KR100598864B1 - Silicon Antifoaming Compounds for Detergents containing Self-emulsible Silicon Antifoaming Capsule and method for preparing thereof - Google Patents

Abstract

The present invention relates to a silicone antifoam composition for a detergent comprising an encapsulated self-emulsifying silicone compound and a method for preparing the same, more specifically, 30 to 60% by weight of a siloxane oil having a kinematic viscosity of 10 to 5,000 cSt and a kinematic viscosity of 5001 to 30 to 60% by weight of a siloxane oil of 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, 2 to 30% by weight of a modified silicone oil having a hydroxyl group at the end, 1 to 20% by weight of a silica filler, and an alkaline earth metal base catalyst 0.01 to 65 to 99.9 wt% of an antifoaming emulsion emulsified in water by mixing an oil-type silicone compound (1) comprising 2 wt%, the two siloxane oils, a self-emulsifying siloxane oil, and a modified silicone oil having a terminal hydroxyl group, An encapsulated self-emulsifying silicone compound (2) comprising 0.001 to 25% by weight of alkylalkoxysilane and 0.0001 to 10% by weight of a silicone polycondensation curing catalyst, By preparing a silicone antifoaming compound for detergents containing the compound (1) and the compound (2) in a weight ratio of 85 to 95: 5 to 15, the dispersibility in water is excellent and the antifoam durability at high temperatures as well as at low temperatures is improved and stored for a long time. The present invention relates to a detergent antifoaming agent composition comprising a encapsulated self-emulsifying silicone compound and a method for preparing the same, which is improved so that phase separation does not occur.

Silicone Defoamer, Encapsulation, Self-Emulsifying Type, Detergent, Drum Washing Machine

Description

Silicon Antifoaming Compounds for Detergents containing Self-emulsible Silicon Antifoaming Capsule and Method for Preparing Acoustic Defoamer comprising Encapsulated Self-Emulsifying Silicone Compound

The present invention relates to a silicone antifoam composition for a detergent comprising an encapsulated self-emulsifying silicone compound and a method for preparing the same, more specifically, 30 to 60% by weight of a siloxane oil having a kinematic viscosity of 10 to 5,000 cSt and a kinematic viscosity of 5001 to 30 to 60% by weight of a siloxane oil of 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, 2 to 30% by weight of a modified silicone oil having a hydroxyl group at the end, 1 to 20% by weight of a silica filler, and an alkaline earth metal base catalyst 0.01 to 65 to 99.9 wt% of an antifoaming emulsion emulsified in water by mixing an oil-type silicone compound (1) comprising 2 wt%, the two siloxane oils, a self-emulsifying siloxane oil, and a modified silicone oil having a terminal hydroxyl group, An encapsulated self-emulsifying silicone compound (2) comprising 0.001 to 25% by weight of alkylalkoxysilane and 0.0001 to 10% by weight of a silicone polycondensation curing catalyst, By preparing a silicone antifoaming compound for detergents containing the compound (1) and the compound (2) in a weight ratio of 85 to 95: 5 to 15, the dispersibility in water is excellent and the antifoam durability at high temperatures as well as at low temperatures is improved and stored for a long time. The present invention relates to a detergent antifoaming agent composition comprising a encapsulated self-emulsifying silicone compound and a method for preparing the same, which is improved so that phase separation does not occur.

Industrial detergents or household detergents include anionic surfactants and nonionic surfactants, and excessive bubbles are generated. When bubbles are generated in this way, not only the processing time is increased to remove the bubbles but also the amount of water is used, which causes problems in terms of environmental pollution. Accordingly, a series of techniques have been proposed for antifoaming agents and methods for preparing the same that can effectively control bubbles by using alone or mixtures of hydrocarbon-based oils, silicone oils, lipophilic silicas, and the like.

In particular, silicone antifoaming agents have various excellent properties compared to other antifoaming agents, so they are widely used in manufacturing processes involving foaming such as chemical industry, food industry, petroleum industry, textile industry, paper industry, paper pulp industry and pharmaceutical industry. Has been. Examples of the representative ones include oil-type antifoaming agents such as dimethylpolysiloxane, methylphenylpolysiloxane, methylvinylpolysiloxane, etc., compound antifoaming agents in which fine powder silica is added to oil-type antifoaming agents, and emulsion-type antifoaming agents that can be dispersed in water using surfactants and the like in siloxane oils. Is proposed. However, the emulsion type antifoaming agent has a problem in that the emulsion breaks and the defoaming function decreases under severe conditions such as high temperature, high alkalinity or high shear.

