JPH08173789A - Foam restrainer composition - Google Patents

Abstract

PURPOSE: To provide a foam restrainer composition which has improved continu ous antifoam and foam breaking characteristics at high temperature by mixing an oil compound composition comprising a hydrophobic organopolysiloxane and fine particles of silica with a polyoxyalkylene denatured silicone oil and a polyoxyalkylene polymer. CONSTITUTION: This foam restrainer composition is represented by formula I and contains 5-60wt.% oil compound comprising 100 pts.wt. hydrophobic organopolysiloxane having a viscosity of 10-500000cts at 25 deg.C and 0.1-20 pts.wt. fine particles of silica having specific surface area of 100m<2> /g or more. And the composition contains a hydrophilic polyoxyalkylene denatured silicone oil represented by formula II and a polyoxyalkylene polymer. In the formula, R<1> is an univalent organic group selected from hydrocarbon groups 1.9<=a<=2.2, R<2> is a hydrocarbon group, R<3> is a group represented by the general formula -R<5> -O(R<6> O)b (R<7> O)c -R<8> , R<4> is R<2> or R<3> , X is 5-10, and Y is 1-10.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to suds suppressors.

[0002]

2. Description of the Related Art Silicone defoamers have various excellent properties as compared with other defoamers.
It is widely used in the industrial fields with foaming such as oil and fat industry, petrochemical industry, rubber industry, paper pulp industry, food industry, textile industry and pharmaceutical industry, and includes dimethylpolysiloxane, methylphenylpolysiloxane, and methylvinylpolysiloxane. An oil compound type defoaming agent in which silicone oil such as siloxane and fine powder silica are mixed, and an emulsion type defoaming agent obtained by dispersing these oil compounds together with a surfactant in water are widely used.

This emulsion type antifoaming agent has a polyoxyalkylene group as an alternative to the emulsion defoaming agent because the emulsion is destroyed under severe conditions such as high temperature, high alkalinity and high shearing force and the defoaming ability is lowered. Self-emulsifying defoaming agent (both Japanese Patent Publication No. 52-19836 and Japanese Patent Publication Sho)
No. 52-22638 and Japanese Patent Publication No. 55-23084) are used for various oil agents, water-based inks and the like. And
Since this self-emulsifying defoaming agent can easily prepare a homogeneous emulsion when mixed with water, the composition, composition, and composition of the polyether-modified silicone that is the emulsifier component and the oil compound that is the defoaming component are Much research has been done on manufacturing methods, etc., and many high value-added varieties with improved properties such as dilution stability, defoaming durability, heat resistance, alkali resistance, dyeability, and paintability have been launched on the market. Demand and uses are increasing rapidly. Most of the foaming systems in which this self-emulsifying defoaming agent is used are water-based, and the addition amount to this is usually a few.
Since it is a minute amount of ppm to several hundred ppm, it is often added in water for several times to several tens of times in actual use, unless it is added to various oils and chemicals. .

[0004]

However, a self-emulsifying defoaming agent diluted with water can be used for one day at room temperature (about 15 to 25 ° C).
Even if it is stable for about one week, if it is exceeded, oil will float when stored under high temperatures such as in summer, and phenomena such as two-layer separation will occur. Diluted products in which such a phenomenon occurs not only have a significantly reduced defoaming power that should be exhibited, but also cause problems such as oil spots and uneven dyeing in products produced using this defoaming agent. Sometimes. In some cases, the self-emulsifying defoamer is added directly without dilution with water to simplify the process, but when the foaming system is at a high temperature, the self-emulsifying defoamer does not disperse. May occur, and as a result, the defoaming power may decrease.

[0005]

The present invention is a foam inhibitor composition which solves the above-mentioned problems, and comprises the following (a), (b),
A foam suppressor composition comprising the component (C). That is, they are represented by the following (Chemical formula 1) which is (a) hydrophobic and has a viscosity at 25 ° C of 10 to 500,000 cSt.
Oil compound 5 consisting of 00 parts by weight and 0.1 to 20 parts by weight of finely divided silica having a BET specific surface area of 100 m ² / g or more
~ 60% by weight

Embedded image (Wherein R ¹ is one or more monovalent organic groups selected from a hydroxyl group or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and 1.9 ≦ a ≦ 2.2).

