KR100298138B1 - Foam inhibitor composition - Google Patents

Abstract

The present invention is characterized in that the addition of a small amount provides a large puffing effect because of excellent papability and bubble continuity, and satisfactory dilution stability because of high affinity between silica and oil, excellent mechanical stability under high temperature and high shear force, It is possible to provide a novel foam inhibitor composition which is useful as a defoamer for high temperature dyeing and an emulsion foam inhibitor composition which is excellent in defoaming property and which achieves a large defoaming effect when added in small amounts and does not lose defoaming even under severe stirring It is aimed at.

The foam inhibitor composition of the present invention comprises,

(A) the general formula ^{(R 1 R 2 R 3 SiO} 1/2) 1 (R 4 R 5 SiO 2/2) m (R 6 SiO 3/2) n ( wherein, R ¹ to R ⁶ is C 1 -C A silicone oil having a viscosity of 10 to 100,000 cS at 25 DEG C, represented by the following formula: 0.005? N / 1 + m + n? 1 to 60% by weight of an organopolysiloxane composition comprising 0.1 to 20 parts by weight of a fine powdery silica,

(B) 5 to 99% by weight of one or more polyoxyalkylene denatured silicone oils,

(C) 0 to 90% by weight of one or more polyoxyalkylene polymers, or (A) a polymer consisting essentially of (R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _3/2 ) _n (wherein R ¹ to R ⁶ are as defined above) having a viscosity at 25 ° C of 10 to 100,000 cS and 100 parts by weight of a fine powder silica 1 to 90% by weight of an organopolysiloxane composition comprising 0.1 to 20 parts by weight,

(D) 0.1 to 50% by weight of one or more surfactants, and (e) a water-remaining portion.

Description

[Title of the Invention]

Foam inhibitor composition

DETAILED DESCRIPTION OF THE INVENTION [

The present invention relates to a foam inhibitor composition, particularly a foam inhibitor composition, which is excellent in defoaming property and has a large defoaming effect when added in a small amount, has good dilution stability and is excellent in mechanical stability under high temperature and high shear force and does not cause coagulation, To a useful foam inhibitor composition. Further, the present invention relates to a foam inhibitor composition which is excellent in defoaming property, gives a large defoaming effect by adding a small amount, and does not lose defoaming even under severe agitation.

Silicone antifoaming agents are widely used in industrial processes involving foaming such as chemical industry, food industry, petroleum industry, textile industry and pharmaceutical industry since they have various properties compared with other types of antifoaming agents. For example, dimethylpolysiloxane, methylphenylpolysiloxane And methylvinylpolysiloxane are mixed with fine powder silica, and an emulsion type antifoaming agent formed by dispersing these oil compounds together with a surfactant in water are commonly used.

In addition, the emulsion type antifoaming agent has a problem that the emulsion breaks down under the harsh conditions of high temperature, high alkylity and high shear force, so that the defoaming ability of the emulsion type defoaming agent is lowered. Therefore, an oil compound A self-emulsifying antifoaming agent (see JP-A 52-19,836, JP-A 52-22,638, JP-A 55-23,084) is used for dyeing, various emulsions, water-based inks and the like. However, these silicone defoaming agents also rapidly disappear after a lapse of time in the case of severe contact with gas in a foamy liquid, or in a system which is severely stirred under heating conditions such as a septic tank or a high-temperature high-pressure dyeing tank of a wastewater treatment plant. It is necessary to increase the addition amount of the defoamer or continuously add the defoamer.

For this reason, with regard to this silicone type antifoaming agent, for example, a method in which silica used in an oil compound is previously treated with dimethyldichlorosilane or the like to make it hydrophobic (see Japanese Patent Publication (Kokoku) No. 52-31,836) (Refer to Japanese Patent Application Laid-Open No. 51-35,556), and the like. However, a long time is required for the hydrophobic treatment of the silica, There is a drawback that it is not economical because it is complicated.

It has also been proposed to add an organopolysiloxane or organohydrogenpolysiloxane, silica and a catalyst to the organopolysiloxane or hydrocarbon (see Japanese Patent Application Laid-Open No. 57-48,307) The surface treatment of the silica is not sufficiently progressed unless the catalyst is added and heat treatment is carried out. In addition, there is a risk that there is a risk of flammability by hydrogen gas generated during the treatment process. Further, the organosilicon compound and the catalyst (See Japanese Examined Patent Publication (Kokoku) No. 3-39,722), a method of adding a siloxane resin composed of (CH ₃ ) ₃ SiO _1/2 unit and SiO _4/2 unit to organopolysiloxane and silica (Japanese Patent Application Laid-Open No. 3-12,923) has also been proposed, but it is necessary for them to have a sustained effect of bubble-formability There is a drawback that this is not the only thing.

