KR100421438B1 - Composition for silicone antifoaming agent - Google Patents

Abstract

PURPOSE: A composition for silicone antifoaming agent is provided which is usefully used for defoaming water system of foodstuff, fermentation, pulp, paper making and drain treatment processes by consisting of silicon oil compound, surfactant, thickener and ion exchange water, thereby securing superior acid and alkali resistance. CONSTITUTION: In an antifoaming agent composition in which silicone oil compound comprising silicon oil and fine silica powder as principal constituents is emulsified, the composition for silicone antifoaming agent comprises 5 to 20 wt.% of silicon oil compound comprising polydimethylsiloxane represented as the following structural formula (I) and fine silica powder as principal constituents; 1 to 40 wt.% of one or more of emulsifiers selected from hydrophilic surfactant and lipophilic surfactant; 1 to 2 wt.% of thickener; and 60 to 90 wt.% of ion exchange water. In the formula 1, n is an integer of 16 to 810, wherein the silicone oil compound comprises 80 to 95 wt.% of polydimethylsiloxane having viscosity of 100 to 1,000 centistokes represented as the foregoing structural formula (I) and 5 to 20 wt.% of fine silica powder, and wherein the composition comprises 80 wt.% or more of emulsion particles having an average particle diameter of 1 to 40 μm.

Description

Silicone antifoam composition

The present invention relates to a silicone antifoam composition, and more particularly, it comprises a silicone oil compound, a surfactant, a thickener, and ion-exchanged water represented by the following structural formula (I), so as to be deformable under acidic or alkaline conditions (foaming), The present invention relates to a silicone antifoam composition useful for aqueous defoaming in food, fermentation, pulp, paper making, and drainage processes due to excellent acid / alkali resistance such as excellent antifoam persistence and storage stability.

Wherein n is an integer from 16 to 810.

Generally, silicone antifoams are prepared by emulsifying silicone oil compounds in which fine powder inorganic fillers such as silica, titanium dioxide, and aluminum oxide are dispersed in silicone oil, and also in order to improve the stability of silicone antifoams. In the process of emulsification, the method of controlling the amount of emulsifier is appropriately adopted to disperse the hydrophilic (hydrophilic) silicone oil compound.

In addition, the silicone antifoaming agent tried to determine the antifoaming (breaking force) expression mainly by an emulsifier. However, if the amount of the emulsifier in the emulsification process is too large, the average particle diameter of the emulsion particles is small, but useful for stabilization of the emulsion to some extent, but there is a problem in that the initial defoaming and foaming properties deteriorate. In addition, when the amount of the emulsifier is too small, the particle size of the emulsion particles is irregular and rough when the phase inversion (phase inversion) is excellent in the initial foaming and foaming properties, but the defoaming effect is not sustained due to the aggregation of the emulsion particles. In addition, even when the amount of the emulsifier is adjusted to an optimal amount, it is difficult to form emulsion particles having a constant particle size due to the amount of ion-exchanged water required for phase inversion and temperature and water temperature differences according to seasons. That is, by the method of controlling the content of the emulsifier, an emulsion of the antifoaming agent and the desired particle size could not be prepared.

Therefore, the improvement of the silicone antifoaming agent is preferably focused on the modification of the silicone oil compound rather than the emulsifier. As an example, Japanese Patent Application Laid-open No. 52-2,887 intends to improve storage stability by adding and emulsifying a silica-based inorganic material treated with silazane to a silicone oil suspension containing an emulsifier. In Japanese Patent Application Laid-Open No. 57-48,307, an organopolysiloxane was added to an organopolysiloxane, silica, and a catalyst to form an annealed layer to provide excellent antifoam durability under alkaline resistance conditions. In Japanese Patent Publication No. 51-35,556, a silicon oil compound consisting of organosilicon oil and silica was treated with an organosilicon compound containing nitrogen and emulsified to improve the defoaming effect. However, in the above methods, it was not possible to satisfy acid / alkali resistance, storage stability, foaming properties, and antifoam persistence at the same time as a method for improving the specific properties of any one of the properties of the antifoaming agent.