For example, Japanese Patent Laid-Open Nos. 51-71886, 52-19836, 52-22638, 54-43015, 55-23084, 6-142410, and 6-142411 Korean Patent No. 2003-24707 discloses a self-emulsifying emulsion antifoaming agent using a combination of an organopolysiloxane modified with a polyoxyalkylene group and a siloxane oil compound. Because of its weakness, when used in practice, it had to be diluted with water several times to several tens of times. In addition, in order to improve storage stability, dilution stability, etc., a synthetic stabilizer such as a surfactant, carboxymethyl cellulose, polyvinyl alcohol, sodium polyacrylate, etc. is used, but there is a problem that the viscosity changes or the defoaming performance decreases with the change over time. .

In Japanese Patent Laid-Open No. 15-230804, a method of stabilizing an oil-in-water silicone emulsion antifoam composition is proposed. EP 0638346 and 0663225 describe foam control compositions comprising a crosslinked organopolysiloxane polymer having a silicone defoamer and at least one polyoxy alkylene group. US Pat. Nos. 4,639,489, 4,749,740, and 5,283,004 describe silicone compositions useful as foam control agents. EP 217,501 describes the preparation of foam control compositions and detergent compositions containing the compositions. US Pat. Nos. 5,380,464 and 5,543,082 describe antifoam compositions made by mixing a silicone defoaming reaction product, a silicone-glycol copolymer, and a hydroxy terminated polydiorganosiloxane at room temperature. U.S. Patent No. 5,908,891 describes a dispersible silicone composition comprising a mineral oil and a silicone compound prepared by reacting a polyorganosiloxane with a silicon compound, a finely divided filler and a catalyst which is a reaction promoter between the other components. Korean Patent Laid-Open Publication No. 2003-0059509 discloses a silicone compound prepared by modifying a silica surface using a polyorganosiloxane, a silane compound, an untreated silica, and an amine catalyst, followed by addition reaction by adding an H-siloxane and a platinum catalyst. It describes the manufacturing method of. Korean Patent Laid-Open Publication No. 2004-75257 discloses hydrolysis of disilane and carbosilane, optionally by addition of methylchlorosilane, dimethyldichlorosilane or a mixture thereof, hydrolysis and reaction of silica and catalyst or polydimethylsiloxane, hydroxy. A method for producing a silicone oil compound antifoaming agent having excellent acid / alkali resistance and antifoaming power by further reacting terminal polydimethylsiloxane or a mixture thereof is described.

While these techniques are innovative in their own way, the above-described antifoaming agents not only have to use a large amount of expensive antifoam active ingredients and antifoaming agents, but also have a high antifoam effect immediately after incorporating the silicone antifoaming agent into other detergent compositions such as surfactants. The antifoaming effect did not persist, and there was a problem in that antifoaming and dispersibility were inferior in high temperature water.

In particular, the drum-type washing machine, which has recently been in the spotlight, is characterized by a relatively small amount of water but a long washing time since washing is performed using gravity when the laundry is dropped from the top of the washing tank. Therefore, in the case of a detergent for use in a drum type washing machine, it is essential that the defoaming effect should be maintained even after a long time and that the rinsing property is good even when using less water. There was an urgent need to develop new antifoam compounds to reflect real needs.

Accordingly, the present inventors have studied and tried to solve the problems of the conventional antifoaming agent, and as a result, untreated silica filler and alkaline earth metal in a mixture of siloxane-based oil, self-emulsifying siloxane oil having different kinematic viscosity, and modified silicone oil having a hydroxyl group at the end Silicone encapsulated antifoam emulsion comprising self-emulsifying siloxane oil in which alkylene oxide is added to the main chain of siloxane oil to oil type silicone compound (1) finely pulverized by milling process after condensation reaction by addition of a base catalyst. When the compound (2) is mixed at a certain ratio, it can be seen that even when using a relatively low temperature water such as tap water, it exhibits sufficient defoaming effect, and that the foaming capacity lasts for a long time even at high temperature and does not phase separate even if stored for a long time. The invention has been completed.

Accordingly, the present invention includes siloxane oils having a kinematic viscosity of 10 to 5,000 cSt, siloxane oils having a kinematic viscosity of 5001 to 50,000 cSt, self-emulsifying siloxane oils, modified silicone oils having hydroxyl groups at the end, silica fillers and alkaline earth metal base catalysts. Defoamer emulsion, alkylalkoxy silane and silicone polycondensation curing catalyst which mixed oil type silicone compound (1), said two types of siloxane type oil, self-emulsifying type | mold siloxane oil, and modified silicone oil whose terminal is a hydroxyl group, and emulsified in water It comprises an encapsulated self-emulsifying silicone compound (2) comprising a, wherein the compound (1) and the compound (2) is contained in an 85 to 95: 5 to 15 weight ratio for the purpose of providing a detergent silicone antifoam composition have.

