8 to 18 carbon atoms, sulfonates of olefins or paraffins with 10 to 20 carbon atoms, other condensed naphthalene sulfonates, and alkyl succinates. Anionic surfactants such as sulfonates, alkyl or alkylphenol phosphate ester salts, or anionic surfactants whose alkyl moiety has 8 carbon atoms
~18 higher alcohols, alkylphenols or fatty acid ethoxylates, higher fatty acid sorbitan esters or their ethoxylates, C8-18 alkylamines or amides ethoxylates, block conipolymers of ethylene oxide and propylene oxide, etc. Examples include surfactants such as nonionic surfactants that can form oil-in-water emulsions with an HLB value of 8 to 18.

These anionic or nonionic emulsifiers have the general formula (
It can be blended in a range of 0.1 to 10 parts by weight per 100 parts by weight of the compound in 1). If it is less than 0.1 parts by weight, it will not be effective, and if it is more than 10 parts by weight, it will not be used in the paper making process. When used as a foaming agent, it may reduce the sizing of paper making, which is not preferable.

Furthermore, as a second embodiment of the antifoaming agent of the present invention, it can be used to prevent foaming troubles in the cleaning process in the manufacture of craft valves, the cleaning process in the manufacture of deinking valves, etc. However, in this case, in order to exhibit excellent foam suppressing and foam breaking effects, it is preferable to contain a certain amount of hydrophobic fine particle solids.

In such an embodiment, 99.5 to 70 parts by weight of the compound of general formula (I) and 0.5 to 30 parts by weight of hydrocarbon wax, hydrophobic silica, higher fatty acid amide, and polyorganosiloxane are used. Contains at least one hydrophobic fine particle solid selected from the following and having a particle size of 30P or less, and preferably further contains 0.1 to 10 parts by weight of anionic or non-ionic solid per 1 part of the compound of general formula (1) 100fEJ. This is a composition containing an ionic emulsifier (surfactant).

Examples of the hydrophobic fine particle solid hydrocarbon wax used here include polyethylene wax and paraffin wax with a melting point of 40°C or higher; examples of the hydrophobic silica include silica hydrophobized with dimethyldichlorosilane and dimethylsiloxane silicone. Examples of higher fatty acid amides include ethylene bisstearamide, methylene bisbehenic acid amide, and lauric acid amide. Examples of polyorganosiloxane include polydimethylsiloxane resin and fluoroalkyl groups. Modified polyorganosiloxane, organosiloxane containing oxyalkylene groups, etc.

Preferably, these hydrophobic solids are dispersed in the composition with a diameter of 61 particles of 30F+ or less, and particles of 30P or more are stably dispersed in the composition. It is difficult to remove the foam, and over time, it settles and separates or floats, making it impossible to obtain a stable defoaming effect.

In addition, the content of these hydrophobic fine particle solids is expressed by the formula (I)
The amount is 0.5 to 30 parts by weight per 99.5 to 70 parts by weight of the compound. If it is less than 0.5 parts by weight, the effect will be small, and if it is more than 30 parts by weight, it will be difficult to stably disperse it in the composition. The composition also contains 0.1-10
It is preferable to incorporate part by weight of an anionic or nonionic emulsifier.By incorporating this emulsifier, when the composition is added to the foaming system, the composition quickly becomes fine particles. Since the composition is dispersed, the antifoaming effect of the composition is immediate and the antifoaming effect is improved. As the anionic or nonionic emulsifier that can be used here, those mentioned above can be used.

Also - the compound of formula (I) is a flammable liquid with a flash point above 150°C, but in order to improve the safety against fire during storage and handling, it has been added to a defoaming liquid in the form of an oil-in-water emulsion. It can be used as an agent. A third such embodiment of the invention comprises - an antifoam composition comprising a compound of formula (I), or an emulsifier as described above, with the addition of a hydrophobic particulate solid as described above; but,
An antifoam composition emulsified in water at a concentration of 1 to 50% by weight.

The emulsion can be produced by emulsifying the composition using a common emulsifying device (for example, a homomixer, a high-pressure homogenizer, an ultrasonic homogenizer, a turbine mixer, etc.). In addition, for the emulsion.

