JPH0824806B2 - Antifoam composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antifoam composition comprising a novel oil-in-water emulsion composition.
More specifically, the present invention has an excellent defoaming effect and has almost no thickening during product storage, and in addition to these properties, formation of soft lumps during freeze-thawing is suppressed. And an antifoam composition.

[0002]

2. Description of the Related Art Conventionally, oil-in-water emulsion defoamers are
It is widely used as a foam suppressor in various manufacturing processes including papermaking processes and wastewater treatment processes. Among these oil-in-water emulsion defoamers, those containing a higher alcohol component are known as those exhibiting excellent effects (JP-A-48-62683 and JP-A-60).
No. 156516). However, this defoaming agent has a drawback that its handleability becomes extremely poor because it thickens violently during storage and solidifies into a cream. As a method of improving such a defect, a method of adding a water-soluble polymer compound such as a homopolymer or a copolymer of acrylic acid, methacrylic acid, acrylamide, methacrylamide, etc. has been attempted (Japanese Patent Laid-Open No. 2000-242242). 60-
156516). However, although this method can suppress the solidification of the oil-in-water emulsion defoaming agent, it has a drawback that it cannot prevent thickening, which is an essential problem. Generally, in liquid products, physical properties such as viscosity are stable even after long-term storage,
Simple handling is required, such that it can be quickly taken out from the storage container and a stable discharge amount can be obtained with a simple chemical injection pump. However, as described above, the oil-in-water emulsion defoaming agent containing a higher alcohol as a component cannot impart the handling property required for general liquid products even if a water-soluble polymer compound is added. For this reason,
It has been desired to develop an oil-in-water emulsion defoaming agent that is excellent in defoaming property and does not thicken even after long-term storage. On the other hand, an oil-in-water emulsion defoaming agent containing a higher alcohol and a fatty acid ester as an oil agent may freeze when stored at a temperature of 0 ° C. or lower, and once frozen, the emulsion particles aggregate even when thawed at the time of use, It is known to produce soft lumps of about several mm. Since this soft lump does not disperse by simple stirring, there is a concern that the chemical dosing pump may be clogged and the application system may be affected. Taking the application to the papermaking process as an example, there is a possibility of causing an unfavorable situation such as deterioration of quality (spots in paper) and deterioration of operability (dirt of rolls, wires, felts, etc.).

[0003]

Under these circumstances, the present invention has an oil-in-water emulsion defoaming agent which has excellent defoaming properties and hardly thickens even after long-term storage,
Further, in addition to these characteristics, the object of the present invention is to provide an oil-in-water emulsion defoaming agent in which the formation of soft lumps during freeze-thawing is suppressed.

[0004]

It is known that in an oil-in-water emulsion containing a higher alcohol, a liquid crystal or gel is formed in a continuous phase (aqueous phase) and the viscosity is increased to stabilize the system [ Handbook of Emulsification and Dispersion Technology Applications, Science Forum (1987), page 131]. It is speculated that the oil-in-water emulsion defoaming agent containing a higher alcohol thickens during storage due to the formation of such liquid crystal or gel.

On the other hand, it is known that the type of higher alcohol and the mixing ratio of other oil phase components and higher alcohol are involved in the formation of liquid crystals and gels ["Emulsification / dispersion technology application handbook" Science Forum. Publication (198
7), page 131].

[0006] The inventors of the present invention have paid attention to such a point, and have conducted diligent research to develop an oil-in-water emulsion defoaming agent having the above-mentioned preferable properties. As a result, a higher alcohol having a specific composition is obtained. An oil-in-water emulsion composition containing a specific fatty acid ester in a predetermined ratio and further containing a nonionic or anionic surfactant has excellent defoaming properties, and even when stored for a long period of time, almost thickens. It was found that, in addition to the above characteristics, the formation of soft lumps during freeze-thawing is suppressed by adding a water-soluble solvent in a specific ratio to the composition.
Based on this finding, the present invention has been completed.