In addition, another object of the present invention is to provide a method for preparing the detergent silicone antifoam composition.

The present invention is 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, the terminal is a hydroxyl group An oily silicone compound (1) comprising 2 to 30% by weight of modified silicone oil, 1 to 20% by weight of silica filler, and 0.01 to 2% by weight of alkaline earth metal base catalyst; 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, and a modified silicone oil having a hydroxyl group Encapsulated self-emulsifying silicone compound containing 65 to 99.9 wt% of antifoam emulsion, 2 to 30 wt%, emulsified in water, 0.001 to 25 wt% of alkylalkoxysilane and 0.0001 to 10 wt% of silicone polycondensation curing catalyst (2), characterized in that the silicone antifoam composition for detergent comprising the compound (1) and the compound (2) in a weight ratio of 85 to 95: 5 to 15.

The present invention will be described in more detail as follows.

The present invention is 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, the terminal is a hydroxyl group Oil type silicone compound (1) containing 2-30 weight% of modified silicone oil, 1-20 weight% of silica fillers, and 0.01-2 weight% of alkaline earth metal base catalysts, and the said 2 types of siloxane oil and self-emulsifying siloxane oil And an encapsulated self-emulsifying agent comprising 65 to 99.9 wt% of an antifoam emulsion, 0.001 to 25 wt% of an alkylalkoxysilane, and 0.0001 to 10 wt% of a silicone polycondensation curing catalyst. Dispersibility in water by preparing a silicone antifoaming compound for a detergent comprising a silicone compound (2), wherein the compound (1) and the compound (2) in a weight ratio of 85 to 95: 5 to 15 The present invention relates to a silicone antifoaming agent composition comprising a self-emulsifying silicone compound encapsulated, which is excellent and improves antifoam durability at low temperatures as well as high temperature storage and does not occur during long-term storage.

The silicone antifoam composition for detergents according to the present invention largely comprises an oil type silicone compound 1 and an encapsulated self-emulsifying silicone compound 2.

1.Oil Type Silicone Compound (1)

The oil type silicone compound (1) comprises (a) two kinds of siloxane oils with different kinematic viscosities, (b) self-emulsifying siloxane oils, (c) modified silicone oils with hydroxyl groups at the ends, (d) untreated silica fillers, and (e) And alkaline earth metal base catalysts.

1- (a) Two types of siloxane oils with different kinematic viscosity

The siloxane oil has the structure of Formula 1 below.

In said formula, R <_1> is a C1-C4 alkyl group, R <_2> is a methyl group and n is an integer of 0-50.

As the main component of the composition of the present invention, the siloxane-based oil serves to destroy the stability of the foam by lowering the surface tension due to the low attraction between the molecules and the water repellency and non-contact of the surface. In addition to the antifoaming performance, due to hydrogen bonding, the chemical stability is excellent, the bonding energy is large, the heat resistance is excellent, and the physiologically inert characteristics are present.

The siloxane-based oil has a kinematic viscosity of 10 to 50,000 cSt at room temperature, but in the present invention, an oil having a kinematic viscosity of 10 to 5,000 cSt and an oil having a kinematic viscosity of 5001 to 50,000 cSt may be used to achieve desired antifoaming performance. If the oil does not meet the range of the kinematic viscosity, it may be difficult to control the reactivity of the antifoaming agent or the handling thereof becomes difficult and it is difficult to exhibit the defoaming performance according to the object of the present invention. In particular, the siloxane-based oil in the above range can act as a solvent when the milling process with the untreated silica filler to control the reactivity to prevent gelation (gel).

As for the siloxane-based oil, it is preferable to use an oil having a kinematic viscosity of 10 to 5,000 cSt and an oil having a kinematic viscosity of 5001 to 50,000 cSt in the oil type silicone compound 1 in an amount of 30 to 60 wt%. If the content is less than 30% by weight, the amount of oil is too small to play a role in controlling the reactivity so that the reaction may gel or rubberize. If the content is more than 60% by weight, the viscosity may be too high to decrease the reactivity. The content of other components is reduced, making it difficult to achieve the desired defoaming performance.