In order to stabilize the emulsion morphology for a long time, known stabilizers can be added prior to emulsification. Stabilizers for emulsions include homopolymers or copolymers of water-soluble polymers such as acrylic acid, methacrylic acid, acrylamide, and methacrylamide, water-soluble polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, and carboxymethyl cellulose. There are compounds. These stabilizers are usually 0.05 to 2
．． 0% by weight used. As a result, the emulsion maintains a stable emulsion form for a long period of time after production, and can be effectively used as an antifoaming agent having a stable antifoaming effect.

The amount of the antifoaming agent of the present invention to be used varies depending on the type of foaming substance, the concentration of the foaming solution, the purpose of defoaming, etc., and cannot be generally specified. A concentration of about 0.1 to 0.0001% by weight is sufficient.

[Examples] Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example 1 268 g of oleyl alcohol and 0 caustic potassium as a catalyst
．． 56g of propylene oxide was charged into a stirring autoclave, and the system was preheated to 13CNL while purging with nitrogen. Then, at this temperature, 174g of propylene oxide was added at 2 to 5 kg/
The temperature was adjusted to 110° C., and 112.2 g of acetic anhydride was gradually introduced to carry out an esterification reaction over a period of 2 hours. After that, acetic acid by-produced in the reaction system and unreacted acetic anhydride were
℃.

Topping was removed under a reduced pressure of 20 TORH, and then 3 g of diatomaceous earth powder was added and adsorption treatment was performed to remove the catalyst. The product contained 95% by weight of acetate ester of a 3-mole adduct of propylene oxide oleyl alcohol oxide corresponding to general formula (I), and 5% by weight of a 3-mole adduct of propylene oxide oleyl alcohol oxide which had not been esterified. The composition was 496.3 g.

This product was used as an antifoaming agent in a 0.001% solution of a commercially available nonionic deinking agent used in the production of deinking valves.
The defoaming effect was tested by adding 2 ppm. The results are shown in Table 1.

Ta.

Example 2 110 g of nonylphenol and 0 caustic soda as a catalyst
．． 4g of the mixture was placed in an autoclave, and 900g of tetrahydrofuran was introduced over 4 hours at a reaction temperature of 130°C to carry out an addition reaction. The product was a compound in which 25 moles of tetrahydrofuran were added to 1 mole of nonylphenol.

202 g of this compound was placed in a 142 flask, 1.04 g of para-toluenesulfonic acid was added as a catalyst, and further 5.0 g of succinic anhydride was added, followed by an esterification reaction at a temperature of 130° C. for 6 hours. Thereafter, the catalyst was removed by adsorption treatment in the same manner as in Example 1, to obtain 215 g of a succinate ester of the above adduct. The ester composition in this product is 15.4% by weight of monoesters and 70.0% by weight of diesters.
It contained 14.5% of the unreacted adduct.

A test similar to Example 1 was conducted using this product as an antifoaming agent. The results were as shown in Table 1.

Example 3 Oxo method synthetic alcohol (Mitsubishi Yuka Co., Ltd. trade name Dopanol 23: The number of carbon atoms in the alkyl group is 12 and 6 is 4.
Using 194 g of a mixed alcohol (3% by weight, 57% by weight of 13, whose average molecular weight is 194), 290 g of propylene oxide and 144 g of butylene oxide, in the presence of 0.56 g of caustic potassium as a catalyst, By this method, 625 g of a random adduct of 5 moles of propylene oxide and 2 moles of butylene oxide to 1 mole of Dopanol 23 was obtained.

Next, 314 g of this random adduct, 56.1 g of ethyl propionate, and para-toluenesulfonic acid (2
1.04 g of water salt) and 150 g of toluene as a solvent were added, and a transesterification reaction was carried out at 90 to 95°C under a N2 stream. After 6 hours of reaction, topping was performed at 120°C to remove by-product ethanol, unreacted ethyl propionate, and toluene.

The catalyst was then further treated with an ion exchange resin to remove the catalyst. The resulting compound was a composition containing 92% by weight of the propionate ester of the random adduct and 8% by weight of the unreacted random adduct.

A test similar to Example 1 was conducted using this product as an antifoaming agent. The results were as shown in Table 1.

