JPH05261206A - Foam inhibitor composition - Google Patents

Abstract

PURPOSE:To obtain a foam inhibitor composition excellent in dilution stability or the like by mixing a specified quantity of a specific polyoxyalkylene modified silicone oil, a blended material of a hydrophobic group oil with an organosilicon compound and a particulate silica, a polyoxyethylene-polyoxypropylene copolymer and a dimethylpolysiloxane oil. CONSTITUTION:This foam inhibitor composition contains 30-80wt.% polyoxyalkylene modified silicone oil expressed by formula 1, 5-50wt.% blended material of 100 pts.wt. hydrophobic group oil selected from dimethylpolysiloxane having 10-100000cS viscosity at 25 deg.C or aminoalkyl modified siloxane expressed by formula II and having 10-100000cS viscosity at 25 deg.C with 0.1-20 pts.wt. organosilicon compound expressed by formula III, 1-40 pts.wt. particulate silica, 5-50wt.% polyoxyethylene-polyoxypropylene copolymer having 500-3000 molecular weight and 2-20wt.% dimethylpolysiloxane having 10-500cS viscosity at 25 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a suds suppressor composition, and more particularly to a suds suppressor composition which exhibits excellent dispersion stability and suds suppressibility when added to an aqueous cutting oil, an oil agent for dyeing process and the like. It is a thing.

[0002]

2. Description of the Related Art Silicone defoaming agents containing dimethylpolysiloxane as a main component have various excellent properties as compared with other defoaming agents. Widely used in the process. Since this dimethylpolysiloxane is essentially hydrophobic, it is practically used as an emulsion type defoaming agent in which it is dispersed in water using a surfactant. If the liquid to be treated is at a high temperature or has a high shearing force, the desired defoaming effect cannot be expected because the emulsion is destroyed, and sometimes foaming may be accelerated. It also cannot be used in non-aqueous systems and has the further disadvantage that the emulsion separates during long term storage.

Therefore, it has been proposed to use an organopolysiloxane modified with a polyoxyalkylene group as the antifoaming agent (US Pat. No. 3,233,986).
However, since it has a disadvantage that the effect of defoaming and defoaming is small, a hydrophilic polysiloxane represented by dimethylpolysiloxane modified with polyoxyalkylene is used as a base oil. It has also been attempted to improve the defoaming effect by simultaneously using a diorganopolysiloxane typified by dimethylpolysiloxane and an oil compound consisting of finely powdered silica (Japanese Patent Publication Nos. 52-19836 and 52-1983). No. 22638, Japanese Patent Publication No. 55-23084), and those using a long-chain alkyl group and a polyoxyalkylene co-modified organopolysiloxane as a base oil have also been proposed (Japanese Patent Publication No. 58-581).
No. 26), it is difficult to disperse it in dimethylpolysiloxane stably with only fine powder silica, and when it is subjected to high temperature or mechanically strong shearing force for a long time, or when diluted or stored for a long time. However, there is a disadvantage in that the aggregation and separation of silica occur.

[0004]

Therefore, in order to improve the dispersibility of dimethylpolysiloxane and silica,
It has also been proposed to subject the silica surface to a hydrophobic treatment, and regarding the treatment of the fine powder silica, a method of subjecting the silica to a hydrophobic treatment with dimethyldichlorosilane in advance (see Japanese Patent Publication No. 52-31836), silica A method of treating nitrogen with a nitrogen-containing organosilicon compound (see Japanese Patent Publication No. 51-35556) has been proposed, but this requires a long period of time for the hydrophobic treatment of silica and requires treatment equipment. However, the process is complicated, which is not economical. In addition, a method of heat-treating a mixture consisting of a diorganopolysiloxane, an organosilicon compound, finely divided silica and a catalyst has also been attempted (see Japanese Patent Publication No. 3-39722 and Japanese Patent Publication No. 2-84), and this method is used. Although the defoaming effect is improved according to the above, since it essentially contains dimethylpolysiloxane as a main component, the above-mentioned versatility and stability are not satisfactory.
Therefore, the inventors of the present invention have proposed the above-described improved foam suppressor composition by using the previously limited polyoxyalkylene-modified silicone oil (see Japanese Patent Application No. 2-414678). Are required to have further improved characteristics.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a foam control agent which solves these disadvantages, which is represented by A) the general formula

