JP2016013507A - Oil-in-water type emulsion defoaming agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oil-in-water type emulsion defoaming agent composition which is a non-silicone compound, which has an excellent defoaming effect and which is almost not thickened when preserved for a long term.SOLUTION: An oil-in-water type emulsion defoaming agent composition includes: (A) an oil phase component containing a 12-30C higher aliphatic alcohol of 5-50 mass%; (B) a nonionic surfactant having a sterol skeleton and 12-19 of HLB of 0.05-5 mass%; and (C) water as the balance. The nonionic surfactant (B) is a polyoxyethylene lanolin alcohol and/or a polyoxyethylene phytosterol. The content of the 12-30C higher aliphatic alcohol in the oil phase component (A) is 50-100 mass%.

Description

  The present invention relates to an antifoaming agent composition, and more particularly to an oil-in-water emulsion antifoaming agent composition having an excellent antifoaming effect and hardly thickening during storage.

Conventionally, oil-in-water emulsion defoamers have been widely used as foam inhibitors in various manufacturing processes including papermaking processes and wastewater treatment processes.
Among oil-in-water emulsion antifoaming agents, those containing a higher alcohol component are known as relatively inexpensive and exhibiting excellent effects (for example, see Patent Document 1). However, an oil-in-water emulsion antifoaming agent containing a higher alcohol has the disadvantage that it thickens vigorously during storage and the handling properties become extremely poor.

As a method for improving such a defect, for example, a method of adding a nonionic surfactant made of an ethylene oxide adduct of nonylphenol has been attempted (for example, see Patent Document 2).
However, this method can prevent the oil-in-water emulsion antifoaming agent from solidifying, but cannot prevent thickening, which is an essential problem.

  Further, a method of adding a nonionic surfactant composed of an ethylene oxide adduct of a secondary alcohol and a nonionic surfactant composed of an alkylene oxide adduct of a primary alcohol having a branched alkyl group has been proposed (for example, However, depending on the composition and the production method, thickening may occur, which is not sufficient.

On the other hand, as another oil-in-water emulsion antifoaming agent, a silicone-based one using dimethylpolysiloxane is known.
Such silicone-based antifoaming agents generally exhibit good foam breaking properties, but dimethylpolysiloxane and the like are poorly soluble in water, so aqueous systems such as water-based paints, latexes, water-based inks, dyes, and sizing agents. When used for applications, repelling, uneven dyeing, fish eyes, oil spots, etc. are likely to occur (see, for example, Patent Document 5).

  In addition, in the above applications, it is important to clean various processing machines with water. However, the silicone antifoaming agent is not easily contaminated with water due to the above-mentioned poor solubility. Removal may be difficult, and a desired cleanliness may not be achieved (see, for example, Patent Document 6).

  Furthermore, although such a silicone-based oil-in-water emulsion antifoaming agent is excellent in its own foam breaking property, it cannot be said that the dispersibility in water is sufficient and the defoaming property may not be sufficiently exhibited. It is also known that when used in a suspension / emulsion polymerization process of copolymer latex containing polystyrene, polyvinyl chloride, polybutadiene, etc., the transparency, gloss, printability, and adhesion of the resulting resin are impaired (for example, And Patent Document 7).

JP-A 48-62683 JP 60-156516 A Japanese Patent No. 3573199 Japanese Patent No. 4595492 JP 2005-125128 A JP2013-202518A JP 2001-212403 A

  Generally, in liquid products, physical properties such as viscosity are stable even after long-term storage, and can be quickly removed from the storage container. Handling is required.

  However, an oil-in-water emulsion defoamer composition containing a higher alcohol as an oil phase component can be converted into a liquid product when manufactured by a general method even when various nonionic surfactants are added as described above. It was not enough to achieve the required handling. Therefore, it has been desired to develop an oil-in-water emulsion antifoaming composition that is excellent in antifoaming properties that can be prepared by a general production method and does not thicken even when stored for a long period of time.

  On the other hand, various problems have been reported for silicone-based oil-in-water emulsion antifoaming agents as described above, and they have not been sufficient as antifoaming agents that are liquid products.

  The present invention has been made in view of such problems of the prior art. The object of the present invention is to have an excellent antifoaming effect in a non-silicone system and to increase viscosity even when stored for a long period of time. An object of the present invention is to provide an oil-in-water emulsion antifoaming composition that does not occur.

  As a result of intensive studies to solve the above problems, the present inventors obtained by emulsifying an oil phase component containing a higher aliphatic alcohol with a predetermined nonionic surfactant obtained by adding an alkylene oxide to a sterol. The oil-in-water emulsion antifoaming agent does not cause thickening or separation due to temperature changes, and does not cause separation over a long period of time, while maintaining excellent properties and excellent defoaming properties The inventors have found that even when stored for a long period of time, the viscosity is hardly increased and the defoaming performance is not lowered, and the present invention has been completed.