Therefore, the inventors of the present invention firstly proposed a defoaming agent composition (Japanese Patent Application No. (JP-A) No. 4-91,813, which is an oil composition in which an organosilicon compound having an alkenyl group is treated with a silica treatment agent for the purpose of improving defoaming property of self- reference herein), and (CH _{3) 3} SiO _1/2 units and SiO _4/2 a foam inhibitor composition containing a siloxane resin consisting of units of compound in the oil (Japanese Patent Application (Kokai) No. 4-93453 reference herein) the However, further improved characteristics are required for these.

The present invention relates to a self-emulsifying foam inhibitor composition which solves such disadvantages, and it relates to a self-emulsifiable foam inhibitor composition which solves the above disadvantages and which comprises (a) a compound represented by the general formula (R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _3/2 ) _n wherein R ¹ to R ⁶ are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, 1, m and n are positive numbers, 0.005? N / (1 + m + 1) 60% by weight of an organopolysiloxane composition comprising 100 parts by weight of a silicone oil having a viscosity at 25 DEG C of 10 to 100,000 cS and 0.1 to 20 parts by weight of a fine powder silica, 5 to 99% by weight of at least two polyoxyalkylene denatured silicone oils, and 0 to 90% by weight of at least one polyoxyalkylene polymer (c).

That is, the inventors of the present invention have made various studies to develop a foam inhibitor composition having particularly excellent foaming property and vesicle persistence, and as a result,

(R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _3/2 ) _n (1)

Wherein R ¹ to R ⁶ are each a monovalent hydrocarbon group of 1 to 18 carbon atoms, and 1, m and n are positive numbers, and 0.005 ≦ n / (1 + m + n) ≦ 0.1. A polyoxyalkylene denatured silicone oil and a polyoxyalkylene polymer were used to form a self-emulsifying type foam inhibitor composition. This was excellent in papermaking property and vesicle persistence, so that a small amount of the foam inhibitor composition gave a lot of foaming effect , It is found that it is stable even when it is diluted with water to give an emulsion and that it is excellent in mechanical stability under high temperature and high shear force and does not cause aggregation and this is useful as a defoaming agent for high temperature dyeing because it has such properties, Troubles such as occurrence of staining unevenness due to the antifoaming agent in the dyeing step can be avoided, and since this is excellent in stability, May be used together with the acid does not damage the minute, and therefore also as to confirm that can be preferably used in various emulsion was added a defoaming agent, or for general paints, water-based cutting useful etc. and completed the present invention.

The present invention also relates to an emulsion-type foam inhibitor composition comprising (A) an emulsion-type foam inhibitor composition having the general formula (R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _{3 / 2} ) _n wherein R ¹ to R ⁶ are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, and 1, m and n are positive numbers of 0.005? N / (1 + m + n)? 0.1) 1 to 90% by weight of an organopolysiloxane composition comprising 100 parts by weight of a silicone oil having a viscosity at 25 DEG C of 10 to 100,000 cS and 0.1 to 20 parts by weight of a fine silica powder, By weight to 50% by weight, and (e) a water-remaining portion.

That is, the inventors of the present invention have conducted various studies to develop a foam inhibitor composition having particularly excellent foaming properties and vesicular persistence, and as a result,

(R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _3/2 ) _n (1)

Wherein R ¹ to R ⁶ are each a monovalent hydrocarbon group of 1 to 18 carbon atoms, and 1, m and n are positive numbers, and 0.005 ≦ n / (1 + m + n) ≦ 0.1. The emulsion type foam inhibitor composition was prepared by dispersing the organopolysiloxane composition and the surfactant in water. The emulsion type foam suppressant composition was excellent in papermaking property and vesicle persistence, and added with a small amount to give a large puffing effect. The emulsion itself was also excellent in stability And it does not lose its bubble property even under severe agitation. This is because it is not necessary to increase the addition amount to the foam system like the conventional defoaming agent, and thus it is possible to prevent the defects of the food, the fermentation pulp, The present inventors have completed the present invention by advancing research on each component used therein and the blending ratio thereof.

This is described in more detail below.

The present invention relates to a self-emulsifiable antifoam agent composition comprising (a) 1 to 60% by weight of an organopolysiloxane composition comprising 100 parts by weight of a silicone oil represented by the formula (1) and 0.1-20 parts by weight of a fine- , (B) 5 to 99% by weight of one or more polyoxyalkylene denatured silicone oils, and (c) 0 to 90% by weight of a polyoxyalkylene polymer, and these compositions Is advantageous in that it is excellent in papermaking and vesicular persistence, gives a lot of puffing effect even with a small amount of addition, and is excellent in dilution stability and does not lose its bubble property even under high temperature and high shearing force.

The organopolysiloxane composition as component (A) constituting the self-emulsifiable foam suppressant composition of the present invention is a main component of the foam inhibitor composition, but it is a silicone oil compound composed of a silicone oil and a fine-particle silica.