That is, the present invention is (A) having 16 to 16 carbon atoms.
24 alkanols, (B) monovalent to trivalent carbon atoms 1
To a fatty acid ester having a melting point of 50 ° C. or lower and composed of an alcohol having 18 to 18 carbon atoms and a fatty acid having 12 to 22 carbon atoms and (C) a nonionic and / or anionic surfactant,
The total amount of component (A), component (B) and component (C) is 5 to
An oil-in-water emulsion composition containing 50% by weight, wherein the component (A) has 16 carbon atoms.
And total amount of alkanols of 18 and 18 and carbon numbers of 20 and 22 and 2
The weight ratio with respect to the total amount of alkanol of 4 is 10:90 to 50:50, and the weight ratio between the component (A) and the component (B) is 35:65 to 80:20. The defoamer composition and a water-soluble solvent as the component (D) in the composition are 4.0% by weight based on the total weight of the composition.
The present invention provides an antifoam composition containing the above proportions.

The present invention will be described in detail below.

The alkanol as the component (A) in the composition of the present invention has 16 to 24 carbon atoms, preferably 18 to 24 carbon atoms.
A mixture of 22 is used. If the number of carbon atoms deviates from the range of 16 to 24, the emulsion obtained will be inferior in defoaming property and the object of the present invention will not be sufficiently achieved. Regarding the composition of the mixture, the ratio of the total amount of alkanols having 16 and 18 carbon atoms and the total amount of alkanols having 20, 22 and 24 carbon atoms is 10:90 to 5 by weight.
It should be in the range of 0:50. If the ratio is out of the above range, the viscosity increases during storage, and the object of the present invention cannot be fully achieved. It should be noted that it is not always the same temperature that the viscosity increases during storage, and generally the temperature range where the viscosity tends to increase differs depending on the alkanol composition, but it is considered to be the general storage temperature range for oil-in-water emulsion defoamers. It must be stable in the entire temperature range above 40 ° C and above 40 ° C. In order to satisfy such a condition, the weight ratio is 10:90 to 50:50, preferably 20:80.
To 40:60.

As the alkanol as the component (A),
For example, palmityl alcohol, stearyl alcohol,
Eicosyl alcohol, behenyl alcohol, etc. are mentioned, and they are appropriately selected and used in combination so as to satisfy the above conditions.

The fatty acid ester as the component (B) in the composition of the present invention comprises a monohydric or trihydric alcohol and a fatty acid having 12 to 22 carbon atoms and has a melting point of 50.
Those below ℃ are used. With a fatty acid ester having a melting point of higher than 50 ° C., even if it is used in combination with the alkanol as the component (A), the viscosity tends to increase during storage, and the object of the present invention cannot be achieved.

The fatty acid ester is not particularly limited as long as it is composed of a monohydric or trihydric alcohol and a fatty acid having 12 to 22 carbon atoms, and examples thereof include animal and vegetable oils and fats and hydrogenated oils thereof. Is preferably used. Specific examples of the oils and fats of the animals and plants and hardened oils thereof include animal fats and oils such as beef tallow, pork oil, sardine oil and whale oil, soybean oil, corn oil, coconut oil, linseed oil, rapeseed oil, cottonseed oil, castor oil, kiri. Examples thereof include vegetable oils and fats such as oils, and hydrogenated oils obtained by subjecting these to a hardening treatment by hydrogenation. You may use 1 type of these fatty acid ester,
You may use it in combination of 2 or more type.

The content ratio of the alkanol as the component (A) and the fatty acid ester as the component (B) in the composition of the present invention is 35:65 to 80:20, preferably 40:60 to 70:30 by weight. Must be in range. If this ratio is outside the above range, the emulsion composition obtained tends to thicken during storage, and the object of the present invention cannot be fully achieved.

In the composition of the present invention, a nonionic and / or anionic surfactant is used as an emulsifying agent for the component (C). Examples of the nonionic surfactant include polyoxyethylene alkyl ether, single chain length polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene polyether. Oxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil and hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, Fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol Fatty acid esters, and sucrose fatty acid esters.

On the other hand, as the anionic surfactant, fatty acid soap, alkyl ether carboxylate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, formalin polycondensate of naphthalene sulfonate,
Dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acylmethyl taurine, sulfated oil, higher alcohol sulfate, alkyl ether sulfate, secondary alcohol ethoxy sulfate, polyoxyethylene alkyl Examples thereof include phenyl ether sulfate, monoglycerate, fatty acid alkylol amide sulfate ester salt, alkyl ether phosphate ester salt, and alkyl phosphate ester salt.