Accordingly, in the present invention, as a result of research to prepare an anti-foaming agent having excellent acid / alkali resistance, such as excellent foaming (foaming property), anti-foaming persistence and storage stability under acidic or alkaline conditions, the physical properties to the average particle diameter of the emulsion particles The present invention was completed by containing a polydimethylsiloxane containing methyl group and a silicone oil compound containing silica as a main component.

Accordingly, an object of the present invention is to provide a new antifoaming composition having excellent acid / alkali resistance such as excellent foaming (foaming property), antifoaming persistence and storage stability under acidic or alkaline conditions.

Hereinafter, the present invention will be described in detail.

The present invention relates to an antifoaming agent composition in which a silicone oil compound containing silicon oil and fine powder silica is emulsified, wherein the polydimethylsiloxane and fine powder silica represented by the following structural formula (I) are 5 to 20% by weight. And a silicone antifoam composition comprising 1 to 40% by weight of one or more emulsifiers, 1 to 2% by weight of thickener, and 60 to 90% by weight of ion-exchanged water, selected from among hydrophilic surfactants and lipophilic surfactants.

Wherein n is an integer from 16 to 810.

Referring to the present invention in more detail as follows.

The present invention emulsifies the silicone oil compound containing polydimethylsiloxane and silica represented by the above structural formula (I) to contain 80% by weight or more of the emulsion particles having an average particle size in the range of 1 to 40 μm, and thus acid or alkali conditions. The present invention relates to a novel silicone antifoaming agent composition having excellent acid / alkali resistance which can satisfy both foamability (foaming property), antifoaming persistence and storage stability at the same time.

The silicone oil compound, which is a feature of the present invention, is a silicone oil containing 80 to 95% by weight of polydimethylsiloxane represented by the above formula (I), and 5 to 20% by weight of silica as a fine powder inorganic filler. . At this time, the polydimethylsiloxane represented by the structural formula (I) is preferably used in the viscosity range 100 ~ 1,000 centistoke (cSt) 200 ~ 1,000 centistoke (cSt), if the viscosity is less than 100 cSt emulsion The particles have a small average particle diameter, which is useful for stabilizing the emulsion. However, the initial foaming and foaming properties are poor. If the particle size exceeds 1,000 cSt, the emulsion particles become irregular and rough, resulting in coagulation of the emulsion particles, which causes problems in storage stability. have. In addition, fine powder silica may be any one of dry silica and wet silica as a silica enhancer that is commonly used. For example, precipitated silica, fumed silica, or a surface thereof is treated with dimethyldichlorosilane. Silica and the like. The fine powder silica has a specific surface area of 70 to 150 m < 2 > In addition, when the fine powder silica is contained less than 5% by weight in the composition of the silicone oil compound, the antifoaming effect of the foamability and the antifoam persistence is not sufficiently exhibited. If the content is more than 20% by weight, the viscosity of the silicone oil compound increases and the workability It is bad and difficult to handle, and there is a problem that the storage stability of the antifoaming agent is lowered.

To prepare the silicone antifoaming agent composition of the present invention by emulsifying the silicone oil compound having the composition as described above, the silicone oil compound in the silicone antifoaming agent composition to contain 5 to 20% by weight. If the content of the silicone oil compound is less than 5% by weight, emulsion particles having an average particle diameter of less than 1 μm are formed, and thus, the initial defoaming property of the antifoaming agent is poor, and there is no foaming effect on the large bubbles. As the average particle diameter of the particles is large, the foaming property and the foaming sustainability of the antifoaming agent are lowered, and the stability of the emulsion itself is lowered. As time passes, the emulsion particles settle or the silicone oil compound is separated and floated.