The silicone oil used herein is a silicone oil represented by the general formula (1)

(R ¹ R ² R ³ SiO _1/2 ) ₁ (R ⁴ R ⁵ SiO _2/2 ) _m (R ⁶ SiO _3/2 ) _n (1)

, Wherein R ¹ to R ⁶ are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, An alkenyl group such as a vinyl group and an allyl group, an aryl group such as a phenyl group and a tolyl group, or a part or all of the hydrogen atoms bonded to the carbon atoms of these groups Chloropropyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, or the like, having 1 to 18 carbon atoms in the same or different types selected from a chloromethyl group substituted by a halogen atom, a cyano group, A substituted or unsubstituted monovalent hydrocarbon group, it is preferable that at least 90 mol% of the entire R ¹ to R ⁶ groups are methyl groups in terms of defoaming property and economical efficiency.

The formula (1) representing the organopolysiloxane the number of moles of each unit in the shown as 1, m, n is a positive number, but none, of the R ⁶ SiO _3/2 units in a mole fraction n / m + n + 1 The value is preferably in the range of 0.005 to 0.1, preferably in the range of 0.01 to 0.05, because the bubble persistence deteriorates even if it is smaller than 0.005 or larger than 0.1.

It is preferable that viscosity is as low as possible in terms of easiness of dispersion and workability. In view of puff sustainability, the viscosity is better as the viscosity is higher. When the viscosity is less than 10 cS, the stability of the obtained composition is insufficient. When the viscosity is more than 100,000 cS, , The viscosity should be in the range of 10 to 100,000 cS, but the preferable range is preferably 100 to 20,000 cS.

Further, the hydrolysis is R ⁶ silicone oil containing SiO _3/2 units can be synthesized by a conventionally known method, but for example, the ^{R 1 R 2 R 3 SiCl,} R 4 R 5 SiCl 2 and R ⁶ SiCl ₃ with Or condensing the condensate with a cyclic low-molecular siloxane in the presence of a strong acid such as an alkali metal hydroxide, an alkali metal silanolate or a tetraalkylphosphonium hydroxide, a hydroxide such as tetraalkylammonium hydroxide or sulfuric acid or an organic sulfonic acid In the presence of a catalyst selected at room temperature or under heating.

The fine powdered silica used herein may be any of known wet type silica and dry type silica. Examples of the fine powdery silica include precipitated silica, silica gel, fumed silica, or the surface treated with an organosilyl group (Trade name of Nippon Aerosil Co., Ltd.), NIPHIL (trade name of Nippon Silica Co., Ltd.), CABOSIL (trade name of Cabot Corporation, USA), SANTHCELL And the like, but they preferably have a specific surface area of not less than 100 m < 2 > / g by the BET method.

When the amount of the fine powder silica is less than 0.1 parts by weight based on 100 parts by weight of the silicone oil, the defoaming performance is poor. When the amount of the fine silica powder is more than 20 parts by weight, the viscosity of the composition is increased and water dispersibility and workability are deteriorated. This should be in the range of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight.

The organopolysiloxane composition as component (A) constituting the self-emulsifiable antifoaming agent composition of the present invention is a silicone oil compound composed of a silicone oil and a fine-powdered silica as described above. This is because a predetermined amount of the silicone oil and the fine- Heat treatment at room temperature to 200 캜, and removing low boiling point oil as necessary. When the content of the component (a) in the foam inhibitor composition of the present invention is less than 1% by weight, the foam inhibiting effect of the composition becomes insufficient. When the content is larger than 60% by weight, the viscosity of the composition becomes high, It becomes difficult to handle. Therefore, it is required to be 1 to 60% by weight, but the preferable range is 5 to 40% by weight.

Next, the polyoxyalkylene-modified silicone oil as component (B) constituting the self-emulsifiable antifoaming agent composition of the present invention, together with the polyoxyalkylene polymer as the component (C) described later, This is for emulsifying and dispersing the organopolysiloxane composition in an aqueous system,

G _a R ⁷ _b SiO _{4-ab / 2} ... (2)

.

In the general formula (2), G represents a group represented by the general formula

-R ⁸ -O- (R ⁹ O) _p -Q- (3)

As a polyoxyalkylene group shown, R ⁸ is a methylene group, an ethylene group, a propylene group, a butylene group, a hexyl sengi, octanoic tengi, having a divalent hydrocarbon group of 1 to 10 carbon atoms such as sengi, R ⁹ is ethylene, and ( Q is a hydrogen atom or a monovalent organic group selected from an alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group octyl group, an acetyl group and an isocyanic group, p is an integer And R ⁷ is one or two or more unsubstituted or substituted monovalent hydrocarbon groups of 1 to 18 carbon atoms which are the same as R ¹ to R ⁶ given above, and a and b are each positive 1.9 ≤ a + b ≤ 2.2 .