That is, the oil-in-water emulsion antifoaming agent of the present invention comprises (A) an oil phase component containing 5 to 50% by mass of a higher aliphatic alcohol having 12 to 30 carbon atoms,
(B) 0.05 to 5% by mass of a nonionic surfactant having an HLB having a sterol skeleton of 12 to 19, and
(C) Water as a remaining amount is contained.

  According to the present invention, an oil phase component containing a higher aliphatic alcohol is emulsified with a predetermined nonionic surfactant obtained by adding an alkylene oxide to a sterol, so that it has an excellent antifoaming effect in a non-silicone system, It is possible to provide an oil-in-water emulsion antifoaming composition that hardly thickens even when stored for a long period of time.

It is the schematic which shows the apparatus used for evaluation of a defoaming effect.

Hereinafter, the oil-in-water emulsion antifoaming composition of the present invention will be described.
As described above, the antifoam composition of the present invention comprises (A) an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms, and (B) a nonionic property having 12 to 19 HLB having a sterol skeleton. It is an oil-in-water emulsion antifoamer composition containing a surfactant and (C) water as a residue.

In the composition of the present invention, the content of the oil phase component (A) containing a higher aliphatic alcohol having 12 to 30 carbon atoms is 5 to 50% by mass, but preferably 15 to 40% by mass.
If the content of the oil phase component (A) is less than 5% by mass, the defoaming effect may not be sufficiently exhibited. Moreover, when content of an oil phase component (A) exceeds 50 mass%, there exists a possibility that the viscosity of the oil-in-water type emulsion antifoamer composition obtained may become high too much, and handleability may fall.

Moreover, in this invention composition, it is preferable that the quantity of a C12-C30 higher aliphatic alcohol in an oil phase component (A) is 50-100 mass%.
If the amount of the higher aliphatic alcohol in component (A) is less than 50% by mass, the defoaming effect may be reduced.

In the composition of the present invention, the higher aliphatic alcohol has 12 to 30 carbon atoms, preferably 16 to 24, and particularly preferably 16 to 22.
Such higher aliphatic alcohols can be used alone or as a mixture of two or more thereof. When the number of carbon atoms of the higher aliphatic alcohol is less than 12, there is a possibility that the defoaming effect of the resulting oil-in-water emulsion defoaming agent composition is lowered, and when it exceeds 30, there is a possibility that the emulsification cannot be performed sufficiently.

Examples of the higher aliphatic alcohol having 12 to 30 carbon atoms include myristyl alcohol, palmityl alcohol, stearyl alcohol, eicosyl alcohol, behenyl alcohol, oleyl alcohol, and cetostearyl alcohol.
As higher aliphatic alcohols, alcohols derived from natural animal and vegetable oils and fats can be used, synthetic alcohols can be used, and residues of synthetic alcohols can also be used.

In the composition of the present invention, examples of the components other than the higher aliphatic alcohol in the oil phase component (A) include, for example, esters of 1 to 22 carbon atoms with 1 to 3 carbons and 12 to 22 fatty acids and paraffins. Examples thereof include waxes and mineral oils, and triglycerides can be preferably used.
The amount of components other than the higher aliphatic alcohol in the oil phase component is preferably 0 to 50% by mass.
In the composition of the present invention, the melting point of the oil phase component is preferably 45 ° C. or higher, and if it is lower than 45 ° C., the defoaming effect may be lowered.

On the other hand, the composition of the present invention contains a nonionic surfactant (B) having an HLB having a sterol skeleton of 12 to 19 in a proportion of 0.05 to 5% by mass, but 0.1 to 3% by mass. Is preferred.
If the content of the nonionic surfactant (B) is less than 0.05% by mass, it may be difficult to obtain an emulsion having a fine particle size. If the content exceeds 5% by mass, the resulting oil-in-water solution is obtained. The type emulsion defoamer composition tends to foam and tends to increase in viscosity over time.

  The nonionic surfactant (B) has an HLB of 12 to 19, but is preferably 15 to 18. When the HLB of the nonionic surfactant is less than 12 or exceeds 19, the emulsifying power may be reduced and an appropriate emulsion product may not be obtained.

Examples of the nonionic surfactant (B) include polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxyethylene cholesteryl ether, polyoxyethylene phytosterol, and polyoxyethylene phytostanol.
The nonionic surfactant (B) can be produced by adding ethylene oxide to alcohol having a sterol skeleton, for example, phytosterol widely distributed in plants, cholesterol and lanolin alcohol widely distributed in animals. it can.

  In this invention, the nonionic surfactant (B) can be used individually by 1 type, and can also be used in combination of 2 or more type. In the present invention, polyoxyethylene lanolin alcohol, polyoxyethylene phytosterol and a mixture thereof can be suitably used.