One of these emulsifiers may be used, or 2
Although more than one kind may be used in combination, preferred emulsifiers include nonionic surfactants having an HLB of 13 to 17. It is desirable to use these emulsifiers in an amount of 1 to 15% by weight, preferably 2 to 5% by weight, based on the oil agent. If the amount is less than 1% by weight, it is difficult to obtain an emulsion having an appropriate particle size, and if it exceeds 15% by weight, the effect is not improved for the amount, and the obtained emulsion composition is likely to foam. At the same time, the viscosity may easily increase during storage.

In the composition of the present invention, the total content of the components (A), (B) and (C) is selected in the range of 5 to 50% by weight, preferably 15 to 40% by weight.
If this amount is less than 5% by weight, the defoaming effect is not sufficiently exerted, the object of the present invention cannot be sufficiently achieved, and 50% by weight.
If it exceeds, the viscosity of the obtained emulsion composition increases, and it tends to be difficult to use.

In the oil-in-water emulsion composition of the present invention, an alkanol and a fatty acid ester are used as an oil agent, but if desired, another oil agent, for example, a boiling point of 200.
Mineral oil having a temperature of 0 ° C. or higher can be used in a ratio of 20% by weight or less based on the total amount of the oil agent.

The composition of the present invention optionally contains a water-soluble solvent as the component (D) in an amount of 4% by weight or more based on the total weight of the composition in order to suppress the formation of soft lumps during freeze-thawing.
Preferably, it can be contained in a ratio of 5 to 20% by weight. If the content of the water-soluble solvent is less than 4% by weight, the effect of suppressing the formation of soft lumps during freeze-thawing cannot be sufficiently exhibited.

Examples of the water-soluble solvent include glycols such as ethylene glycol and propylene glycol, and glycerin. These water-soluble solvents are 1
One kind may be used, or two or more kinds may be used in combination.

If desired, the composition of the present invention may contain a known water-soluble preservative for the purpose of preventing spoilage during long-term storage.

The method for producing the oil-in-water emulsion composition of the present invention is not particularly limited, and a method conventionally used in the production of oil-in-water emulsions can be used. At this time, as long as the object of the present invention is not impaired,
Known emulsion stabilizers can be added if desired. Examples of this emulsion stabilizer include water-soluble polymer compounds composed of homopolymers or copolymers of monomers such as acrylic acid, methacrylic acid, acrylamide, and methacrylamide.

The average particle size of oil fine particles in the oil-in-water emulsion is preferably 2 to 15 μm, more preferably 4 to 8 μm.

The defoaming agent composition comprising the oil-in-water emulsion of the present invention is foamed in various production processes including the paper manufacturing industry such as papermaking and coating, and various wastewater treatment processes such as activated sludge and discharge. Can be applied to all the processes in which the above problem becomes a problem, but it is particularly preferably used as a foaming inhibitor in a papermaking process or a wastewater treatment process such as activated sludge.

The defoaming agent composition comprising the oil-in-water emulsion of the present invention is usually 0.1 to 1,000 mg / treatment liquid.
It is used in the range of 1 liter, preferably 1 to 100 mg / liter.

[0026]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Industrial-use behenyl alcohol (containing alkanol having 22 carbon atoms as a main component, having 18 carbon atoms, 20 carbon atoms and 2 carbon atoms)
14.0 parts by weight, industrial stearyl alcohol (mainly containing an alkanol having 18 carbon atoms and also containing an alkanol having 16 carbon atoms) 1.
6 parts by weight, hydrogenated beef tallow oil (mp 45 ° C.) 10.4 parts by weight and polyoxyethylene nonylphenyl ether (HLB 15.5) 0.8 part by weight as an emulsifier were mixed and melted, and this melt was heated to 70 ° C. At turbine blades, the peripheral speed is 5.
While stirring at 2 m / s, 73.2 parts by weight of hot water at 70 ° C. was added for phase inversion emulsification. Next, sodium polyacrylate having a molecular weight of about 3,000,000 was added to the emulsion composition in an amount of 0.03% by weight, and then 1
The mixture was gradually cooled from 70 ° C. to about 30 ° C. over 8 hours to prepare an antifoam composition composed of an oil-in-water emulsion having an average particle size of 4.5 to 8 μm and a viscosity of about 100 centipoise. The composition of alkanol in this composition is shown in Table 1. The weight ratio of alkanol / fatty acid ester is 6/4.