The viscosity of the polyoxyalkylene-modified silicone oil is preferably in the liquid state at room temperature. However, if the viscosity at 25 ° C is lower than 10 cS, the obtained foam inhibitor composition tends to be easily separated and the stability is lowered. If the viscosity is higher than 100,000 cS, It is difficult to separate the inhibitor composition when it is diluted with water and workability is deteriorated. Therefore, the inhibitor composition is preferably 10 to 100,000 cS, but the preferred range is 100 to 10,000 cS.

This polyoxyalkylene-modified silicone oil may be a commercially available polyether-modified silicone, but it may be a conventionally known method, for example, a method in which an organopolysiloxane containing a? SiH group is added with a vinyl group or an allyl group Can be easily obtained by subjecting a polyoxyalkylene compound having an unsaturated group such as an alkyl group, an alkenyl group or the like to an addition reaction in the presence of a platinum catalyst.

It is also possible to use not only a silicone oil modified with a single polyoxyalkylene compound but also a silicone oil containing two or more kinds of polyoxyalkylene groups having different molar ratios of ethyleneoxy group and propyleneoxy group in the same molecule, May be used as the polyoxyalkylene-modified silicone oil.

The blending amount of the component (B) in 100 wt% of the self-emulsifiable antifoaming agent composition of the present invention is such that the water dispersibility is deteriorated when the content is less than 5 wt%, and the defoaming property is deteriorated when the content is more than 99 wt% To 99% by weight, and more preferably from 10 to 80% by weight.

Next, the polyoxyalkylene polymer as the component (C) constituting the self-emulsifiable antifoaming agent composition of the present invention is an emulsifying auxiliary as described above, but if it is blended, the viscosity of the foam inhibitor composition may be lowered , And the workability in water dispersion is improved.

The polyoxyalkylene polymer as the component (c) may have any structure as long as it has an (R ¹⁰ O) group (wherein R ¹⁰ is an ethylene group or a propylene group) in the molecule, expression

(R ¹¹ ... terminal group, R ¹² ... 1 alkyl group)

Examples of the terminal group include a hydrogen atom, an alkyl group such as methyl group, ethyl group, butyl group, decyl group and octadecyl group, an alkenyl group such as vinyl group and allyl group, an acetyl group, a stearyl group And isocyanic groups, but are not particularly limited to these groups.

It is preferable that this is liquid at room temperature, but since the viscosity is low at an average molecular weight of less than 500, stability of the resultant bubble inhibitor composition deteriorates over time, and if it exceeds 5,000, viscosity increases and affects dispersibility and workability , Which is preferably in the range of 500 to 5,000 in average molecular weight, but preferably in the range of 1,000 to 3,000.

The component (C) used herein is not limited to one kind of polyoxyalkylene polymer, and it may be used in combination with two or more different polyoxyalkylene polymers such as HLB or a terminal group. However, the bubble inhibitor composition 100 When the content of the component is more than 90% by weight, the storage stability and the dilution stability are deteriorated. The content of the component is preferably 0 to 90% by weight, more preferably 0 to 70% by weight.

Further, in the self-emulsifiable foam suppressant composition of the present invention, the weight ratio of the ethyleneoxy group / propyleneoxy group in the component (B) + (C) above is less than 0.1, the hydrophobicity is strengthened and the action as an emulsifier becomes insufficient, If the ratio exceeds 5, the HLB becomes too large. In this case, too, the action as an emulsifier is not sufficiently exhibited. Therefore, the HLB is preferably in the range of 0.1 to 5, but preferably in the range of 0.4 to 3.

The self-emulsifiable antifoaming agent composition of the present invention can be obtained by mixing predetermined amounts of the respective components (a), (b) and (c) described above. These components can be mixed by using a mixer such as a homomixer And the mixing order is not particularly limited. However, it may be heated in the range of 40 to 150 占 폚 at the time of mixing.

The present invention also relates to an emulsion-type foam inhibitor composition, which comprises (a) 1 to 90 weight parts of an organopolysiloxane composition comprising 100 parts by weight of a silicone oil represented by the above-mentioned formula (1) and 0.1 to 20 parts by weight of fine- (D) 0.1 to 50% by weight of (d) 0.1 to 50% by weight of one or more surfactants, and (e) a residual water part. The emulsion type air bubble retarder composition according to Also has a merit that it does not lose its bubble property under high temperature and high shear force.

The organopolysiloxane composition as the component (A) constituting the emulsion type antiperspirant composition of the present invention is as described above.

Next, any of the nonionic, cationic, and anionic surfactants may be used as the component (D) constituting the emulsion type foam inhibitor composition of the present invention. It is more preferable to use a hydrophilic surfactant in combination with a lipophilic surfactant. However, when the HLB is 3 or less, the surfactant does not function as a dispersion stabilizer. When the HLB is 19 or more, To 19% by weight or a hydrophilic surfactant having an HLB of 8 to 20 and a lipophilic surfactant having an HLB of 2 to 7 are mixed so that the HLB is in the range of 3 to 19.