[Chemical 3] [Wherein G ¹ is a group selected from R ¹ , G ² or G ³ , G ² , G ³
Is a formula (CH ₂ ) _r —O— (R ² O) _s Q having a molecular weight of 500 to 3,000 (R ² is an ethylene group and a propylene group, Q is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, an acetyl group, Monovalent organic group selected from isocyanic acid group, r is 2 to 6 and s is 5 to 50)
In the group represented by, G ² is an ethyleneoxy group in the (R ² O) group.
10 to 30 mol%, G ³ has an ethyleneoxy group in the (R ² O) group of 65
Is of 85 mol%, G ² / G ³ (molar ratio) is 0.3 / 1 to 3
/ 1, R ¹ is a monovalent hydrocarbon group having 3 to 20 carbon atoms, a is 0 or 1, m and n are positive numbers from 1 to 30, p is 10 to 100, and q is 1
~ 10 positive number] polyoxyalkylene-modified silicone oil 30 to 80% by weight B) Viscosity at 25 ℃ is 10 to
100,000cS dimethyl polysiloxane and / or general formula

[Chemical 4] [Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁴ is R ³ or a hydroxyl group, and R ⁵ is a formula-R ⁶ (NHCH ₂ C
H ₂ ) _b NR ⁷ R ⁸ (R ⁶ is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁷ ,
R ⁸ is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, b is an aminoalkyl group represented by 0 ≦ b ≦ 4), k is a positive number of 10 to 5,000, and l Is 0.01
~ 500 positive number], the amine equivalent is 5,000-500,
100 parts by weight of a hydrophobic base oil selected from linear aminoalkyl-modified siloxanes having a viscosity of 10 to 100,000 cS at 25 ° C and a general formula R ⁹ _c Y _d Si (-R ¹⁰ -CH = CH ₂ ) _4-cd (3) [wherein R ⁹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms, an acyloxy group, an alkenyloxy group] A group selected from the group, R ¹⁰ is a divalent hydrocarbon group having 0 to 8 carbon atoms, c is 0, 1 or 2, d is 1, 2 or 3, and an organic group represented by c + d ≤ 3] 5 to 50 parts by weight of a compound consisting of 0.1 to 20 parts by weight of a silicon compound and 1 to 40 parts by weight of finely divided silica, C) having a molecular weight range of 5
00 to 3,000, 5 to 50% by weight of polyoxyethylene-polyoxypropylene copolymer having an ethyleneoxy group of 10 to 85 mol%, D) Both ends of the molecular chain are blocked with monohydroxydimethylsilyl groups, Viscosity at 25 ℃ is 10-50
It is characterized by comprising 2 to 20% by weight of dimethylpolysiloxane of 0 cS.

That is, the inventors of the present invention have made various investigations on methods for solving the disadvantages of the defoaming agent containing a conventionally known polyoxyalkylene-modified organopolysiloxane as a main component, and as a result, the polyoxyalkylene-modified organopolysiloxane The amount of ethyleneoxy groups and propyleneoxy groups contained in and the molar ratio are specified, and dimethylpolysiloxane and /
Alternatively, a blend of a hydrophobic base oil selected from limited aminoalkyl modified silicone oils, an organosilicon compound containing an alkenyl group, and finely divided silica, and a polyoxyethylene-polyether in which the amount of ethyleneoxy groups is specified. Addition of oxypropylene copolymer and linear dimethylpolysiloxane whose molecular chain ends are blocked with monohydroxydimethylsilyl groups will result in a foam inhibitor with dilution stability, defoaming stability and high temperature stability. It was found that it would be excellent in sex.

Further, when a polysiloxane containing two kinds of polyoxyalkylenes in the same molecule as described above is used as compared with a polysiloxane modified with a single polyoxyalkylene, this product is excellent in dilution. Stability, high temperature stability, and dimethylpolysiloxane and / or limited aminoalkyl-modified silico-
It was confirmed that when an organosilicon compound containing an alkenyl group was added to a blend consisting of a hydrophobic base oil selected from a silicone oil and finely divided silica, it exhibited excellent defoaming durability and defoaming property, and The present invention has been completed by conducting research on the type and mixing ratio of each component. This will be described in more detail below.