1- (b) self-emulsifying siloxane oil

The self-emulsifying siloxane oil has a structure in which alkylene oxide is added to the ends of silicone oil main chains such as dimethylpolysiloxane, methylethylpolysiloxane, and diethylpolysiloxane, which are added in order to maintain sustainability of antifoaming ability at high temperature. As the silicone oil main chain, dimethyl polysiloxane is preferable, and as the alkylene oxide having 2 to 4 carbon atoms, one or two selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butene oxide and 2,3-butene oxide The above copolymer is preferable. In particular, in the alkylene oxide, a compound containing ethylene oxide and propylene oxide may be more preferably used as shown in the following Chemical Formula 2.

의 화학식을 갖는 에틸렌옥사이드와 프로필렌옥사이드의 중합체이며, m과 l의 비는 1 : 1에서 1 : 3의 범위를 갖는다.In the above formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is a methyl group, n is an integer of 0 to 50, R ₃ is

It is a polymer of ethylene oxide and propylene oxide having the formula of, and the ratio of m and l ranges from 1: 1 to 1: 3.

The content of the self-emulsifying siloxane oil is 2 to 30% by weight in the oily silicone compound 1, preferably 2 to 10% by weight. If the content is less than 2% by weight, it is difficult to show the desired vesicle persistence at high temperature, and if it exceeds 30% by weight, the amount of self-emulsifying siloxane oil is relatively small, so that the initial bubble generation amount is large, so that the defoaming performance is not easy and economical. Can not do it.

Modified silicone oil having 1- (c) terminal hydroxyl group

In order to perform the condensation reaction of the silica with the hydroxyl group (-OH) smoothly and effectively, a siloxane oil having a kinematic viscosity of 10 to 50,000 cSt represented by the following Chemical Formula 3 is preferably used, and the content thereof is 2 to 30 in the oil type silicone compound (1). Weight percent is preferred. If the content is less than 2% by weight, the condensation reaction of the silica with the hydroxyl group is not smooth, and thus it is difficult to show the desired antifoam persistence at high temperature. It is not easy and economical.

In the above formula, R ₁ is an alkyl group having 1 to 4 carbon atoms, R ₂ is a methyl group, n is an integer of 0 to 50, and R ₃ is H.

1- (d) untreated silica filler

The untreated silica filler is dispersed in the siloxane-based oil in the silicone antifoam composition of the present invention to lower the surface tension to improve the defoaming force, to exhibit resistance in acidic and basic conditions and to increase the antifoam duration. The raw silica filler is selected from dry silica, wet silica and silica airgel. The untreated silica filler is preferably contained 1 to 20% by weight in the oil type silicone compound (1), if the content is less than 1% by weight, there is a problem that the antifoaming agent does not exhibit sufficient defoaming power, if it exceeds 20% by weight It is difficult to disperse and sinks due to precipitation, which causes a problem of lowering the defoaming force.

1- (e) alkaline earth metal base catalyst

The alkaline earth metal base catalyst is representative as an accelerator for facilitating the condensation reaction of various siloxane oils and untreated silica with hydroxyl groups used in the present invention. Sodium hydroxide, potassium hydroxide and the like can be used. It is preferable to be contained in the oil-type silicone compound (1) 0.01 to 2% by weight, if the content is less than 0.01% by weight, the amount of the catalyst is not enough, condensation reactivity is poor, if it exceeds 2% by weight of the reaction Adjustment becomes difficult.

2. Encapsulated self-emulsifying silicone compound (2)

The encapsulated self-emulsifying silicone compound 2 comprises (a) an antifoaming emulsion, (b) an alkylalkoxysilane and (c) a silicone polycondensation curing catalyst.

2- (a) antifoam emulsion

Antifoam emulsion is 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 500 to 50,000 cSt, and self-emulsifying oil used in preparing the oil type silicone compound (1). 2-30 weight% of a type | mold siloxane oil and 2-30 weight% of modified silicone oil whose terminal is a hydroxyl group are mixed, and this mixture is prepared by emulsifying in water. The amount of water in the antifoam emulsion is preferably 30 to 70% by weight. If the content is less than 30% by weight, the amount of oil is too large, the resulting capsules are too large to encapsulate smoothly. If the amount is more than 70% by weight, the amount of water is too large to facilitate the encapsulation reaction due to the crosslinking reaction.

The antifoam emulsion is preferably added in an amount of 65 to 99.9 wt% in the encapsulated self-emulsifying silicone compound (2). If the content is less than 65% by weight, it is difficult to expect the desired physical properties. If the content is more than 99.9% by weight, the encapsulation reaction is not smooth.