Examples of such surfactants include sorbitan fatty acid esters, glycerin fatty acid esters, sucrose fatty acid esters, higher fatty acid esters of polyoxyethylene compounds, higher alcohol esters, alkylphenol condensates, alkyl quaternary ammonium salts and higher alkylsulfonic acid salts However, it is preferable to use a lipophilic surfactant such as a fatty acid sorbitan ester having 12 to 18 carbon atoms, glycerin ester, propylene glycol ester, or polypropylene glycol, and specifically, sorbitan monostearate, sorbitan monostearate Oleate, monoglycerin monooleate, triglycerin distearate, propylene glycol monolaurate, stearic acid, oleic acid, and the like.

As the surfactant, a fatty acid polyethylene glycol ester having 12 to 18 carbon atoms, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid alcohol ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene Polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan distearate, polyoxyethylene glycerin monooleate, polyoxyethylene cetyl alcohol, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan monooleate. Ether, sucrose monostearate, polyoxyethylene nonylphenyl ether, polyoxyethylene tridecyl ether, and the like.

The addition amount of the surfactant should be sufficient to make the silicone oil compound of the component (A) as an emulsion, but if it is less than 0.1% by weight, the stability of the obtained foam inhibitor composition is insufficient, %, The bubble suppression effect is deteriorated. Therefore, the content is preferably in the range of 0.1 to 50 wt%, but the preferable range is 1 to 10 wt%.

The thickening agent may be added to the emulsion-type foam suppressant composition of the present invention if necessary. Examples of the thickening agent include cellulose ethers such as carboxymethyl cellulose and carboxyethyl cellulose, partially saponified polyvinyl alcohol, crystalline cellulose, sodium alginate, Sodium and the like are exemplified, but the addition amount thereof is usually 5 parts by weight or less based on 100 parts by weight of the organopolysiloxane composition as the above-mentioned component (A).

In addition, it is optional to add a small amount of the bactericide to the emulsion-type foam suppressor composition of the present invention for the purpose of preservation. Examples of the bactericide include sodium hypochlorite, sorbic acid and the like. It may be 0.01 to 0.5 parts by weight based on 100 parts by weight of the organopolysiloxane composition.

In the emulsion-type foam suppressant composition of the present invention, it is necessary to add water necessary for the phase to the system constituted of the organopolysiloxane composition and the surfactant as described above. This means that the emulsion is changed from the W / O type to the O / W type , But it is preferably in the range of 50 to 8,000 parts by weight based on 100 parts by weight of the organopolysiloxane composition as the above component (a).

The emulsion type bubble inhibitor composition of the present invention can be obtained by mixing and uniformly stirring predetermined amounts of the components (a), (d), and (e) described above. The emulsion has a volume average particle diameter 6 to 18 占 퐉, and the volume distribution ratio of the particles within the particle diameter range is preferably 40% or more.

Such an emulsion can be prepared, for example, by: (i) uniformly mixing and dispersing an organopolysiloxane composition and a surfactant, (ii) dissolving the thickener in water, and (iii) (ii) adding a predetermined amount of the thickened water obtained in the step (ii) to a homogenous emulsion by using a homogenizer such as a homomixer, a homodizer or a colloid mill, and then (iv) With the thickened water obtained in the step (1).

In this emulsification, a mixture of the organopolysiloxane composition and a surfactant may be heated as required. The temperature of the water to be added to the dispersion is adjusted to 5 to 50 ° C and the temperature (phase temperature) Deg.] C. By controlling the temperature at the time of the transfer, emulsions that maintain the particle diameter range described above can be reproducibly obtained.

[Example]

Examples of the silicone oil used in the present invention and comparative examples, the example of the production of the oil compound, and the examples and the comparative examples are shown. The viscosity in the examples is a value measured at 25 ° C, The physical properties show the test results by the following method.

[Parasol test by anionic foaming liquid]

100 ppm of a foam inhibitor composition was added to 500 g of a 0.1% aqueous solution of sodium polyoxyethylene alkyl ether sulfate / perox EK (product name of Nippon Oil Co., Ltd.), stirred at 25 ° C for 30 seconds with a juicer mixer, And the change with time of the bubble volume (ml) was measured.

[Parasol test by non-ionic foaming liquid]

100 ppm of a foam inhibitor composition was added to 500 g of a 0.05% aqueous solution of polyoxyethylene nonylphenyl ether-EMALGEN 909 [product name of Hanao Co., Ltd.], stirred at 25 캜 for 30 seconds with a juicer mixer, And the change with time of the bubble volume (ml) was measured.

[Dilution stability test]

100 g of a 10% aqueous dispersion of the foam inhibitor composition was placed in a 200 ml glass beaker and allowed to stand at 25 占 폚 for one day, and the appearance of the liquid was visually evaluated as follows.

○ ... No good emulsion, no oil spill, no silica precipitation.