Next, the change in viscosity with time and the defoaming effect of the defoaming agent composition thus prepared during storage were determined by the following methods. The results are shown in Tables 2 and 3, respectively.

(1) Change in viscosity over time during storage The antifoam composition was allowed to stand in a constant temperature bath at 5 ° C., 20 ° C., 30 ° C. and 40 ° C., and the viscosity was measured over time for 30 days. Viscosity was measured using a B type viscometer under the conditions of 30 rpm and 2 minutes.
It was carried out at a temperature of 25 ° C.

(2) Defoaming Effect Using 600 ml of newsprint paper white water, 4 ppm of the defoaming agent composition was added by the apparatus shown in FIG. 1, and the defoaming effect was examined at 30 ° C. 600 ml of test solution 2 in graduated cylinder 1
Then, the test solution 2 was circulated through the flow meter 4 by the circulation pump 3 and the foaming amount was measured to examine the defoaming effect.

Examples 2 to 4, Comparative Examples 1 to 3 The relationship between the composition of the alkanol and the performance of the antifoam composition was investigated.

An antifoam composition comprising an oil-in-water emulsion was prepared in the same manner as in Example 1 except that the type and amount of alkanol shown in Table 1 were used as the industrial alkanol. The change in viscosity with time and the defoaming effect during storage were determined. The results are shown in Tables 2 and 3, respectively, and the composition of the alkanol is shown in Table 1. The industrial eicosyl alcohol contains an alkanol having 20 carbon atoms as a main component and also contains an alkanol having 18 carbon atoms, 22 carbon atoms and 24 carbon atoms.

[0033]

[Table 1]

[0034]

[Table 2] (Note) The product stored in Comparative Example 1 at 30 ° C. was stored in Comparative Example 2 after 10 days.
The product stored at 20 ° C. had a viscosity of 4,000 cp or more after 23 days, and the product stored at 5 ° C. in Comparative Example 3 had a viscosity of 4,000 cp or more after 15 days.

[0035]

[Table 3]

As can be seen from these tables, in the composition of the alkanol, when the weight ratio of C ₁₈ / (C ₂₀ + C ₂₂ + C ₂₄ ) is 5/95 or less and 60/40, the storage temperature of 5-40 ° C. The viscosity is significantly increased and the viscosity is 4,000 cp
As described above, the paste was formed with extremely low fluidity, but when the weight ratio was in the range of 14/86 to 42/58, the increase in viscosity was suppressed at any storage temperature, and the viscosity had no problem in handling in practical use. became.

The composition of alkanol did not have a great influence on the defoaming effect, and good results were obtained in both the examples and comparative examples.

Examples 5 to 8 and Comparative Examples 4 to 6 The relationship between the type of fatty acid ester and the performance of the antifoam composition was investigated.

In Example 4, an antifoam composition comprising an oil-in-water emulsion was prepared in the same manner as in Example 4, except that the fatty acid ester shown in Table 4 was used, and the composition was stored for storage. The viscosity change and the defoaming effect were determined. The results are shown in Table 5 and Table 6, respectively.

[0040]

[Table 4]

[0041]

[Table 5] (Note) The viscosity of the product stored at 40 ° C. in Comparative Example 4 after 1 day and the viscosity of the product stored at 40 ° C. in Comparative Example 5 after 15 days becomes 4000 cp or more.

[0042]

[Table 6]

As can be seen from these tables, the viscosity during storage is not affected by the number of hydroxyl groups of the alcohol constituting the fatty acid ester, but is greatly affected by the melting point of the ester. That is, when the melting point of the fatty acid ester is 51 ° C. or higher, it tends to be thickened to form a paste, but when the melting point is 48 ° C. or lower, the thickening is significantly suppressed, and the viscosity has practically no problem in handling.