2- (b) alkylalkoxysilane

As the alkylalkoxysilane, methylmethoxysilane, methylethoxysilane and the like may be preferably included, and 0.001 to 25% by weight of the self-emulsifying silicone compound 2 may be added. If the content is less than 0.001% by weight, the encapsulation is not smoothly performed. If the content is 25% by weight or more, the encapsulation reaction cannot be performed smoothly.

The alkylalkoxysilane serves to cause the polycondensation reaction of the antifoam emulsion and to generate a shell of the organopolysiloxane around the antifoam oil phase.

2- (c) silicone polycondensation curing catalyst

The silicone polycondensation curing catalyst includes dibutyl tin diacetate, aqueous triethanolamine, ammonium hydroxide and the like, and preferably contains 0.0001 to 10% by weight of the self-emulsifying silicone compound 2. If the content is less than 0.0001% by weight, the condensation reaction is not smooth, so it is difficult to prepare a capsule of the desired physical property, and if it exceeds 10% by weight, it is difficult to release the effective antifoaming agent smoothly.

The encapsulated self-emulsifying silicone compound 2 is prepared by reaction with an antifoam emulsion, an alkylalkoxysilane and a silicone polycondensation curing catalyst. An alkylalkoxysilane is added to the antifoam emulsion, heated to 65-75 ° C., and a silicone polycondensation curing catalyst is added to prepare an encapsulated self-emulsifying silicone compound. Encapsulation of the siloxane oil serves to stabilize vesicle persistence by controlling the release of the antifoam active ingredient of the silicone antifoam composition of the present invention. The reaction of the encapsulated self-emulsifying silicone compound 2 is known as the sol-gel reaction and the antifoam emulsion is carried out by mixing the composition and emulsifying it in water. Oil-soluble alkylalkoxysilane is added to this aqueous emulsion to cause a polycondensation reaction and to form a shell of organopolysiloxane around the antifoam oil phase. If the reaction rate is not important, the encapsulation reaction temperature is not very important.

When the detergent containing the antifoaming agent including the encapsulated self-emulsifying silicone compound (2) is introduced into a drum washing machine or the like, the encapsulated particles are destroyed by the mechanical force of washing, and when the emulsion antifoam is released through the micropore of the capsule, The action can be controlled.

Method for producing a silicone antifoam composition for detergents comprising an encapsulated self-emulsifying silicone compound according to the present invention is as follows.

Self-emulsifying type siloxane oil having a kinematic viscosity of 10 to 5,000 cSt at room temperature, a siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, and a copolymer of ethylene oxide and propylene oxide introduced at the end of the main chain to treat the surface of silica. The siloxane oil, the modified silicone oil having a hydroxyl group at the end, the untreated silica filler and the alkaline earth metal base catalyst are mixed in the reactor by the content according to the present invention and reacted in a nitrogen atmosphere for 3 to 5 hours at a reaction temperature of 100 to 250 ° C. After the reaction is completed, the temperature is lowered to 70 ° C. or lower and the siloxane compound mixture is milled finely to prepare an oily silicone compound 1. If the milling process is omitted, coarse particles of silica will settle down during precipitation, resulting in insufficient defoaming and poor compound long-term preservation.

In addition, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt at room temperature, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of self-emulsifying siloxane oil, and a terminal Self-emulsifying type encapsulated by emulsifying a mixture of 2 to 30% by weight of a hydroxyl group modified silicone oil in an aqueous solution, followed by a polycondensation reaction at 65 to 75 ° C by adding an alkylalkoxysilane, and encapsulating with a silicone polycondensation curing catalyst. The silicon compound 2 is manufactured.

The oil-type silicone compound (1) and the encapsulated self-emulsifying silicone compound (2) are mixed in a weight ratio of 85 to 95: 5 to 15 to prepare a silicone antifoaming agent composition according to the present invention. If the content of the oil type silicone compound (1) is larger than the content of the encapsulated self-emulsifying silicone compound (2), it is difficult to expect the antifoaming persistence at high temperature, and the encapsulating self-emulsifying silicone compound (2) If the content of R is relatively out of the above content, the water dispersibility is deteriorated, and it is difficult to expect the initial defoaming ability.

If the temperature range is out of the above range when reacting and encapsulating the surface of silicon, there is a problem that the reaction does not occur well under the catalyst or evaporates, thereby decreasing the reactivity. Or side reactions.