△ ... Oil float or silica sedimentation slightly.

× ... There are many oil injuries and many silica sediments.

[Dyeability test ... Oil spot test]

Three drops of the original solution of the foam inhibitor composition and 75% and 50% water dilution were added to the polyester fabric three times at 150 ° C for 3 minutes. Then, the resultant was dried with a rotary pot dyeing tester MINI-COLOR 12 EL type [ And then stained with the following conditions.

Staining solution ... Dianix Violet 3R-FS 0.1% O.W.F.

Acetic acid 0.3 ml / l

Temperature … 2 ° C / min cooling

60 占 폚? 120 占 폚 占 30 minutes? Room temperature

Bathrobes ... 1: 20

Thereafter, the dyeing fabric was washed with water, dried, and visually observed for uneven dyeing, and evaluated as follows.

○ ... Decolorization and partial thickening are not observed.

△ ... There is a little discoloration and partial thickening.

× ... Discoloration and partial thickening are remarkable.

[Emulsion stability test]

100 g of the foam inhibitor composition was placed in a glass bottle, and the stability of the composition after 20 days at 40 DEG C was visually evaluated as follows.

○ ... Separation and scum occurrence are not confirmed.

△ ... There is little splash or scum occurrence.

× ... Two-layer separation or scum generation is high.

[Synthesis Example 1]

3,000 g of water was placed in a 5 liter internal flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device. While stirring, a mixture of 490 g of trimethylchlorosilane, 560 g of dimethyldichlorosilane and 650 g of methyltrichlorosilane was added to the reaction product Was dropwise added over 3 hours while cooling to 50 占 폚 or lower. The mixture was stirred at 30 ° C for 2 hours to separate and remove the aqueous layer (hydrochloric acid + water), and 1,700 g of 3% sodium carbonate aqueous solution was added to the organic layer. The mixture was stirred at room temperature for 2 hours to separate and remove the aqueous layer. And 70 g of anhydrous sodium sulfate was added. The mixture was stirred at room temperature for 3 hours and then filtered to obtain a colorless transparent base oil A having a viscosity of 14 cS.

[Synthesis Example 2]

10 g of the base oil A obtained in Synthesis Example 1, 22 g of trimethylsilyl end-blocked polydimethylsiloxane having a viscosity of 10 cS, and 300 g of octamethylcyclotetrasiloxane were placed in a 500 ml internal volume flask equipped with a stirrer, a thermometer, a cooling tube and a nitrogen gas- And the mixture was heated to 120 DEG C with nitrogen gas being passed through with stirring. Then, 0.3 g of potassium hydroxide was added, and the mixture was further heated to 150 캜 and stirred for 4 hours. Then, the mixture was cooled to 100 캜, 2 g of ethylenechlorohydrin was added, and stirring was continued at 100 캜 for 2 hours. The obtained reaction product was heated at 160 DEG C under a reduced pressure of 100 mmHg for 2 hours to remove unreacted low-molecular siloxane to obtain a silicone oil A having a viscosity of 16,000 cS. The structure was analyzed by ²⁹ Si-NMR, and the CH ₃ SiO _3/2 unit contained 0.012 mole fraction.

[Synthesis Example 3]

Following the Synthesis Example 2, by the base oil A 25g and octamethylcyclotetrasiloxane was used in the same manner except that 308g synthetic bar, jyeoteuna yield a silicone oil B a viscosity of 2,200cS, ²⁹ Si-NMR about its origin as a starting material As a result of structural analysis, CH ₃ SiO _3/2 units contained 0.023 mole fraction.

[Synthesis Example 4]

The reaction was carried out in the same manner as in Synthesis Example 1 except that 113 g of trimethylchlorosilane, 640 g of dimethyldichlorosilane and 740 g of methyltrichlorosilane were used, to give a colorless transparent base oil B having a viscosity of 110 cS.

[Synthesis Example 5]

Except that 35 g of Base Oil B obtained in Synthesis Example 4, 22 g of trimethylsilyl end-blocked polydimethylsiloxane having a viscosity of 10 cS and 292 g of octamethylcyclotetrasiloxane were used as the starting materials in Synthesis Example 2, Silicone oil C having a viscosity of 3,100 cS was obtained. Structural analysis of this was carried out by ²⁹ Si-NMR. As a result, CH ₃ SiO _3/2 unit contained 0.047 mole fraction.

[Synthesis Example 6]

The reaction was carried out in the same manner as in Synthesis Example 2 except that 80 g of base oil B, 12 g of trimethylsilyl end-blocked polydimethylsiloxane having a viscosity of 10 cS and 220 g of octamethylcyclotetrasiloxane were used, Silicone oil D was obtained, and the structure was analyzed by ²⁹ Si-NMR. As a result, the CH ₃ SiO _3/2 unit contained 0.122 mole fraction.