In the composition of the present invention, the content of the nonionic surfactant (B) is preferably 0.5 to 10 parts by weight, and 0.5 to 5 parts by weight per 100 parts by weight of the oil phase component (A). More preferred.
If the nonionic surfactant (B) is less than 0.5 parts by weight per 100 parts by weight of the oil phase component (A), it may be difficult to obtain an emulsion having an appropriate particle size, and if it exceeds 10 parts by weight. The improvement of the effect is not recognized for the added amount of the nonionic surfactant, but rather the resulting emulsion composition tends to foam and tends to thicken during storage.

In the present invention, particularly when preparing an emulsion antifoaming agent, other anionic surfactants and nonionic surfactants can be used in combination as long as the effects of the component (B) are not impaired.
In this case, examples of the anionic surfactant include monoalkylsulfosuccinic acid ester salts, dialkylsulfosuccinic acid ester salts, alkylbenzene sulfonates, alkyl sulfates, and polyoxyethylene alkyl ether sulfates. Examples of the activator include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene alkyl ether.

There is no restriction | limiting in particular in the manufacturing method of the antifoamer composition of this invention, The well-known method conventionally used in manufacture of an oil-in-water emulsion can be used.
For example, an oil phase component (A) containing a higher aliphatic alcohol having 12 to 30 carbon atoms and the above nonionic surfactant (B) are mixed and heated and melted, and hot water is added while stirring. The oil-in-water emulsion defoamer composition can be obtained by phase emulsification.
When emulsifying, a high-efficiency emulsifying disperser such as a commercially available disper mixer, homomixer, or milder, and a high-pressure emulsifier can be used.

The antifoaming composition of the present invention can contain 0.01 to 2% by mass of a water-soluble thickener as necessary. Water-soluble thickeners include microbial polysaccharides such as xanthan gum, rhamzan gum and welan gum, and vegetable polysaccharides such as guar gum, and poly (meth) acrylic acid, poly (meth) acrylic acid- (meth) acrylamide and carboxyvinyl polymer. Synthetic polymer thickeners can be used, and one or more of these can be selected and used.
Moreover, a polyhydric alcohol, an antiseptic | preservative, etc. can be added in the range which does not impair the performance of this antifoamer as needed.

  The antifoam composition of the present invention is applied to all processes in which foaming is a problem, such as various production processes including the paper industry such as papermaking and coating, and various wastewater treatment processes such as activated sludge and discharge. However, in particular, it can be suitably used as a foaming inhibitor in a papermaking process or a wastewater treatment process such as activated sludge.

Although there is no restriction | limiting in particular in the addition amount (dose) of the antifoamer composition of this invention, It is preferable to add normally 0.1-1,000 mg / liter with respect to a process liquid, and adding 1-100 mg / liter. Is more preferable.
The antifoam composition of the present invention has an excellent defoaming effect and hardly thickens during product storage, so it can be used stably without special consideration for quality deterioration over time. can do.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
In the following Examples and Comparative Examples, the change in viscosity with time and the antifoaming effect of the antifoaming agent composition were measured by the following methods.

(1) Viscosity change over time After the antifoam composition was allowed to stand in a thermostatic bath at room temperature, 5 ° C. and 40 ° C. for 30 days, using a B-type viscometer, spindle rotation speed 60 rpm, 1 minute Measure the viscosity at Products stored at room temperature were adjusted to 20 ° C., and those stored in a constant temperature bath at 5 ° C. and 40 ° C. were taken out of the constant temperature bath and immediately measured for viscosity.

(2) Defoaming effect FIG. 1 is a schematic view of an apparatus used for evaluating the defoaming effect.
1000 mL of foam test water having the following composition to which 2 mg of the antifoam composition of each example was added was placed in a transparent acrylic cylindrical container 1 with an inner diameter of 90 mm and a height of 700 mm, and passed through a flow meter 3 by a circulation pump 2. It is circulated at a flow rate of 1200 ml / min and dropped into the cylindrical container 1 from a height of 500 mm from the water surface in the cylindrical container 1. The test is performed at 40 ° C., and after the start of circulation, the amount of foaming (height of the foam) in the graduated transparent acrylic cylindrical container is read every minute until 5 minutes later.