[Chemical 4] [Wherein R ² is the same or different hydrocarbon group having 1 to 18 carbon atoms, R ³ is a general formula -R ⁵ -O (R ⁶ O) _b (R ⁷ O) _c -R ⁸ (R ⁵ is a carbon atom) Number 1
4, a divalent hydrocarbon group, R ⁶ is an ethylene group, R ⁷ is a propylene group, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A monovalent organic group selected from an acetyl group and an isocyanic acid group, 3 ≦ b ≦ 100, and 0 ≦ c ≦ 100), R ⁴ is R ² or R ³ , and X is 5 to 5; 100, Y is 1 to 10], the cloud point of a 1% aqueous solution is 40 ° C. or higher, and the viscosity at 25 ° C. is 10 to 100,000 cSt. C) A polyoxyalkylene polymer having a molecular weight of 500 to 5,000 is 0 to 90% by weight.

That is, the inventors of the present invention have conducted various studies to develop a self-emulsifying foam inhibitor composition which is easily dispersed in warm water, and whose diluted solution has a large stabilizing effect even at high temperatures. Of a 1% aqueous solution of an oil compound composition comprising a water-soluble organopolysiloxane and finely divided silica
A composition having excellent properties was obtained by mixing with a polyoxyalkylene-modified silicone oil and a polyoxyalkylene polymer at 40 ° C. or higher. This composition has good high temperature stability of the diluted solution, shows excellent defoaming sustainability and foam breaking property even at high temperature, and does not break the emulsion even under high shearing force, and has excellent mechanical stability. The present invention was completed by confirming that it is economical and safe, since this composition can be easily obtained by simply mixing the above-mentioned components.

The present invention will be described in detail below. The oil compound as the component (a) constituting the foam inhibitor composition of the present invention is the main component for imparting the defoaming property to the composition as described above, and the hydrophobic organopolysiloxane and It is made of fine powder silica. The hydrophobic organopolysiloxane used here may be linear or branched and is represented by the formula (1).

R ¹ in the chemical formula ¹ is a hydroxyl group or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group,
Alkyl groups such as decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group; 2-phenyl Aralkyl groups such as ethyl group and 2-methyl-2-phenylethyl group; or chloro obtained by substituting a part or all of hydrogen atoms bonded to carbon atoms of these groups with halogen atoms, cyano groups, amino groups and the like. Monovalent carbonization selected from methyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, 3-aminopropyl group, N- (β aminoethyl) -γ-aminopropyl group, etc. From the viewpoint of defoaming property and economical efficiency, it is preferable that 80 mol% or more of the hydrogen group is a methyl group. 'S a represented by 1.9 ≦ a ≦ 2.2. It should be noted that this may be a liquid at room temperature, but from the viewpoint of defoaming property and workability, the viscosity at 25 ° C is 10 to 500,000c.
St is necessary, more preferably 50 to 20,000
cSt.

The fine powder silica used here may be a known one, and may be either wet silica or dry silica. Examples thereof include precipitated silica, silica xerogel, fumed silica, and those whose surface is treated with an organic silyl group. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], Nipsil [Japan silica ( Co., Ltd. product name], Cabosil [US Cabot Company product name], Santocel [US Monsanto product name] and the like. These have affinity with silicone oil,
From the viewpoint of dispersibility, it is necessary that the BET method has a specific surface area of 100 m ² / g or more, and particularly preferably 200 m ² / g or more. If the amount of the finely divided silica added is less than 0.1 parts by weight with respect to 100 parts by weight of the above-mentioned hydrophobic organopolysiloxane, the defoaming performance will be poor, and if it is more than 20 parts by weight, the viscosity of the composition will increase, resulting in water dispersion. 0.1-
It is necessary to use 20 parts by weight, preferably 1 to 15 parts by weight.

The silicone oil compound as the component (a) is prepared by mixing the above-mentioned hydrophobic organopolysiloxane and a predetermined amount of finely divided silica and heat-treating at room temperature or at a temperature of 200 ° C. or lower, and then, if necessary, a low boiling point distillation compound. It can be manufactured by removing the minutes. In addition, an inorganic ammonium salt, an organic silicon compound, a siloxane resin, etc. may be added to the composition to improve defoaming durability, high temperature characteristics, dilution stability, etc. (Japanese Patent Publication No. 4-42043, JP-A-5-261206).
And Japanese Patent Laid-Open No. 5-261207) are optional. If the content of the component (a) in the foam suppressor composition of the present invention is less than 5% by weight, the foam suppressing effect of this composition becomes insufficient, and if it exceeds 60% by weight, dispersibility in water. Is inferior and difficult to handle, so 5 to 60% by weight is necessary, preferably 10 to 50% by weight, more preferably 20 to
40% by weight.