As the emulsifier, any of nonionic, cationic and anionic may be used, but it is preferable to use a nonionic in view of the dispersion effect of the antifoaming agent. As the nonionic emulsifier, a hydrophilic surfactant or a hydrophobic surfactant may be used, and these are preferably used together. In the emulsification process, if the HLB (Hydrophilic-Lipophilic Balance) of the emulsifier is less than 3, it does not act as a dispersion stabilizer. If the HLB exceeds 19, the anti-foaming property is deteriorated. Therefore, the hydrophilic surfactant having an HLB of 8 to 20 is most preferred. And a lipophilic surfactant having an HLB of 2 to 7 are mixed and mixed so that the HLB of the emulsification process is in the range of 3 to 19. Specific examples of hydrophilic surfactants include sulfitan monostearate, propylene glycol monolaurate, stearic acid and oleic acid, and particularly preferably polyoxyethylene monostearate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene Storage stability of silicone antifoaming agent when selected from among sorbitan distearate, polyoxyethylene glycerin monooleate, polyoxyethylene cetyl ether, sucrose monostearate, polyoxyethylene nonyl phenyl ether and polyoxyethylene tridecyl ether Is excellent. Specific examples of the lipophilic surfactant include sorbitan fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, fatty acid esters of polyoxyethylene compounds, glycerin esters, propylene glycol esters and polypropylene glycols. The storage stability against acid / alkali is excellent.

The amount of the emulsifier contained in the silicone antifoaming agent composition of the present invention is 1 to 40% by weight, preferably 2 to 20% by weight, in an amount sufficient to emulsify the silicone oil compound. If the amount of the emulsifier is less than 1% by weight, the silicone oil compound may not be sufficiently emulsified and there is a problem in storage stability due to the floating layer separation phenomenon, and if the content exceeds 40% by weight, the average particle diameter of the emulsion particles The defoaming effect is small in the foam which is formed small and the thickness of the foam is large.

In addition, the silicone antifoaming agent composition of the present invention contains 1 to 2% by weight of one or more selected from fibrous ethers such as carboxymethyl cellulose and carboxyethyl cellulose, partially saponified polyvinyl alcohol, crystalline cellulose, sodium alginate, etc. If the amount of the thickener is less than 1% by weight, there is a problem in long-term storage stability. If the amount of the thickener is more than 2% by weight, the viscosity increases rapidly, and a homogeneous emulsion cannot be prepared.

The silicone antifoaming agent composition of the present invention having the above composition has an emulsion particle having an average particle diameter of 1 to 40 μm or more and thus 80 wt% or more. Thus, the foaming property (foaming property), the antifoaming property, and the storage stability under acid or alkali conditions are present. It can be easily seen that the acid / alkali resistance such as this is excellent.

Referring to the manufacturing process of the silicone defoamer by the silicone antifoam composition of the present invention in detail.

First, some of the total thickeners are dissolved in water and the hydrophilic surfactant, the lipophilic surfactant and the silicone oil compound are dissolved in this order, and then the remaining thickener is added thereto. Then, after adding water required for phase inversion, the pH of the mixture is adjusted to 6.5 to 7.5, and then an emulsion is prepared using a grinder such as a homomixer, homogenizer, colloid mill, or the like. The water is mixed with the emulsion and then pulverized again using the above pulverizer to obtain a silicone antifoaming agent.

In the manufacturing process of the silicone antifoaming agent, the thickener is preferably added in two portions rather than one at a time, because the first addition to improve the stability of the w / o emulsion formed during the addition of the silicone compound, The addition improves the dispersion stability of the emulsifier during phase inversion of the w / o emulsion into the o / w emulsion. The thickener is preferably 85 to 98% of the total thickener amount in the first injection, and the remainder is added in the second. When the thickener, hydrophilic surfactant, and lipophilic surfactant are dissolved, 40 to 70 ° C. should be maintained. If the temperature is less than 40 ° C., the dissolution state and dispersion state are uneven. Is lowered. When dissolving the silicone oil compound, it should be maintained at 70 ~ 100 ℃ If the temperature is less than 70 ℃ emulsion particles are irregular and coarse formed there is a problem in the storage stability due to the aggregation of the emulsion particles, if the temperature exceeds 100 ℃ due to moisture evaporation Phase inversion is difficult. In addition, the ion-exchanged water input for phase inversion is preferably heated to 50 to 60 ℃ for uniform dispersion of the thickener and emulsifier, the dosage is usually o / w at the emulsion w / o 10 to 20 parts by weight is used as the amount required to transfer to 100 parts by weight of the total amount of the reactants. It is also possible to control the emulsion particle size distribution by adjusting the temperature and the amount of the ion exchanged water.