[Oil compound production examples 1 to 9]

As silicone oil, silicone oils A to D obtained in Synthesis Examples 2, 3, 5, and 6 and dimethyl silicone oil KF-96 having a viscosity of 3,000 cS and 350 cS (product name of Shin-Etsu Chemical Industries Co., Ltd.) (Trade name, available from Nippon Aerosil Co., Ltd., specific surface area: 300 m 2 / g) and treated silica (Aerosil 200 [manufactured by Nippon Aerosil Co., Ltd.]) as fine powder silica, (Product name, specific surface area: 200 m 2 / g) treated with (CH ₃ ) ₃ SiNH ₂ were mixed in the respective compositions shown in Table 1 and mixed at 150 ° C. for 3 hours under a stream of nitrogen gas, Organopolysiloxane compositions A to I were prepared.

[Table 1]

[Example 1]

100 g of the organopolysiloxane composition A obtained in Oil Composition Production Example 1 and an average composition formula of G ¹ _0.1 (CH ₃ ) _2.0 SiO _0.95 wherein G ¹ is -C ₃ H ₆ O (C ₂ H ₄ O) ₂₅ (C _{3 H 6 O) 25 C 4 H} 9] is a polyoxyalkylene-modified silicone to an oil viscosity is shown 1,400cS a 60g, the average composition formula of _{C 4 H 9 O (C 2} H 4 O) 30 (C 3 H 6 O ) ₁₀ C ₄ H ₉ , 220 g of a polyoxyethylene-polyoxypropylene copolymer A having an average molecular weight of 2,030 and a viscosity of 200 cS and an average composition formula of C ₄ H ₉ O (C ₂ H ₄ O) ₅ (C ₃ H ₆ O) ₂₀ H, 120 g of a polyoxyethylene-polyoxypropylene copolymer B having an average molecular weight of 1.454 and a viscosity of 150 cS were mixed and stirred with a homomixer for 10 minutes to prepare a foam inhibiting composition A, The freeness, dilution stability and dyeability of the composition were examined. As a result, the results shown in Table 2 were obtained in the latter period.

[Examples 2 to 5 and Comparative Examples 1 to 4]

Except that the organopolysiloxane compositions B to I shown in the following Table 2 were used in the same weight in place of the organopolysiloxane composition A used in Example 1 to prepare the foam inhibitor compositions B to I Dilution stability and dyeability were examined. As a result, the results as shown in the following Table 2 were obtained.

[Example 6]

150 g of the organopolysiloxane composition A used in Example 1, 260 g of the polyoxyalkylene-modified silicone oil A used in Example 1 and 260 g of the polyoxyalkylene-modified silicone oil A having an average composition formula of G ² _0.03 (CH ₃ ) _1.98 (C ₁₀ H ₂₁ ) _0.03 SiO _0.98 G ² is mixed with 90 g of a polyoxyalkylene-modified silicone oil B having a viscosity of 1,100 cS, represented by -C ₃ H ₆ O (C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₂₄ H, And the mixture was stirred with a mixer for 10 minutes to prepare a foam inhibitor composition A '. The foamability, dilution stability and dyeability of the composition were examined, and the results as shown in the following Table 2 were obtained.

[Examples 7 to 10, Comparative Examples 5 to 8]

Except that the organopolysiloxane compositions B to I shown in the following Table 2 were used in the same weight in place of the organopolysiloxane composition A used in Example 6 to prepare the foam inhibitor compositions B ' I 'were prepared, and their fibrillation properties, dilution stability and dyeability were examined. As a result, the results shown in Table 2 were obtained.

[Table 2]

[Oil compound production examples 10 to 18]

Organopolysiloxane compositions A to I were prepared in the same manner as described in Oil Compounds Production Examples 1 to 9 except that the respective compositions shown in the following Table 3 were used.

[Table 3]

[Example 11]

Oil Composition 100 g of the organopolysiloxane composition A obtained in Production Example 1, 15 g of sorbitan monostearate / nonion SP-60R (product name of Nippon Oil Co., Ltd.), polyethylene glycol monostearate / Emanon 3199 20 g of polyoxyethylene polyoxypropylene block polymer, propone 201 (product name of Nippon Oil Co., Ltd.), 15 g of castor oil, 15 g of carboxymethylcellulose diacell # 1271 ) Product Product Name] were mixed at 80 DEG C for 30 minutes to prepare a preliminary mixture. Subsequently, 350 g of water at 50 DEG C was added to the mixture, and the resultant mixture was dispersed in a homomixer for 5 minutes. Then, 470 g of water at 20 DEG C and 1.2 g of sorbic acid were added and stirred for 10 minutes , Filtered through a filter paper to prepare a foam inhibitor composition (Emulsion A).

The freeness and the emulsion stability of this composition were examined, and the results as shown in the following Table 4 were obtained.