[0008]

The present invention relates to a foam inhibitor composition which is particularly useful for an aqueous cutting oil, a fiber dyeing bath, a scouring bath and the like because it has excellent dilution stability, defoaming durability and high temperature stability. is there. The foam control composition of the present invention comprises A) a polyoxyalkylene-modified silicone oil represented by the general formula (1), B) dimethylpolysiloxane and / or an aminoalkyl-modified siloxane represented by the general formula (2). A blend comprising a hydrophobic base oil selected from the group consisting of the organosilicon compound represented by the general formula (3) and finely divided silica, C) a polyoxyethylene-polyoxypropylene copolymer, and D) a molecular chain. It is formed by mixing a predetermined amount of dimethylpolysiloxane whose both ends are blocked with monohydroxydimethylsilyl groups.

The polyoxyalkylene-modified silicone oil as the component A) constituting the foam control composition of the present invention has the general formula

[Chemical 5] , Where G ¹ is selected from R ¹ , G ² or G ³ ,
Either one or both of them may be used, and G ² and G ³ are represented by the formula (CH ₂ ) _r -O- (R ² O) _s -Q,
R ² is an ethylene group and a propylene group, Q is a hydrogen atom or a monovalent organic group selected from an alkyl group having 1 to 8 carbon atoms, an acetyl group and an isocyanic acid group, r is 2 to 6, preferably 2 to 3 , S is 5 to 50, preferably 15 to 45, and G ² is an ethyleneoxy group in the (R ² O) group of 10 to 30.
Mol%, G ³ is required to have an ethyleneoxy group in the (R ² O) group of 65 to 85 mol%.

When the average molecular weight of G ² and G ³ is less than 500, the effect of the alkyleneoxy group as a hydrophilic group is not sufficiently exhibited, and when it exceeds 3,000, the viscosity becomes too high and the dispersibility,
Since the workability becomes poor, it is necessary to set it in the range of 500 to 3,000, preferably 1,000 to 2,000. Also this
Regarding G ² and G ³ , when G ² / G ³ (molar ratio) in the formula is less than 0.3, the hydrophobic portion increases and the dispersibility deteriorates, and when it exceeds 3, the defoaming property deteriorates. It must be in the range of 3.

In the above, Q is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group or an octyl group, an acetyl group or an isocyanic acid group. A monovalent organic group selected from R ¹ is a monovalent hydrocarbon group, but if the carbon number exceeds 20, the defoaming property and the water dispersibility will be deteriorated, so that the carbon number is 3 to 20. When m and n are positive numbers of 1 to 30 and m + n is 3 to 40, preferably 3 to 20, and p is less than 10, the defoaming property deteriorates and the viscosity decreases. 9) Separation stability also deteriorates, and when it exceeds 100, the viscosity becomes high when diluted and the workability deteriorates.
0, preferably 20 to 60, and q is a positive number of 1 to 20, which is based on the content of the hydrophobic moiety represented by siloxane in the molecule, that is, from the total molecular weight. The amount excluding the molecular weights of G ² and G ³ is preferably 5 to 30% by weight.

This polyoxyalkylene-modified silicone oil can be synthesized by a conventionally known method. For example, two kinds of polyoxyalkylene-modified silicone oil having a methyl group containing an ≡SiH group and a vinyl group or an allyl group at the terminal of the molecular chain are used. The above polyoxyalkylene compound and an unsaturated olefin having 3 to 20 carbon atoms are subjected to an addition reaction in the presence of a platinum catalyst, or an organopolysiloxane containing an ≡SiH group and an R ¹ group is added to a vinyl group or The foam inhibitor composition of the present invention can be easily obtained by addition reaction of two or more polyoxyalkylene compounds having an allyl group.
If the content of the component A) in the weight% is less than 30% by weight, the water dispersibility is poor, and if it is more than 80% by weight, a uniform and stable self-emulsifying emulsion is hard to be obtained.
The amount may be in the range of 50% by weight, more preferably 50 to 70% by weight.

Next, the foam inhibitor composition of the present invention is constituted.
The formulation as component B) is the main component for imparting antifoam persistence to the foam suppressor composition of the present invention, which is selected from dimethylpolysiloxane and / or aminoalkyl modified siloxane. It is composed of a hydrophobic base oil, an organosilicon compound having an alkenyl group, and finely divided silica.

The dimethylpolysiloxane used here may be either linear or branched, but it is preferable that the molecular chain end is blocked with a trimethylsilyl group.
This dimethylpolysiloxane should have a viscosity as low as possible from the viewpoint of easy dispersion and workability,
From the viewpoint of defoaming durability, it is better to have a high viscosity, but if the viscosity is less than 10 cS, the resulting composition will have poor stability, and if the viscosity is more than 100,000 cS, the composition obtained will be used as a foam inhibitor composition. As the viscosity increases significantly when diluted with water before use, there is a problem in workability.
It is preferably in the range of up to 100,000 cS, preferably 100 to 5,000 cS.