The polyoxyalkylene-modified silicone oil as the component (b) of the foam control composition of the present invention is a silicone oil as the component (a) together with a polyoxyalkylene polymer as the component (c) described later. It is for emulsifying and dispersing the compound in an aqueous system, which is represented by (Chemical Formula 2), in which R ² is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group; alkenyl groups such as vinyl group, allyl group; aryl groups such as phenyl group, tolyl group; cyclohexyl group Such as a cycloalkyl group or a hydrogen atom bonded to a carbon atom of these groups with a halogen atom, a cyano group or the like substituted with a chloromethyl group, a 3-chloropropyl group, 3,3,3- It is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, which is the same or different and is selected from a trifluoropropyl group, a cyanoethyl group, etc., but 90 mol% or more of all R ² groups is methyl. It is preferably a group.

R ³ is represented by the general formula -R ⁵ -O (R ⁶ O) _b (R ⁷ O) _c -R ⁸ , and R ⁵ is the number of carbon atoms such as methylene group, ethylene group, propylene group and butylene group. 1 to 4 divalent hydrocarbon groups, R ⁶ is an ethylene group, R ⁷ is a propylene group, R ⁸ is a hydrogen atom or a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
A monovalent organic group selected from an alkyl group having 1 to 6 carbon atoms such as a hexyl group, an acetyl group and an isocyanic acid group;
When the value of b is less than 3, it becomes difficult to emulsify the oil compound composition, and when it exceeds 100, the viscosity upon dilution becomes high and the workability deteriorates. Therefore, 3 ≦ b ≦ 100, preferably 10 ≦ b ≦ 50 is good. When c exceeds 100, it becomes difficult to emulsify the oil compound composition, and therefore 0 ≦ c ≦ 100, preferably 0 ≦ c ≦ 20. R ⁴ is R ² or R ³ .

If the value of X is less than 5, the defoaming property becomes poor, and the storage stability becomes poor due to the decrease in viscosity. If it exceeds 100, the viscosity upon dilution becomes high and the workability becomes poor.
00, especially 10 to 60 is preferred. When Y is less than 1, it is difficult to emulsify the oil compound composition, and when it exceeds 10, the viscosity at the time of dilution becomes high and the workability deteriorates, so 1 to 10, preferably 3 to 7 is preferable.

If the cloud point of a 1% aqueous solution is less than 40 ° C., the high temperature stability of the resulting diluted solution of the foam inhibitor composition will deteriorate.
C. or higher, preferably 60.degree. C. or higher. The polyoxyalkylene-modified silicone oil is preferably liquid at room temperature. Further, when the viscosity at 25 ° C is lower than 10 cSt, the foam inhibitor composition obtained is easily separated and has low stability, and when it is higher than 100,000 cSt, the foam inhibitor composition obtained is diluted with water. Since it becomes difficult to disperse when doing so and workability is deteriorated, it is preferable to set it to 10 to 100,000 cSt, and the preferable range is 100 to 10,000 cSt. As this polyoxyalkylene-modified silicone oil, one commercially available as a polyether-modified silicone may be used, or a conventionally known method, for example, organopolysiloxane containing ≡SiH group, vinyl group or allyl group at the terminal of the molecular chain may be used. It can be easily obtained by subjecting a polyoxyalkylene compound having an unsaturated group such as a group to an addition reaction in the presence of a platinum catalyst.

It should be noted that this is not limited to silicone oil modified with a single polyoxyalkylene compound, but two or more kinds of polyoxyalkylene groups having different molar ratios or molecular weights such as ethyleneoxy group / propyleneoxy group. Silicone oils contained in the same molecule can be used, and two or more kinds of polyoxyalkylene-modified silicone oils having different structures can also be used. If the content of the component (B) in the composition of the present invention is less than 5% by weight, the water dispersibility becomes poor, and if it exceeds 95% by weight, the defoaming property becomes poor, so that 5 to 95% by weight is required. However, it is more preferably 10 to 80% by weight. More preferably, it is 20 to 70% by weight.