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

Examples and Comparative Examples

For Example 1, 96.5 g of dimethylpolysiloxane (KF96-350) with a kinematic viscosity of 350 cSt, 107.2 g of dimethylpolysiloxane (KF96-10000) with a kinematic viscosity of 10000 cSt, EO / PO containing self-emulsifying siloxane oil (TSA 780) 10.8 g, 10.8 g of modified silicone oil (YF3807D) having a hydroxyl group at the end, 14.9 g of untreated silica (SS-230), 1.0 g of another silica (D-10), and 0.056 g of catalyst KOH were added at 150 ° C under a nitrogen atmosphere. The reaction was carried out for 3 hours. After the reaction was finished, finely ground using a three-stage roll mill to prepare an oil type silicone antifoaming compound (1). Examples 2 to 5 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1, except that dimethylpolysiloxane, EO / PO-containing self-emulsifying polysiloxane, hydroxyl-modified siloxane, untreated silica, and catalyst were mixed in different amounts. After the reaction was completed, finely ground using a three-stage roll mill to prepare a silicone antifoaming compound. Comparative Example 7 is a particle defoamer for drum washing machines of Dow Corning (DC4248S), and Comparative Example 8 is a particle defoamer for drum washing machines of Wakasa (ASP-15).

And the antifoamer emulsion was encapsulated using the following method. 96.5 g of dimethylpolysiloxane (KF96-350) with a kinematic viscosity of 350 cSt under nitrogen atmosphere, 107.2 g of dimethylpolysiloxane (KF96-10000) with a kinematic viscosity of 10000 cSt, 10.8 g of EO / PO containing self-emulsifying siloxane oil (TSA 780) An antifoaming emulsion was prepared by dropwise addition of 10.8 g of modified silicone oil (YF3807D), which is a hydroxyl group, and 100 g of deionized water. 0.025 g of methyl trimethoxy silane was added thereto, and the mixture was heated to 65 to 75 ° C, and 0.01 g of dibutyl tin diacetate condensation catalyst was added to carry out encapsulation.

division Example Comparative Example One 2 3 4 5 One 2 3 4 5 6 7 8 Oil Type Silicone Compound (1) (wt%) KF96-50 - - - - - 40.00 - 40.00 - - - - - KF96-100 - - - - - - 40.00 - - - - - - KF96-350 40.00 - 40.00 40.00 40.00 - - - 40.00 40.00 - - - KF96-1000 - 40.00 - - - - - - - 44.43 - - - KF96-10000 44.43 44.43 44.43 44.43 - 44.43 44.43 - - - 40.00 - - RF20000 - - - - 44.43 - - 44.43 44.43 - 44.43 - - TSA 780 4.48 4.48 4.48 4.48 4.48 4.48 - 4.48 - 4.48 - - - YF3807D 4.48 4.48 4.48 4.48 4.48 - 4.48 - 4.48 - 4.48 - - SS-230 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 6.18 - - D-10 0.41 0.41 0.41 0.41 0.41 4.89 4.89 4.89 4.89 4.89 4.89 - - KOH 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 - - sub Total 100 100 100 100 100 100 100 100 100 100 100 - - Temperature (℃) 150 150 150 150 150 150 150 150 150 150 150 - - Hours (h) 3 3 3 3 3 3 3 3 3 3 3 - - Compound (2) (wt%) KF96-350 29.66 29.66 29.66 29.66 29.66 - - - - - - - - KF96-1000 32.95 32.95 32.95 32.95 32.95 - - - - - - - - TSA 780 3.32 3.32 3.32 3.32 3.32 - - - - - - - - YF3807D 3.32 3.32 3.32 3.32 3.32 - - - - - - - - Deionized water 30.74 30.74 30.74 30.74 30.74 - - - - - - - - Methyltrimethoxysilane 0.008 0.008 0.008 0.008 0.008 - - - - - - - - Curing catalyst 0.003 0.003 0.003 0.003 0.003 - - - - - - - - Total (weight ratio) Compound (1) 90 90 90 90 90 100 100 100 100 100 100 100 100 Compound (2) 10 10 10 10 10 - - - - - - - -  -KF96-50: Dimethyl polysiloxane oil, kinematic viscosity 50 cSt, Shin-Etsu Co., Ltd.-KF96-100: Dimethyl polysiloxane oil, kinematic viscosity 100 cSt, Shin-Etsu Co., Ltd.-KF96-350: Dimethyl polysiloxane oil, kinematic viscosity 350 cSt, Shin-Etsu Co., Ltd.-KF96 -1000: Dimethyl polysiloxane oil, kinematic viscosity 1000 cSt, Shin-Etsu Co., Ltd.-KF96-10000: Dimethyl polysiloxane oil, kinematic viscosity 10000 cSt, Shin-Etsu Co., Ltd.-RF20000: Dimethyl polysiloxane oil, kinematic viscosity 20000 cSt, Shin-Etsu Co., Ltd.-TSA 780: Self-emulsifying Type siloxane oil, GE Toshiba Silicone Co., Ltd.-YF3807D: modified silicone oil with hydroxyl group at the end, Dongyang Silicone-SS-230: untreated silica, emerging silica-D-10: silica, degussa