Further, in the present invention, an aminoalkyl-modified siloxane can be used as the hydrophobic base oil in the component B). This aminoalkyl modified siloxane has the general formula

[Chemical 6] R ³ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
Octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, alkyl group such as octadecyl group, alkenyl group such as vinyl group and allyl group, aryl group such as phenyl group and tolyl group, cyclohexyl group, etc. Cycloalkyl groups, or chloromethyl group, chloropropyl group, tolufluoropropyl group, cyanoethyl group, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. An unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, preferably 90 mol% or more is a methyl group, R ⁴ is the same as R ³ or a hydroxyl group, and R ⁵ is a formula. -R ⁶ (NHCH
₂ CH ₂ ) _b NR ⁷ R ⁸ and R ⁶ is a divalent hydrocarbon group having 1 to 4 carbon atoms, which is a methylene group, a dimethylene group, a trimethylene group, a tetramethylene group, preferably a trimethylene group,
R ⁷ and R ⁸ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms which is the same as R ³ described above, and b is an aminoalkyl group in which 0 ≦ b ≦ 4, k is 1
It has a linear structure in which a positive number of 0 to 5,000 and 1 is a positive number of 0.01 to 500, and is preferably blocked with a trimethylsilyl group or a monohydroxydimethylsilyl group in which R ⁴ is a methyl group or a hydroxyl group. I shall.

If the amine equivalent is less than 5,000 or more than 500,000, the foam stability of the foam inhibitor composition obtained is lowered in dilution stability and troubles may occur during dyeing. However, it is preferably in the range of 10,000 to 100,000. In addition, it is preferable that the viscosity is as low as possible from the viewpoint of ease of dispersion and workability, and it is better that the viscosity is high from the viewpoint of defoaming durability, but if the viscosity is less than 10 cS. The resulting composition has poor stability, and when it is more than 100,000 cS, the viscosity increase becomes remarkable when the composition is diluted with water before it is used as a suds suppressor composition, resulting in difficulty in workability. So 1
It should be in the range of 0 to 100,000 cS, preferably 100 to 5,000 cS.

The organosilicon compound used here is represented by the general formula R ⁹ _c Y _d Si (-R ¹⁰ -CH = CH ₂ ) _4-cd (3), where R ⁹ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group,
1 carbon atom selected from alkyl groups such as octyl group, nonyl group and decyl group, aryl groups such as phenyl group and tolyl group, and cycloalkyl groups such as cyclohexyl group
~ 10 monovalent hydrocarbon groups, Y is a hydroxyl group or 1 to 1 carbon atoms
6 is a functional group selected from an alkoxy group, an acyloxy group and an alkenyloxy group, specifically, a group exemplified by a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an acetoxy group, a methoxyethoxy group and a propenoxy group. R ¹⁰ is a divalent hydrocarbon group having 0 to 8 carbon atoms selected from a covalent bond, a methylene group, a dimethylene group, a tetramethylene group, an octamethylene group, c is 0, 1 or 2, and d is 1 2 or 3, and C + d ≦ 3, and examples thereof include the following compounds.

CH ₂ = CHSi (OH) ₃ , CH ₂ = CHSi (OCH ₃ ) ₃ , CH ₂ = CHSi (OC ₂ H ₅ ) ₃ , CH ₂ = CHSi (OCH ₂ CH ₂ OCH ₃ ) ₃ ,

[Chemical 7] CH ₂ = CHSiCH ₃ (OCH ₃ ) ₂ , CH ₂ = CHSi (CH ₃ ) ₂ OCH ₃ , CH ₂ = CHSiC ₆ H ₅ (OCH ₃ ) ₂ , CH ₂ = CHCH ₂ Si (OC ₂ H ₅ ) ₃ , CH ₂ = CHCH ₂ CH ₂ Si (OCH ₃ ) ₃ , CH ₂ = CHCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ , CH ₂ = CH (CH ₂ ) ₄ Si (OCH ₃ ) ₃ , CH ₂ = CH _{(CH 2) 4 SiCH 3 (} OCH 3) 2, CH 2 = CH (CH 2) 4 Si (OC 2 H 5) 3, CH 2 = CH (CH 2) 8 Si (OCH 3) 3 In this organic Silicon compounds are hydrophobic base oils in component B) 10
If it is less than 0.1 parts by weight with respect to 0 parts by weight, the initial effect cannot be obtained, and if it is more than 20 parts by weight, the defoaming property becomes worse, so this should be 0.1 to 20 parts by weight. However, it is more preferably in the range of 0.5 to 10 parts by weight.