[Examples 12 to 15 and Comparative Examples 11 to 14]

Except that the organopolysiloxane compositions B to I shown in the following Table 4 were used in the same weight in place of the organopolysiloxane composition A used in Example 11 to prepare a foam inhibitor composition (emulsion B To I) were prepared, their fibrillation properties and emulsion stability were examined, and the results as shown in the following Table 4 were obtained.

[Example 16]

Except that 300 g of the organopolysiloxane composition A used in Example 11, 50 g of sorbitan monostearate / nonion SP-60R [product name of Nippon Oil Co., Ltd.], sorbitan monostearate / nonion LP-20R ), 25 g of polyoxypropylene glycol 占 올 ol D-2000 (product name, manufactured by Nippon Oil Co., Ltd.), 5 g of polyoxyethylene cetyl ether 占 Nicol BC-20 TX (trade name, manufactured by Nikko Chemicals Co., , 10 g of polyoxyethylene monostearate NIKOL MYS-IEX (trade name, manufactured by Nikko Chemicals Co., Ltd.) and 10 g of polyoxyethylene nonylphenyl ether / Nyukol 520 (trade name of Nippon Nyuka K.K.) were mixed at 80 ° C for 30 minutes To prepare a premix. Subsequently, 10 g of carboxymethylcellulose-lectin PR (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) dissolved in 270 g of water was added to the preliminary mixture adjusted to 50 DEG C, and the resulting mixture was dispersed for 5 minutes with a homomixer The foam inhibitor composition (emulsion A ') was prepared by adding 295 g of water at 20 캜 and 1 g of sorbic acid, followed by stirring for 10 minutes and filtering with a filter paper. The fibrillation resistance and emulsion stability of this composition were examined, The results are shown in Table 4 below.

[Examples 17 to 20, Comparative Examples 15 to 18]

Except that the organopolysiloxane compositions B to I shown in the following Table 4 were used in the same weight in place of the organopolysiloxane composition A used in Example 16 to prepare a foam inhibitor composition (emulsion B ' To I ') were prepared. The foliar properties and the emulsion stability thereof were examined, and the results shown in Table 4 were obtained.

[Table 4]

The present invention relates to a self-emulsified foam inhibitor composition, which, as above-mentioned (a) the general formula ^{(R 1 R 2 R 3 SiO} 1/2) 1 (R 4 R 5 SiO 2/2) m (R 6 SiO 3 _{/ 2} ) _n wherein R ¹ to R ^{6 each} represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, 1, m and n are positive numbers, 0.005? N / (1 + m + n) 1 to 60% by weight of an organopolysiloxane composition comprising 100 parts by weight of a silicone oil having a viscosity at 25 DEG C of 10 to 100,000 cS and 0.1 to 20 parts by weight of a fine silica powder, (C) 0 to 90% by weight of one or more polyoxyalkylene polymers, which is excellent in both pore and vesicle persistence, so that a small amount The addition of a large scavenging effect gives a good dilution stability, so that it has good mechanical stability under high temperature and high shear force, Because it has the advantage that also as available and useful as anti-foaming agents for high temperature dyeing, the various emulsions within a defoaming agent is added, for general paints, water-based cutting useful like. The present invention also relates to an emulsion-type foam inhibitor composition, which comprises 100 parts by weight of a silicone oil represented by the general formula (1) and having a viscosity at 25 DEG C of 10 to 100,000 cS and 0.1 to 20 parts by weight of a fine- Characterized in that it consists essentially of 1 to 90% by weight of an organopolysiloxane composition to be formed, (d) 0.1 to 50% by weight of one or more surfactants, and (e) The addition of a small amount gives a large puffing effect, and the emulsion stability is good, so that the puffiness is not lost even under severe agitation.

Claims (2)

(A) the general formula ^{(R 1 R 2 R 3 SiO} 1/2) 1 (R 4 R 5 SiO 2/2) m (R 6 SiO 3/2) n ( wherein, R ¹ to R ⁶ is C 1 -C 100 parts by weight of a silicone oil having a viscosity at 25 占 폚 of 10 to 100,000 cS represented by the following formula: 0.005? N / (1 + m + n)? 0.1) (B) 5 to 99% by weight of one or more polyoxyalkylene denatured silicone oil, (c) 1 to 60% by weight of an organopolysiloxane composition comprising one or more polyoxyalkyl Wherein the composition comprises up to 90% by weight of a polymeric polymer. (A) the general formula ^{(R 1 R 2 R 3 SiO} 1/2) 1 (R 4 R 5 SiO 2/2) m (R 6 SiO 3/2) n ( wherein, R ¹ to R ⁶ is C 1 -C 100 parts by weight of a silicone oil having a viscosity at 25 占 폚 of 10 to 100,000 cS represented by the following formula: 0.005? N / (1 + m + n)? 0.1) 1 to 90% by weight of an organopolysiloxane composition comprising 20 to 20% by weight of a surfactant, (d) 0.1 to 50% by weight of one or more surfactants, and (e) water.