The antifoaming agent composition of the present invention as described above has excellent foaming properties and foaming sustainability under acidic / alkali conditions, and has a good foaming effect on the vesicles having a large surface film thickness, and the emulsion itself is also very safe and has excellent storage stability for food, fermentation, and pulp. It is especially useful for water-based defoaming in water, papermaking and drainage processes.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, but the present invention is not limited thereto.

Example 1

Silicone oil compound A was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the structural formula (I) having a viscosity of 100 cSt and 50.0 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared.

400 g of ion-exchanged water was put in a 2 L container, and heated to 40-50 ° C., and then 15.2 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 12.1 g of a hydrophilic surfactant (ICI, SPAN 60) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 14.1 g of a lipophilic surfactant (ICI, TWEEN 60) was added and stirred for 30 to 40 minutes. 100 g of the silicon oil compound A prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 0.7 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, and then stirred at 70 ° C. for 20 to 30 minutes. 100 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 100 g of ion-exchanged water was slowly added to the reaction solution for 5 minutes. After stirring for 10 minutes, the reaction solution was ground using a colloid mill and cooled to room temperature, and 100 g of ion-exchanged water was added thereto and stirred for 10 minutes to prepare a silicone antifoaming agent. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 2

50 g of silicone oil compound A, primary thickener (UNION CARBIDE, QP 40) 16.0 g, hydrophilic surfactant (ICI, SPAN 40) 10.0 g, lipophilic surfactant (ICI, TWEEN 40) 16.2 g, secondary A silicone antifoam was prepared by the same method as Example 1 using 1.0 g of a thickener (Carbopol 934, Goodrich), 750 g of ion-exchanged water, and 0.6 g of sodium hydroxide. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 3

80 g of silicone oil compound A, primary thickener (UNION CARBIDE, QP 40) 10.0 g, hydrophilic surfactant (LONZA, SPAN 20) 48.4 g, lipophilic surfactant (LONZA, TWEEN 20) 56.4 g, secondary A silicone antifoam was prepared by the same method as Example 1 using 1.0 g of a thickener (Carbopol 934, Goodrich, 60 g of ion-exchanged water and 0.6 g of sodium hydroxide). The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 4

180 g of silicone oil compound A, primary thickener (UNION CARBIDE, QP 40) 10.0 g, hydrophilic surfactant (ICI, SPAN 80) 96.8 g, lipophilic surfactant (ICI, TWEEN 80) 112.8 g, secondary A silicone antifoam was prepared by the same method as Example 1 using 0.7 g of a thickener (Carbopol 934, Goodrich, 610 g of ion-exchanged water, and 0.6 g of sodium hydroxide). The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 5

100 g of silicone oil compound A, primary thickener (UNION CARBIDE, QP 40) 16.0 g, hydrophilic surfactant (LONZA, SPAN 40) 24.2 g, lipophilic surfactant (LONZA, TWEEN 40) 28.2 g, secondary A silicone antifoaming agent was prepared in the same manner as in Example 1 using 1.0 g of a thickener (Carbopol 934, Goodrich), 700 g of ion-exchanged water, and 0.6 g of sodium hydroxide. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 6