Further, the finely divided silica used here may be a known one and may be either wet silica or dry silica. Therefore, precipitated silica, silica xerogel, fumed silica, and further its surface may be used. Those treated with an organic silyl group are shown. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], Nipsil [trade name of Nippon Silica Co., Ltd.], Cabosil [trade name of Cabot Corporation of the United States], Examples include Santocell [trade name of Monsanto Chemical Co., USA], and it is preferable that these have a specific surface area by the BET method of 100 m ² / g or more.

When the amount of the finely divided silica is less than 1 part by weight relative to 100 parts by weight of the hydrophobic base oil in the component B), the defoaming performance becomes poor. However, it is necessary to set the amount to 1 to 40 parts by weight, more preferably 5 to 20 parts by weight.

The composition as component B) used in the present invention comprises a hydrophobic base oil 100 selected from the above-mentioned dimethylpolysiloxane and / or amylalkyl-modified siloxane.
It can be produced by mixing 0.1 to 20 parts by weight of an organosilicon compound and 1 to 40 parts by weight of finely divided silica with respect to parts by weight, heat-treating at room temperature to 200 ° C., and removing a low-boiling fraction as necessary. However, if the blending amount of this component B) in 100% by weight of the suds suppressor composition of the present invention is less than 5% by weight, the defoaming performance is not sufficiently exhibited, and if it is more than 50% by weight, this system increases. This is 5 because it is sticky and causes a problem in workability.
It is good to be in the range of 50 to 50% by weight, more preferably 10 to 30% by weight.

It also constitutes the suds suppressor composition of the present invention.
The polyoxyethylene-polyoxypropylene copolymer as the component C) serves as an emulsification aid for emulsifying and dispersing the components A), B) and the component D) described below.
If the molecular weight is less than 500, the resulting composition will have poor stability over time, and if it exceeds 3,000, the viscosity will increase and the dispersibility will be affected.
It is required to be in the range of 3,000 to 3,000, preferably 1,500 to 2,500.

When the ethyleneoxy group contained therein is less than 10 mol%, the hydrophobicity becomes so strong that the function as an emulsification aid becomes insufficient, and when it exceeds 85 mol%.
Since the HLB becomes too large and the function as an emulsification aid cannot be sufficiently exerted in this case, the content of ethyleneoxy groups is in the range of 10 to 85 mol%, preferably 30 to 70 mol%. Although it is required, if the content of this product in 100% by weight of the foam suppressor composition is less than 5% by weight, the storage stability becomes poor, and if it exceeds 50% by weight, the dilution stability of the composition becomes poor. So this is 5-50
The amount may be in the range of 10% by weight, more preferably 10 to 30% by weight.

It also constitutes the foam control composition of the present invention.
The dimethylpolysiloxane as the component (D) is one in which both ends of the molecular chain are blocked with monohydroxydimethylsilyl groups. This is effective as a binder of the above-mentioned A) component and B) component in the foam suppressor composition of the present invention, and the interface between A) component and B) component in which monohydroxydimethylsilyl group is originally less compatible. It has the function of lowering the tension and improves the compatibility of these components, but this causes oil spots when the viscosity is less than 10 cS,
When the viscosity is higher than 0 cS, the viscosity cannot be lowered, and the effect of addition thereof becomes insufficient, so that the viscosity of this foam suppressor composition is not increased, the viscosity is 10 to 500 cS, preferably 30 to 2
Must be of 00cS.

If the content of the D) component in 100% by weight of the foam suppressor composition is less than 2% by weight, the above effects are not sufficiently exhibited, and if it is more than 20% by weight, the viscosity becomes too low. Since the storage stability over time becomes poor, for example, the silica content settles down, this may be in the range of 2 to 20% by weight, more preferably 5 to 15% by weight.

The foam control composition of the present invention has the above A) to D).
It can be obtained by mixing a predetermined amount of the components, which can be uniformly mixed by using a mixer such as a homomixer, and the mixing order is not particularly limited, but at the time of mixing. You may heat in the range of 40-150 degreeC.