On the other hand, the defoaming effect is good regardless of the number of hydroxyl groups of the alcohol constituting the fatty acid ester and the melting point of the fatty acid ester.

Examples 9, 10 and Comparative Example 7 The relationship between the alkanol / fatty acid ester weight ratio and the performance of the antifoam composition was investigated.

Using the alkanols and fatty acid esters in the types and amounts shown in Table 7, the composition of the alkanol was determined as in Example 4.
In the same manner as in Example 4, an antifoam composition consisting of an oil-in-water emulsion was prepared, and the change in viscosity with time during storage and the defoaming effect were determined. The results are shown in Tables 8 and 9, respectively.

However, in Example 10, HL was used as an emulsifier.
B17 polyoxyethylene nonylphenyl ether was used.

[0048]

[Table 7]

[0049]

[Table 8]

[0050]

[Table 9]

As can be seen from these tables, when the weight ratio of alkanol / fatty acid ester was 30/70, the viscosity was considerably increased, and although it had fluidity, it had a problematic workability, but the weight ratio was At 40/60 to 80/20, the thickening was significantly suppressed, and the viscosity became practically no problem in handling.

On the other hand, with respect to the defoaming effect, when the weight ratio of alkanol / fatty acid ester is 30/70, the effect tends to be slightly decreased, but when it is 40/60 or more, a good effect is exhibited.

Example 11 9.4 parts by weight of industrial behenyl alcohol, 6.2 parts by weight of industrial stearyl alcohol, hydrogenated tallow oil (mp45)
C.) 10.4 parts by weight, polyoxyethylene nonylphenyl ether (HLB15.5) 0.8 parts by weight, ethylene glycol 5 parts by weight and water 68.2 parts by weight in the same manner as in Example 1 using an oil-in-water type. An antifoam composition consisting of an emulsion was prepared.

Next, this composition was left to stand in a freezer at -25 ° C. overnight and then left to stand at room temperature for one day and thawed. No lumps were formed, and when observed under a microscope, emulsion particles were homogeneously dispersed. Was. Moreover, no change in viscosity was observed after thawing.

For comparison, a similar test was conducted on the composition obtained in Example 4 to find that it was 1-2 mm.
Many soft lumps were formed. When observed under a microscope, it was confirmed that the emulsion particles were aggregated.

Furthermore, when the defoaming effect of the composition of this example after thawing was examined, the same results as the composition of Example 4 (before freezing) were obtained as shown in the tenth display.

[0057]

[Table 10]

[0058]

INDUSTRIAL APPLICABILITY According to the present invention, a defoaming agent composition comprising an oil-in-water emulsion which is excellent in defoaming property, hardly thickens even after long-term storage, and is excellent in stability over time is obtained. To be Furthermore, in addition to the above characteristics, an antifoam composition comprising an oil-in-water emulsion in which the formation of soft lumps during freeze-thawing is suppressed can also be obtained.

[0059]

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus used to evaluate the defoaming effect.

[0060]

[Explanation of symbols]

 1 1 liter graduated cylinder 2 600 ml test solution 3 Circulation pump 4 Flow meter 5 Cock

Claims (2)

[Claims] 1. An (A) alkanol having 16 to 24 carbon atoms,
(B) a melting point composed of a monovalent to trivalent alcohol having 1 to 18 carbon atoms and a fatty acid having 12 to 22 carbon atoms and having a melting point of 50.
A ratio such that the total amount of (A) component, (B) component and (C) component is 5 to 50% by weight of the fatty acid ester and (C) nonionic and / or anionic surfactant having a temperature of ℃ or less. An oil-in-water emulsion composition containing in,
The weight ratio of the total amount of alkanols having 16 and 18 carbon atoms to the total amount of alkanols having 20, 22 and 24 carbon atoms in component (A) is from 10:90 to 50:50, and A defoaming agent composition characterized in that the weight ratio with the component B) is 35:65 to 80:20. 2. A defoamer composition comprising the defoamer composition according to claim 1 and further containing (D) a water-soluble solvent in a proportion of 4% by weight or more based on the total weight of the composition.