Experimental Example

Dispersibility in the aqueous solution was observed using the silicone antifoaming agent composition prepared according to Examples 1 to 5 and Comparative Examples 1 to 8, and the antifoaming performance with temperature and time was evaluated and shown in Table 2 below. At this time, the dispersion performance of the antifoaming agent was added to water at room temperature, and the antifoaming agent after stirring for 10 minutes was observed in the dispersion state in aqueous solution. The defoaming performance was blended with a 2% by weight in a general detergent to observe the defoaming performance according to the temperature using a drum washing machine. A ruler was attached to the glass front of the drum washing machine to compare the defoaming performance by measuring the height of the bubble (mm) over time.

division Example Comparative Example One 2 3 4 5 One 2 3 4 5 6 7 8 Dispersibility ⊙ ⊙ ○ ⊙ ⊙ △ X △ X ○ X ⊙ ⊙ Bubble height (mm) Test temperature: Room temperature 1 minute 35 35 50 40 70 70 65 65 35 30 60 65 25 5 minutes 40 30 40 30 70 55 55 70 50 45 65 40 25 10 minutes 40 40 40 30 30 65 80 85 65 60 75 80 45 15 mins 45 50 55 40 35 80 100 90 80 90 90 85 65 20 minutes 50 60 65 60 40 85 105 95 80 90 100 95 70 25 mins 65 70 75 75 50 70 100 80 75 85 95 100 75 30 minutes 60 60 65 50 40 85 110 95 90 95 105 90 80 40 mins 65 70 80 75 60 90 115 105 105 110 110 100 85 Bubble height (mm) Test temperature: 50 ℃ 1 minute 35 45 35 20 75 75 55 80 40 35 55 60 20 5 minutes 40 40 25 15 35 50 40 60 30 40 50 35 25 10 minutes 45 50 35 30 35 50 45 55 30 45 50 35 30 15 mins 55 55 45 40 35 70 60 75 45 50 55 40 50 20 minutes 55 65 55 50 50 80 80 80 65 70 75 55 65 25 mins 65 70 70 75 60 90 90 95 85 90 85 70 80 30 minutes 55 65 60 65 55 85 80 100 60 85 80 60 70 40 mins 70 75 85 85 70 95 115 110 105 110 110 70 95 Bubble height (mm) Test temperature: 70 ℃ 1 minute 10 20 15 10 40 100 55 95 70 60 55 48 23 5 minutes 20 30 30 25 55 100 80 95 60 60 75 58 68 10 minutes 25 60 50 35 60 80 75 70 70 70 70 53 80 15 mins 60 80 80 60 75 90 85 80 70 75 80 58 98 20 minutes 75 90 90 80 90 95 105 95 90 90 95 65 105 25 mins 90 95 95 85 95 120 105 115 115 110 100 78 120 30 minutes 80 80 85 60 85 115 125 110 105 110 95 79 125 40 mins 90 95 110 85 90 120 135 120 110 115 115 80 130  ⊙: Very good, ○: Excellent, △: Normal, X: Bad

As can be seen in Table 2, in the case of Examples 1 to 5 according to the present invention was very excellent in dispersibility except in the case of Example 3. Of course, in the case of Example 3 also has excellent dispersibility, it is considered that there is no difficulty in adding to detergent. In particular, it can be seen from the data that the more self-emulsifying antifoaming agent is blended, the dispersibility in the aqueous solution is improved. When the comparative examples were analyzed, the dispersibility of Comparative Examples 2, 4, and 6 was poor because the self-emulsifying silicone emulsion TSA 780 was not blended.

As a result of analyzing the defoaming performance according to the temperature, it was confirmed that the silicone antifoaming compound of Examples 1 to 5 according to the present invention has excellent sustainability of the defoaming performance at low and high temperatures. That is, the more the encapsulated defoaming agent is contained, the better the defoaming persistence, and Comparative Examples 1 to 6, which do not contain the encapsulating defoaming agent, are generally poor in dispersibility and have a particular problem in sustaining the defoaming at high temperature. In the case of 8, the dispersibility was excellent, but the vesicle persistence was found to be remarkably inferior to the present invention.