The foam inhibitor composition of the present invention thus obtained imparts an excellent low foaming property to the liquid to which it is added for a long period of time, and it also has excellent dispersion stability and high temperature, Since it has excellent mechanical stability under high shear and does not cause agglomeration, it can be suitably used as an antifoaming agent for aqueous cutting oils and oil agents or general paints in various dyeing processes, and various oil agents. it can.

[0028]

[Examples] Examples and comparative examples of the present invention will be given below. In the examples, the viscosity shows the measured value at 25 ° C, and the various physical properties show the measured values by the following test methods.

(Dilution Stability Test Method) 10 of foam control composition
Add 100 g of 100% aqueous dispersion to a 200 ml glass beaker and add 25
The temporal stability after storage at 1 ° C for 1 day was visually evaluated as follows. ⊚: Good emulsion and oil floating are not observed. ○: There is some oil floating or silica sedimentation. Δ: A lot of oil floats and a lot of silica sediments.

(Defoaming Test Method) 100 g of 0.2% sodium oleate aqueous solution was put into a 1,000 cc measuring cylinder,
1.0 g of 10% aqueous dispersion of suds suppressor composition (as an active ingredient 1,
000ppm) is added, and air is blown at 1,000cc / min through a glass dephasor stone by the air bubbling method.
The foaming amount (foaming amount + liquid amount) after 20 minutes was measured at 25 ° C.

Example 1 Average composition formula

[Chemical 8] 650 g of polyoxyalkylene-modified silicone oil (A-1) having a viscosity of 950 cS is used as the A component, and the viscosity is 10
450 g of 0 cS dimethyl silicone oil (B-1),
Dimethyl silicone oil with a viscosity of 1,000 cS (B-
2) 450 g, average particle size 1.4 μm and specific surface area 300 m ² / g
100 g of wet silica and 60 g of vinyltrimethoxysilane were heat-treated in a glass 2 liter flask under a nitrogen gas stream at 150 ° C. for 3 hours and mixed and stirred with a homomixer to prepare 150 g of the component B.

Expression

[Chemical 9] A linear dimethyl chain having 150 g of polyoxyethylene-polyoxypropylene copolymer having a viscosity of 250 cS as the component C, a viscosity of 50 cS, and both molecular chain ends blocked with monohydroxydimethylsilyl groups. 80 g of silicone oil is used as the component D, the components A to D are mixed, and the mixture is stirred for 5 to 10 minutes with a homomixer to prepare a foam inhibitor composition. When examined, the results as shown in Table 1 described later were obtained.

Examples 2 to 10 A foam inhibitor was prepared in the same manner as in Example 1 except that 60 g of vinyltrimethoxysilane in the component B used in Example 1 was replaced by the weight of the organosilicon compound shown in Table 1. Prepare a composition,
When the dilution stability and the defoaming property of each were examined, the results shown in Table 1 were obtained.

Example 11 Average composition formula

[Chemical 10] A foam inhibitor composition was prepared in the same manner as in Example 1 except that 650 g of a polyoxyalkylene-modified silicone oil (A-2) having a viscosity of 920 cS was used as the component A. When the defoaming property was examined, the results shown in Table 1 were obtained.

Example 12 Components A, C and D used were the same as in Example 1, and the average composition formula was used.

[Chemical 11] 900 g of aminoalkyl-modified silicone oil (B-3) having a viscosity of 330 cS and an amine equivalent of 14,000,
100 g of wet silica having an average particle size of 1.4 μm and a specific surface area of 300 m ² / g and 60 g of vinyltris (2-methoxyethoxy) silane were heat-treated in a glass 2-liter flask at 150 ° C. for 3 hours under a nitrogen gas stream. , Homomixer
When 150 g of the mixed and stirred mixture was used as the component B, the foaming inhibitor composition prepared from the components A to D in the same manner as in Example 1 was examined for dilution stability and defoaming property. The following results were obtained.

Comparative Example 1 Component B vinyltrimethoxysilane 60 used in Example 1
A foam inhibitor composition was prepared in the same manner as in Example 1 except that g was not used, and the dilution stability and defoaming property of this composition were examined. The results shown in Table 1 were obtained. ..

Comparative Examples 2 to 4 A suds suppressor composition was prepared in the same manner as in Example 1 except that the component used in Example 1, vinyltrimethoxysilane, was changed to the organosilicon compound shown in Table 1. When the respective dilution stability and defoaming property were examined, the results shown in Table 1 were obtained.