Silicone oil compound B was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the above structural formula (I) having a viscosity of 1,000 cSt and 300 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 400 g of ion-exchanged water was added to a 2 L container, and heated to 40-50 ° C., and then 10.0 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 36.3 g of a hydrophilic surfactant (ICI, BRIJ 72) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 42.3 g of a lipophilic surfactant (ICI, BRIJ 78) were added and stirred for 30 to 40 minutes. 180 g of the silicon oil compound B prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 0.7 g of a secondary thickener (Goodrich, Carbopol 934) in 50 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, and then stirred at 70 ° C. for 20 to 30 minutes. 60 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution in which 0.6 g of sodium hydroxide was dissolved in 100 g of ion-exchanged water was slowly added for 5 minutes. After stirring for 10 minutes, the reaction solution was ground using a colloid mill and cooled to room temperature, and 100 g of ion-exchanged water was added thereto and stirred for 10 minutes to prepare a silicone antifoaming agent. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 7

Silicone oil compound B 150 g, primary thickener (UNION CARBIDE, QP 40) 16.0 g, hydrophilic surfactant (ICI, BRIJ 52) 10.0 g, lipophilic surfactant (ICI, BRIJ 52) 16.2 g, secondary A silicone antifoam was prepared by the same method as Example 6 using 1.0 g of a thickener (Carbopol 934, Goodrich, 650 g of ion-exchanged water, and 0.6 g of sodium hydroxide). The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 8

Silicone oil compound C was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the above formula (I) having a viscosity of 500 cSt and 100 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 400 g of ion-exchanged water was added to a 2 L container, and heated to 40-50 ° C., and then 16.0 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 25.0 g of a hydrophilic surfactant (ICI, BRIJ 93) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 85.0 g of a lipophilic surfactant (ICI, BRIJ 98) were added thereto, followed by stirring for 30 to 40 minutes. 100 g of the silicon oil compound C prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 1.0 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 60 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 50 g of ion-exchanged water was slowly added for 5 minutes and stirred for 10 minutes to prepare a silicone antifoaming agent. . The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 9

Silicone oil compound C 50.0 g, primary thickener (UNION CARBIDE, QP 40) 16.0 g, hydrophilic surfactant (ICI, BRIJ 72) 10.0 g, lipophilic surfactant (ICI, BRIJ 721) 16.2 g, secondary A silicone antifoam was prepared by the same method as Example 6 using 1.0 g of a thickener (Carbopol 934, Goodrich, 650 g of ion-exchanged water and 0.6 g of sodium hydroxide), and was further ground using a colloid mill. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 10

Silicone oil compound D was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the above structural formula (I) having a viscosity of 350 cSt and 200 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 400 g of ion-exchanged water was added to a 2 L container, and heated to 40-50 ° C., and then 10.0 g of a first thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 48.4 g of a hydrophilic surfactant (ICI, SPAN 60) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 56.4 9 was added to the lipophilic surfactant (ICI, TWEEN 60) and stirred for 30 to 40 minutes. 90 g of the silicon oil compound D prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 1.0 g of a second thickener (Goodrich, Carbopol 934) dissolved in 90 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 100 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 100 g of ion-exchanged water was slowly added to the reaction solution for 5 minutes. Stirring for 10 minutes produced a silicone antifoam. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Example 11

50 g of the silicone antifoaming agents prepared in Examples 1, 6, 8 and 10, respectively, were quantified, mixed uniformly, and then ground using a colloid mill. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Comparative Example 1

Silicone oil compound E was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16-810) represented by the above structural formula (I) having a viscosity of 100 cSt and 20 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 300 g of ion-exchanged water was put in a 2 L container, and then heated to 40-50 ° C., and 15.2 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 12.1 g of a hydrophilic surfactant (ICI, SPAN 20) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 14.1 g of a lipophilic surfactant (ICI, TWEEN 20) was added and stirred for 30 to 40 minutes. 200 g of the silicon oil compound E prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 0.7 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 100 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 100 g of ion-exchanged water was slowly added to the reaction solution for 5 minutes. After stirring for 10 minutes, the reaction solution was pulverized using colloidal work, cooled to room temperature, 100 g of ion-exchanged water was added thereto and stirred for 10 minutes to prepare a silicone antifoaming agent, and further pulverized with a colloid mill. Silicone antifoam was prepared. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Comparative Example 2