Next, (C) of the foam control composition of the present invention
The component polyoxyalkylene polymer serves as an emulsification aid as described above, but since the viscosity of the foam inhibitor composition can be reduced by incorporating this component, workability during water dispersion is improved. improves. The polyoxyalkylene polymer as the component (c) may have any structure as long as it has a (R ⁹ O) group (where R ⁹ is an ethylene group or a propylene group) in the molecule. Even if it is linear,

Embedded image (R ¹⁰ is a monovalent organic group, R ¹¹ is a monovalent alkyl group, q,
(r and s are integers) may be a branched one, and the terminal group represented by R ¹⁰ is a hydrogen atom,
Generally, an alkyl group such as a methyl group, an ethyl group, a butyl group, a decyl group, and an octadecyl group; an alkenyl group such as a vinyl group and an allyl group; an acyl group such as an acetyl group and a stearoyl group; and an isocyanic acid group. It is not particularly limited to these.

Further, when the molecular weight is less than 500, the viscosity is low, so that the stability of the foam inhibitor composition obtained becomes poor, and when it exceeds 5,000, the viscosity becomes high and the dispersibility and workability are deteriorated. The average molecular weight is preferably 500 to 5,000, and more preferably 1,000 to 3,000. The component (c) used here is not limited to one type of polyoxyalkylene polymer, and two or more types of polyoxyalkylene polymers having different HLB or terminal groups may be used in combination. Good. When the compounding amount of the component (c) in the foam inhibitor composition is more than 90% by weight, the defoaming property deteriorates, so 0 to 90% by weight, preferably 0 to 50% by weight, more preferably 0 to 40% by weight. It is good to set it as the weight%. The suds suppressor composition of the present invention can be obtained by mixing predetermined amounts of the above-mentioned components (a), (b) and (c), and these respective components can be mixed using a mixer such as a homomixer. However, the mixing method is not particularly limited, but 40
You may heat-mix in the range of -150 degreeC.

[0018]

EXAMPLES Examples and comparative examples of the present invention will be given below.
The viscosities in these examples are the values measured at 25 ° C. Various physical properties were measured by the following methods. Regarding the components used in the examples and comparative examples, the production method is shown below only for the oil compounds (a) -1 and (a) -2, and for the other components, the chemical formulas are shown at the end. [Production method of oil compound] Oil compounds (a) -1 and (a) -2 were obtained by the following method. [Production method of oil compound (a) -1] As a hydrophobic organopolysiloxane, dimethylpolysiloxane KF-96 having a viscosity of 1,000 cSt [trade name of Shin-Etsu Chemical Co., Ltd.] 100 parts by weight, fine powder silica (surface Hydrophobized silica) Aerosil 200 [trade name of Nippon Aloezil Co., Ltd., specific surface area 200 m ² / g] treated with (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ 10 parts by weight, and further ammonium carbonate [Kanto Chemical Co., Ltd.] 0.5 part by weight was added and mixed under a nitrogen gas stream at 150 ° C. for 3 hours to obtain (a) -1. [Production method of oil compound (a) -2] 100 parts by weight of branched dimethylpolysiloxane as a hydrophobic organopolysiloxane (having a viscosity of 2,200 cSt and containing CH ₃ SiO _3/2 units in a 0.023 mole fraction) , Fine powder silica Nipsil HD-2 [product name of Nihon Silica Co., Ltd., specific surface area 3
00m ² / g] 3 parts by weight under a nitrogen gas stream at 150 ° C.
After mixing for a time, (a) -2 was obtained. (Dilution stability test) The foam inhibitor composition diluted to 5% with deionized water was placed in a glass bottle with a stopper and allowed to stand at room temperature and 50 ° C.
The appearance of the liquid after standing for 7 days was visually observed and evaluated according to the following criteria. ∘: No good emulsion, layer separation, or precipitate is observed. Δ: Generation of precipitates or separation of light and shade is observed. X: Non-uniform emulsion and two-layer separation are observed. (Defoaming test for nonionic foaming liquid) Polyoxyethylene nonylphenyl ether Emulgen 909 [trade name of Kao Corporation] 0.05 in 1 liter measuring cylinder
% 100% aqueous solution, 100 ppm of the foam inhibitor composition prepared by the following method was added as the active ingredient, and air was blown through the glass diffuser stone at a rate of 1 liter / minute. Foaming after 20 minutes by the air bubbling method. The volume [(total volume of foam volume + liquid volume) in ml] was measured at 25 ° C. (Examples 1 to 7), (Comparative Examples 1 to 4) Components (a), (b), and (c) were mixed with the components shown in (Table 1) at room temperature and stirred at 2,000 rpm for 10 minutes with a homomixer. ,
A suds suppressor composition was prepared. The obtained compositions were all white to off-white uniform liquid compositions. The test results for these compositions are shown in (Table 1).