Comparative Example 5 Average composition formula

[Chemical 12] The foam inhibitor composition was prepared in the same manner as in Example 1 except that 650 g of polyoxyalkylene-modified silicone oil (A-3) having a viscosity of 1,300 cS was used as the component A. When the properties and antifoaming properties were examined, the results shown in Table 1 were obtained.

[0039]

[Table 1]

[0040]

The present invention relates to a suds suppressor composition, which comprises A) a polyoxyalkylene-modified silicone oil represented by the general formula (1), B) a dimethylpolysiloxane and / or a general formula as described above. A blend comprising a hydrophobic base oil selected from aminoalkyl-modified siloxanes represented by (2), an organosilicon compound represented by general formula (3), and finely divided silica, C) polyoxyethylene-polyoxypropylene copolymer It is characterized by comprising a polymer and D) a dimethylpolysiloxane having both ends of its molecular chain blocked with monohydroxydimethylsilyl groups, which is diluted as compared with conventionally known silicone antifoaming agents. Stability, defoaming durability, and high temperature properties are excellent, which gives an industrial advantage of reducing the added amount. There, this thing is excellent especially stability, for aqueous cutting oils, for various oils, textile dyeing process, can be suitably used as a defoaming agent for scouring process.

Front page continued (72) Inventor Kunihiro Yamada 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Satoshi Kuwata Otomi-mi, Matsuida-cho, Usui-gun, Gunma Address 1 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Center

Claims (1)

[Claims] 1. A) General formula: [G ¹ is a group selected from R ¹ , G ² or G ³ , and G ² and G ³ are of the formula (CH ₂ ) _r -O- (R ² O) _s Q (R ² is Ethylene group and propylene group, Q is a hydrogen atom or a carbon number of 1 to
8 is a monovalent organic group selected from an alkyl group, an acetyl group and an isocyanic acid group, r is 2 to 6 and s is a group represented by 5 to 50), and G ² is a group in the (R ² O) group. 10 to 30 ethyleneoxy groups
Mol%, G ³ is such that the ethyleneoxy group in the (R ² O) group is 65 to 85 mol%, G ² / G ³ (molar ratio) is 0.3 / 1 to 3/1, R ¹
Is a monovalent hydrocarbon group having 3 to 20 carbon atoms, a is 0 or 1,
m and n are positive numbers from 1 to 30, p is 10 to 100, and q is a positive number from 1 to 10] 30 to 80% by weight of polyoxyalkylene-modified silicone oil, B) the viscosity at 25 ° C is 10 to Dimethylpolysiloxane with 100,000 cS and / or general formula [Wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, R ⁴ is R ³ or a hydroxyl group, and R ⁵ is a formula —R ⁶ (NHCH ₂ C
H ₂ ) _b NR ⁷ R ⁸ (R ⁶ is a divalent hydrocarbon group having 1 to 4 carbon atoms,
R ⁷ and R ⁸ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, b is an aminoalkyl group represented by 0 ≦ b ≦ 4), and k is a positive number of 10 to 5,000. Number, l
0.01 to 500 positive number] and the amine equivalent is 5,000 to 50
100 parts by weight of a hydrophobic base oil selected from linear aminoalkyl-modified siloxanes having a viscosity of 10,000 to 100,000 cS at 25 ° C and a general formula R ⁹ _c Y _d Si (-R ¹⁰ -CH = CH ₂ ) _4-cd [wherein R ⁹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydroxyl group or a group selected from an alkoxy group having 1 to 6 carbon atoms, an acyloxy group and an alkenyloxy group, R ¹⁰ Is a divalent hydrocarbon group having 0 to 8 carbon atoms, c is 0, 1 or 2, d is 1, 2 or 3, and 0.1 to 20 parts by weight of an organosilicon compound represented by c + d ≤ 3] And 5 to 50% by weight of a mixture of 1 to 40 parts by weight of finely divided silica, C) a polyoxyethylene-polyoxypropylene copolymer having a molecular weight range of 500 to 3,000 and an ethyleneoxy group of 10 to 85 mol%. Polymer 5 to 50% by weight, D) Viscosity at 25 ° C, where both ends of the molecular chain are blocked with monohydroxydimethylsilyl groups. There linear dimethylpolysiloxane 2-20 wt% which is a 10～500CS, suds suppressor composition characterized in that it consists of and.