Silicone oil compound F was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the above formula (I) having a viscosity of 350 cSt and 500 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 40 g of ion-exchanged water was added to a 2 L container, and heated to 40-50 ° C., and then 16.2 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 10.0 g of a hydrophilic surfactant (ICI, SPAN 60) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 16.2 g of a lipophilic surfactant (ICI, TWEEN 60) were added and stirred for 30 to 40 minutes. To this was added 30 g of the silicone oil compound F prepared above and stirred for 30 to 40 minutes while maintaining 70 ℃. A solution of 1.0 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 100 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 100 g of ion-exchanged water was slowly added to the reaction solution for 5 minutes. After stirring for 10 minutes, the reaction solution was pulverized using a colloid mill, cooled to room temperature, 100 g of ion-exchanged water was added thereto, stirred for 10 minutes, and further pulverized with colloidal work to prepare a silicone antifoaming agent. . The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Comparative Example 3

Silicone oil compound G was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16 to 810) represented by the above formula (I) having a viscosity of 500 cSt and 100 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 400 g of ion-exchanged water was put in a 2 L container, and heated to 40-50 ° C., and then 15.2 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 6.9 g of a hydrophilic surfactant (ICI, SPAN 80) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 120 g of a lipophilic surfactant (ICI, TWEEN 80) was added and stirred for 30 to 40 minutes. 100 g of the silicon oil compound G prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 0.7 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 50 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution in which 0.6 g of sodium hydroxide was dissolved in 50 g of ion-exchanged water was slowly added for 5 minutes. After stirring for 10 minutes, the reaction solution was ground using a colloid mill and cooled to room temperature, and 100 g of ion-exchanged water was added thereto and stirred for 10 minutes to prepare a silicone antifoaming agent. The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Comparative Example 4

Silicone oil compound H was added by mixing and mixing 1,000 g of polydimethylsiloxane (molecular weight or n value of 16-810) represented by the above formula (I) having a viscosity of 100 cSt and 200 g of silica (Aerosil, Degussa, Germany) in a 3 L container. Was prepared. 300 g of ion-exchanged water was put in a 2 L container, and then heated to 40-50 ° C., and 15.2 g of a primary thickener (UNION CARBIDE, QP 40) was added with vigorous stirring at 6,000 rpm or more. After stirring for 20 minutes, 198.0 g of a hydrophilic surfactant (ICI, SPAN 60) was added thereto, stirred for 20 to 30 minutes, and the reaction temperature was increased to 70 ° C. Subsequently, 7,0 g of a lipophilic surfactant (ICI, TWEEN 40) were added and stirred for 30 to 40 minutes. 100 g of the silicon oil compound H prepared above was added thereto and stirred for 30 to 40 minutes while maintaining 70 ° C. A solution of 0.7 g of a secondary thickener (Goodrich, Carbopol 934) in 100 g of ion-exchanged water at 70 ° C. was slowly added to the reaction solution for 10 minutes, followed by stirring at 70 ° C. for 20 to 30 minutes. 50 g of 70 ° C. ion-exchanged water was slowly added to the reaction solution for 5 minutes, and then a solution of 0.6 g of sodium hydroxide dissolved in 60 g of ion-exchanged water was slowly added for 5 minutes. After stirring for 10 minutes, the reaction solution was pulverized using a colloid mill, cooled to room temperature, 100 g of ion-exchanged water was added thereto, stirred for 10 minutes, and further pulverized with a colloid mill to prepare a silicone antifoaming agent. . The average particle size and particle size distribution of the emulsion particles of the silicone antifoaming agent composition are shown in Table 1 below.

Table 1

Test Example

The defoaming force test for each of the silicone defoaming agents prepared in Examples 1 to 11 and Comparative Examples 1 to 4 was carried out by the following method, wherein the test equipment used was a general pump test and JIS K It was carried out by -2518 sieve test method. The results are shown in Tables 2 and 3 below.

<Defoaming test by acid foaming solution>

① Dissolve the alkylaryl polyether sulfate (ROAM & HASS, X-100) in 0.1N HCl solution to prepare 1% by weight of acidic foam.