As described above, the detergent silicone antifoam composition comprising the encapsulated self-emulsifying silicone compound of the present invention and a method for preparing the same are siloxane oils having a kinematic viscosity of 10 to 5,000 cSt, siloxane oils having a kinematic viscosity of 5001 to 50,000 cSt, and magnetic Oil type silicone compound (1) containing an emulsified siloxane oil, a modified silicone oil having a hydroxyl group at the end, a silica filler, and an alkaline earth metal base catalyst, and the two kinds of siloxane-based oils, a self-emulsifying siloxane oil, and a modified modified terminal having a hydroxyl group. An encapsulated self-emulsifying silicone compound (2) comprising an antifoam emulsion, an alkylalkoxysilane, and a silicone polycondensation curing catalyst mixed with silicone oil and emulsified in water, wherein the compound (1) and the compound (2) Is contained in a weight ratio of 85 to 95: 5 to 15, so that even if a relatively low temperature water such as tap water is used, It represents the effect, and also long-lasting ability even at a high temperature that a parcel has an excellent effect that is not a phase separation and also long-term storage. In addition, the present invention is excellent in chemical, food, petroleum, textile industry, paper industry, because it is excellent in acid and alkali resistance, low-temperature and high-temperature defoaming when used in the preparation of detergents and cleaning products defoamers It is expected to be suitable for use in paper pulp industry, pharmaceutical industry and industrial wastewater treatment process.

Claims (5)

30 to 60 wt% of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60 wt% of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30 wt% of a self-emulsifying siloxane oil, and a modified silicone oil having a hydroxyl group at the end An oily silicone compound (1) comprising 2 to 30% by weight, silica filler 1 to 20% by weight and an alkaline earth metal base catalyst of 0.01 to 2% by weight, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, and a modified silicone oil having a hydroxyl group Encapsulated self-emulsifying type comprising 65 to 99.9 wt% of an antifoam emulsion prepared by mixing 2 to 30 wt% and emulsifying in water, 0.001 to 25 wt% of alkylalkoxysilane and 0.0001 to 10 wt% of silicone polycondensation curing catalyst A silicon compound (2), A silicone antifoam composition for detergents, characterized in that the compound (1) and the compound (2) is contained in a weight ratio of 85 to 95: 5 to 15. 2. The silicone antifoaming agent composition according to claim 1, wherein the content of the self-emulsifying siloxane oil contained in the oil type silicone compound (1) is 2 to 10% by weight. 3. The self-emulsifying siloxane oil according to claim 1 or 2, wherein the self-emulsifying siloxane oil is a compound in which an alkylene oxide is bonded to a terminal of a silicone oil main chain selected from the group consisting of dimethylpolysiloxane, methylethylpolysiloxane and diethylpolysiloxane. Silicone antifoam composition for detergents. 4. The detergent silicone according to claim 3, wherein the alkylene oxide is one or two or more copolymers selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butene oxide and 2,3-butene oxide. Antifoam composition. 30 to 60 wt% of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60 wt% of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30 wt% of a self-emulsifying siloxane oil, and a modified silicone oil having a hydroxyl group at the end A first step in which 2 to 30% by weight, 1 to 20% by weight of silica filler and 0.01 to 2% by weight of an alkaline earth metal base catalyst are placed in a reactor and condensation reaction in a nitrogen atmosphere at a reaction temperature of 100 to 250 ° C. for 3 to 5 hours; A second step of milling the product obtained in the first step at 70 ° C. or lower to obtain an oily silicon compound (1) in which finely ground unreacted silica is ground; 30 to 60% by weight of siloxane oil having a kinematic viscosity of 10 to 5,000 cSt, 30 to 60% by weight of siloxane oil having a kinematic viscosity of 5001 to 50,000 cSt, 2 to 30% by weight of a self-emulsifying siloxane oil, and a modified silicone oil having a hydroxyl group A third step of mixing 2-30 wt% and emulsifying in water to prepare an antifoam emulsion; An agent for obtaining an encapsulated self-emulsifying silicone compound (2) by reacting 65 to 99.9 wt% of the antifoam emulsion obtained in the third step, 0.001 to 25 wt% of the alkylalkoxysilane and 0.0001 to 10 wt% of the silicone polycondensation curing catalyst. 4 steps; And A fifth step of mixing the oil-type silicone compound (1) and the encapsulated self-emulsifying silicone compound (2) in a weight ratio of 85 to 95: 5 to 15 Method for producing a silicone antifoam composition for detergents comprising a.