Comparative Example 1 Chemical formula C+aHssO(csusol *a (CJ
The same test as in Example 1 was conducted using a polyalkylene glycol fatty acid ester compound represented by 4015cOc+ +Hia as an antifoaming agent. The results were as shown in Table 1.

Comparative Example 2 The same test as in Example 1 was conducted using a higher alcohol oxide propylene adduct compound represented by the chemical formula c,,H,,O(C,H,Ol+sH) as an antifoaming agent. It was as shown in Table 1.

Comparative Example 3 A test similar to Example 1 was conducted using a commercially available silicone emulsion antifoaming agent. The results were as shown in Table 1.

Table 1 Defoaming effect on deinking agents Note) Test method for defoaming effect.

Glass double cylindrical tube (inner diameter 45mm, length 660mm)
Stand vertically, put 500 mm of test liquid into the inner tube, draw out the test liquid from the bottom with a circulation pump (22/min), guide it to the top of the cylindrical inner tube, and from a height of 450 mm perpendicular to the surface of the test liquid. Drip. The mixture is circulated for 10 minutes, and the foaming height at that time is measured and taken as the foam suppression value.

Thereafter, the circulation was stopped, and after the mixture was allowed to stand still for 10 minutes, the foam height was measured again and used as a foam-breaking value. (This is called the cyclic defoaming power test.) Also.

The test liquid contained commercially available nonionic deinking agent o, ooi % by weight, and antifoaming agent 2 ppm, had a pH of 7.5, and a temperature of 25°C.

As is clear from Table 1, it can be seen that the antifoaming agents of Examples 1 to 3 of the present invention have significantly better antifoaming effects than known antifoaming agents.

Example 4 97 parts by weight of the compound of Example 1 and nonylphenol ethoxylate (HLB value 12.0) as a nonionic emulsifier
3 parts by weight was prepared, and 5 ppm of this was added as an antifoaming agent to a 0.03% by weight solution of a commercially available rosin sizing agent used in the acidic papermaking process to obtain an antifoaming effect. Tested. The results were as shown in Table 2.

Example 5 92 parts by weight of the compound of Example 2 and anionic emulsifier lauryl alcohol ethoxysulfate ammonium salt (EO
A composition was prepared by mixing 8 parts by weight of P3 mol), and the antifoaming effect was tested in the same manner as in Example 4 using this as an antifoaming agent. The results were as shown in Table 2.

Table 2 Defoaming effect on rosin sizing agent) The method for testing the defoaming effect is the same as the cyclic defoaming power test described above.

However, the test solution contained 0.03% by weight (solid content equivalent) of a commercially available rosin sizing agent and 5 ppm of an antifoaming agent, and the pH
4,5 (controlled with sulfuric acid band!, temperature was 50°C).

As is clear from Table 2, it can be seen that the antifoaming agents of Examples 4 and 5 of the present invention have significantly better antifoaming effects than the antifoaming agents of Comparative Examples.

Example 6 1010 g of solid paraffin wax with a melting point of 60° C. and 30.0 g of the compound of Example 1 were placed in a dropping funnel equipped with a heating device and heated to 65° C. to melt and mix. Separately, in a flask with a stirrer, 60.0 g of Example 1
This was cooled to 10° C., and the above 65° C. molten mixture was gradually added dropwise thereto while stirring.

During this time, the temperature of the mixture in the flask was maintained at 10-15°C.

This composition consists of 85.5% by weight of oleyl alcohol propylene oxide 3-mole adduct acetate, 4.5% by weight of oleyl alcohol propylene oxide 3-mole adduct, and 10% by weight of paraffin wax fine particles (average particle size 11.2F). It contained.

This composition was mixed with black liquor after cooking Kraft valves (solid content 24.8 fE amount %, pH 1
2,6) (7) 10x diluted solution 400+d! , : against 5
ppm was added and a cyclic defoaming power test was conducted.

Defoaming effect and durability of defoaming power were tested. The result is the third
It was as shown in the table.

Example 7 9 g of ethylene bisstearamide and 81 g of the compound of Example 3 were placed in a dropping funnel equipped with a heating device, and
The mixture was heated to 0° C. to melt and mix. Separately, compound 201 of Example 3 was added to a flask (500-) equipped with a stirrer.
g, and while controlling the temperature to 20 to 25°C, the 150°C molten mixture was gradually added dropwise thereto, and the mixture was mixed and stirred. Thereafter, 3 g of ammonium nonylphenol ethoxy sulfate as an emulsifier and 6 g of lauryl alcohol ethoxylate (HLB value 10) were added and mixed.