② The silicone antifoaming agent prepared in Examples and Comparative Examples was diluted in ion-exchanged water to prepare a 5% by weight silicone antifoam solution.

③ Put 200 ml of the acidic foam solution prepared in ① above into a 1 liter glass filter tube, and then add 4.0 g of the silicone antifoam solution prepared in ②.

④ Gently shake the above ③ solution so that the silicone antifoaming agent is spread evenly in the foaming solution.

⑤ After the glass filter tube is installed in JIS K-2518 inlet tester, nitrogen gas is introduced in 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes to investigate the change of bubble amount with time.

<Defoaming test by alkaline foaming solution>

① Dissolve alkylaryl polyether sulfate (ROAM & HASS, X-100) in 0.1N NaOH solution to prepare 1% by weight alkaline foam solution.

② A silicon antifoaming agent solution of 5% by weight is prepared by seating each silicon antifoaming agent prepared in Examples and Comparative Examples in ion-exchanged water.

③ Put 200 ml of the alkali foaming solution prepared in ① above into 1 liter glass filter tube, and then add 4.0 g of the silicone antifoaming agent solution prepared in ②.

④ Gently shake the above ③ solution so that the silicone antifoaming agent is spread evenly in the foaming solution.

⑤ After the glass filter tube is installed in JIS K-2518 inlet tester, nitrogen gas is introduced in 1 minute, 2 minutes, 3 minutes, 4 minutes, and 5 minutes to investigate the change of bubble amount with time.

Table 2. Antifoam Test with Acidic Foam

Table 3. Defoaming Test with Alkaline Foaming Solution

According to the results of Tables 2 and 3, the silicone antifoaming agent composition prepared in Examples according to the present invention is excellent in the antifoaming power (foaming force) of the antifoaming agent as it is seen that the initial bubble generation amount is significantly smaller than that of the antifoaming agent composition of the comparative example. It can be seen that.

In addition, it can be easily seen that the silicone antifoaming agent composition prepared in the example according to the present invention has a small bubble amount even after 3 minutes and 5 minutes of elapsed time, so that the storage stability and the antifoam persistence under acid / alkali conditions are excellent.

Claims (5)

In the antifoaming agent composition in which the silicone oil compound mainly containing silicone oil and fine powder silica is emulsified, 5 to 20% by weight of a silicone oil compound containing polydimethylsiloxane and fine powder silica represented by the following structural formula (I), 1 to 40% by weight of one or more emulsifiers selected from a hydrophilic surfactant and a lipophilic surfactant, and a thickener 1 to Silicone antifoam composition, characterized in that consisting of 2% by weight, 60 to 90% by weight of ion-exchanged water: Wherein n is an integer from 16 to 810. The silicone oil compound of claim 1, wherein the silicone oil compound is composed of 80 to 95% by weight of polydimethylsiloxane represented by the structural formula (I) having a viscosity of 100 to 1,000 centistokes, and 5 to 20% by weight of fine powder silica. Antifoam composition. The silicone antifoam composition of claim 1, wherein the silicone antifoam composition has an emulsion particle having an average particle diameter of 1 to 40 μm of 80% by weight or more. 85 to 98% of the total amount of the thickener is firstly added to water, and the hydrophilic surfactant, the lipophilic surfactant, and the silicone oil compound are dissolved in this order, and then the remaining amount of the thickener is added to the total amount of the reactant added. Silicone antifoaming agent, characterized in that 10 to 20 parts by weight of water at 50 to 60 ° C. is added, the pH of the mixture is adjusted to 6.5 to 7.5, and then pulverized with a pulverizer so that emulsion particles having an average particle diameter of 1 to 40 μm or more are present at least 80 wt% Method of Preparation of the Composition. The method of claim 4, wherein the thickener, the hydrophilic surfactant, and the lipophilic surfactant are dissolved at 40 to 70 ° C, and the silicone oil compound is dissolved at 70 to 100 ° C.