[0019]

[Table 1]

The chemical formulas and physical property values of the components (b) and (c) in Table 1 are shown. _{(B) -1 (CH 3) 3 SiO} - [(CH 3) 2 SiO] 25 - (CH 3 R 12 SiO) 5 -Si (CH 3) 3 R 12 = -C 3 H 6 O (C 2 H ₄ O) ₄₀ (C ₃ H ₆ O) ₁₀ H Viscosity: 8,600 cSt, cloud point: 72 ° C (b) -2 (CH ₃ ) ₃ SiO-[(CH ₃ ) ₂ SiO] _30- (CH ₃ R ¹³ _{SiO) 5 -Si (CH 3)} 3 R 13 = -C 3 H 6 O (C 2 H 4 O) 30 (C 3 H 6 O) 10 C 4 H 9 viscosity: 1,250cSt, cloud point: 65 ° C. ( _{b) -3 (CH 3) 3 SiO} - [(CH 3) 2 SiO] 10 - (CH 3 R 14 SiO) 5 -Si (CH 3) 3 R 14 = -C 3 H 6 O (C 2 H 4 O) ₁₃ CH ₃ viscosity: 110cSt, cloud point: 65 ° C. _{(b) -4 (CH 3) 3 SiO} - [(CH 3) 2 SiO] 25 - (CH 3 R 15 SiO) 5 -Si (CH 3) ₃ R ¹⁵ = -C ₃ H ₆ O (C ₂ H ₄ O) ₂₅ (C ₃ H ₆ O) ₂₅ C ₄ H ₉ Viscosity: 1,600 cSt, Cloud point: 35 ° C (b) -5 (CH ₃ ). _{3 SiO - [(CH 3)} 2 SiO] 50 - (CH 3 R 16 SiO) 6 -Si (CH 3) 3 R 16 = -C 3 H 6 O (C 2 H 4 O) 20 (C 3 H 6 O) ₂₀ COCH ₃ Viscosity: 3,900 cSt, Cloud point: 38 ° C (C) -1 C ₄ H ₉ O (C ₂ H ₄ O) ₃₀ (C ₃ H ₆ O) ₁₀ C ₄ H ₉ Viscosity: 220 cSt (C) ) -2 C ₄ H ₉ O (C ₂ H ₄ O) ₅ (C ₃ H ₆ O) ₁₀ H Viscosity: 150 cSt

[0021]

EFFECTS OF THE INVENTION Since the foam suppressor composition of the present invention uses a polyoxyalkylene-modified silicone oil having a high cloud point as an emulsifying component, the high temperature stability of the diluting liquid is remarkably improved, and in the high temperature foaming liquid. Also, a long-term foam suppression effect can be expected.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Sachiko Nezu 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. A foam suppressor composition comprising the following components (a), (b) and (c): (A) A hydrophobic organopolysiloxane 100 represented by the following chemical formula 1 and having a viscosity at 25 ° C. of 10 to 500,000 cSt.
5 parts by weight and 0.1-20 parts by weight of finely divided silica having a specific surface area of 100 m ² / g or more by BET method 5
~ 60% by weight [Chemical formula 1] (Here, R ¹ is one or more monovalent organic groups selected from a hydroxyl group or a monovalent hydrocarbon group having 1 to 18 carbon atoms, and 1.9 ≦ a ≦ 2.2) (b) 2] [Wherein R ² is the same or different hydrocarbon group having 1 to 18 carbon atoms, R ³ is a general formula -R ⁵ -O (R ⁶ O) _b (R ⁷ O) _c -R ⁸ (R ⁵ is a carbon atom) Number 1
4, a divalent hydrocarbon group, R ⁶ is an ethylene group, R ⁷ is a propylene group, R ⁸ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A monovalent organic group selected from an acetyl group and an isocyanic acid group, 3 ≦ b ≦ 100, and 0 ≦ c ≦ 100), R ⁴ is R ² or R ³ , and X is 5 to 5; 100, Y is 1 to 10], the cloud point of a 1% aqueous solution is 40 ° C. or higher, and the viscosity at 25 ° C. is 10 to 100,000 cSt. C) Polyoxyalkylene polymer having a molecular weight of 500 to 5,000 0 to 90% by weight