This composition consists of dopanol 23 propylene oxide 5 moles butylene oxide 2 moles adduct propionic acid ester 86.5
Weight %, Dopanol 23 propylene oxide 5 mol, butylene oxide 2 mol adduct 7.5 weight %, ethylene bisstearamide fine particles (average particle size 14.8F) 3 weight %
, nonylphenol ethoxy ammonium sulfate 1% by weight
and lauryl alcohol ethoxylate in an amount of 2% by weight.

This composition was applied to a 10-fold diluted black liquor after cooking Kraft Bulb in the same manner as in Example 6! 5 ppm was added, and the defoaming effect and durability of defoaming power were tested. The results were as shown in Table 3.

Example 8 In a 300-meter beaker, put 139 g of pure water and 1 g of a water-soluble polymer compound, which is a copolymer of acrylamide (60% by weight) and acrylic acid (40% by weight), as a stabilizer. Industrial ■, TK homomixer) 10
．． Composition 60 of Example 6 while rotating at 000 rpm.
g was gradually added and emulsified for 2 minutes. Further, caustic soda was added to this emulsion to adjust the pH to 8.5 to prepare an oil-in-water emulsion antifoaming agent.

This emulsion was added at 5 ppp to a 10-fold diluted black liquor after Kraft Bulb cooking in the same manner as in Example 6.
m was added, and the antifoaming effect and antifoaming power sustainability were evaluated. The results were as shown in Table 3.

Table 3 Defoaming effect on bulb-cooked black liquor Emulsion 8 2.8 0.8 2.4 (Unit, foam height cm) Note) The test method for defoaming effect is the same as the cyclic defoaming power test described above. .

However, the test liquid was prepared after cooking the kraft pulp.

Add 55% of the antifoaming agents of Examples and Comparative Examples to a 10-fold dilution of black liquor.
ppm was added and the temperature was adjusted to 50°C.

In addition, the sustainability was determined by performing the above cyclic antifoaming power test three times in succession using each of the above test liquids, and performing the third circulation (10 minutes).
The subsequent foaming height (cm) was measured to determine the value of foam suppression, and then the foaming height (cm) after being allowed to stand for another 10 minutes was measured and this was determined to be the value of foam-breaking property.

As is clear from Table 3, the antifoaming agents of Examples 6 to 8 were:
The antifoaming effect is exceptionally superior to that of the antifoaming agent in the comparative example.
Furthermore, the antifoaming effect was sustained well.

[Effects of the Invention] When the antifoaming agent of the present invention is used to prevent and eliminate various troubles caused by foaming in each process of a paper mill, it can be used in a wide range of processes in a paper mill. Demonstrates stable and remarkable defoaming effect and its sustainability.

Claims (4)

[Claims] (1) General formula [RO(AO)_n]_mX(I) (wherein, R represents a linear or branched alkyl group, alkenyl group, or alkylphenyl group having 8 to 18 carbon atoms, and AO represents one unit of an oxyalkylene chain having 3 to 4 carbon atoms, n represents an integer of 1 to 30, m represents an integer of 1 to 3, and X represents a monovalent to trivalent carboxylic acid residue having 1 to 6 carbon atoms. and when the carboxylic acid is a polyvalent carboxylic acid, the residue is a carboxyl group, a salt thereof, or an ester thereof. (2) Compound 99 of general formula (I) according to claim (1)
．． 5 to 70 parts by weight, and 0.5 to 30 parts by weight of one or more types of hydrophobic waxes selected from hydrocarbon waxes, hydrophobic silica, higher fatty acid amides, and polyorganosiloxanes, and having a particle size of 30 μm or less. An antifoam composition containing particulate solids. (3) Compound 10 of general formula (I) according to claim (1)
Claim (1) or claim (1) in which 0.1 to 10 parts by weight of an anionic or nonionic emulsifier is blended to 0 parts by weight.
2) Antifoam composition as described. (4) Add the antifoam composition according to claim (3) to 1 part in water.
Antifoam composition emulsified at a concentration of ~50% by weight.