[Foaming test water composition]
Styrene acrylamide sizing agent [Modern Chemical Industry Co., Ltd. NS-18S]: 0.2% by mass
Polyacrylamide paper strength enhancer [Arakawa Chemical Industry Co., Ltd. POLYSTORON 117]: 0.08% by mass
10% aqueous aluminum sulfate solution: 0.02% by mass
Tap water: 99.7% by mass

(Example 1)
(B) Ethanol oxide 40 mol adduct of lanolin alcohol as a nonionic surfactant as a component [Nikko Chemicals Co., Ltd., NIKKOL BWA-40, HLB17.0]
As the higher aliphatic alcohol, cetostearyl alcohol [NOF Corporation, NAA-48] was used.
30 parts by weight of the above higher aliphatic alcohol and 0.5 part by weight of a nonionic surfactant are mixed and heated to melt, and the melt is stirred at 70 ° C. with a disper mixer at a peripheral speed of 4.4 m / s. Then, 64.5 parts by weight of hot water at 70 ° C. was added to carry out phase inversion emulsification.
Next, after adding 5 parts by weight of a 1% by weight aqueous solution of xanthan gum [Sansho Co., Ltd., Kelzan], the mixture was cooled for about 2 hours to give an oil-in-water emulsion defoamer composition having a viscosity of 385 mPa · s at 20 ° C. Obtained.

  The viscosity after 30 days was 844 mPa · s after standing at 5 ° C., 848 mPa · s after standing at room temperature, and 681 mPa · s after standing at 40 ° C. The amount of foaming was 22 mm after 1 minute, 23 mm after 2 minutes, 23 mm after 3 minutes, 24 mm after 4 minutes, and 22 mm after 5 minutes.

(Example 2)
As the nonionic surfactant of component (B), the same operation as in Example 1 was repeated except that 30 moles of an adduct of phytosterol in ethylene oxide [Nikko Chemicals, NIKKOL BPS-30, HLB18.0] was used. An antifoam composition of this example was prepared. The viscosity at 20 ° C. was 345 mPa · s.
The viscosity after 30 days was 905 mPa · s after standing at 5 ° C., 1056 mPa · s after standing at room temperature, and 495 mPa · s after standing at 40 ° C. The amount of foaming was 22 mm after 1 minute, 24 mm after 2 minutes, 22 mm after 3 minutes, 25 mm after 4 minutes, and 22 mm after 5 minutes.

(Example 3)
As a nonionic surfactant for component (B), an ethylene oxide 40 mol adduct of lanolin alcohol [Nikko Chemicals, NIKKOL BWA-40, HLB 17.0] and an ethylene oxide 30 mol adduct of phytosterol [Nikko Chemicals, NIKKOL, Inc.] BPS-30, HLB18.0] was used.
18 parts by weight of cetostearyl alcohol [NOA Corp. NAA-48] as the higher aliphatic alcohol, and 7 parts by weight of triglyceride [NOF Corporation, beef tallow 45 ° hardened oil HO] as components other than the higher aliphatic alcohol, In addition, 0.15 parts by weight of the above-mentioned nonionic surfactant lanolin alcohol ethylene oxide 40 mole adduct and 0.1 part by weight of phytosterol ethylene oxide 30 mole adduct were mixed and heated to melt, and then the melt was heated to 70 ° C. While stirring at a peripheral speed of 4.4 m / s with a disper mixer, 69.75 parts by weight of hot water at 70 ° C. was added to carry out phase inversion emulsification.
Next, 5 parts by weight of a 1% by weight aqueous solution of xanthan gum [Sansho Co., Ltd., Kelzan] was added, and then cooled for about 2 hours, and the oil-in-water emulsion antifoaming agent of this example having a viscosity of 278 mPa · s at 20 ° C. A composition was obtained.

  The viscosity after 30 days was 837 mPa · s after standing at 5 ° C, 485 mPa · s after standing at room temperature, and 504 mPa · s after standing at 40 ° C. The amount of foaming was 22 mm after 1 minute, 24 mm after 2 minutes, 25 mm after 3 minutes, 26 mm after 4 minutes, and 26 mm after 5 minutes.

Example 4
As a nonionic surfactant of the component (B), a 40-mol adduct of lanolin alcohol with ethylene oxide [Nikko Chemicals, NIKKOL BWA-40, HLB 17.0] was used.
As higher aliphatic alcohols, 33 parts by weight of cetostearyl alcohol [NOF Corporation, NAA-48], 2 parts by weight of behenyl alcohol [NOF Corporation, NAA-422], and the above nonionic surfactant 0.4 After mixing parts by weight and heating and melting, while stirring this melt at 70 ° C. with a disper mixer at a peripheral speed of 4.4 m / s, 59.6 parts by weight of hot water at 70 ° C. was added to perform phase inversion. Emulsification was performed. Next, 5 parts by weight of a 1% by weight aqueous solution of xanthan gum [Sansho Co., Ltd., Kelzan] was added and mixed uniformly, and then treated with a high-efficiency emulsifying disperser (Pacific Kiko Co., Ltd., Milder MDN303V). This treatment liquid was cooled while being stirred with a disper mixer to obtain an oil-in-water emulsion defoamer composition of this example having a viscosity of 223 mPa · s at 20 ° C.

  The viscosity after 30 days was 428 mPa · s after standing at 5 ° C, 799 mPa · s after standing at room temperature, and 434 mPa · s after standing at 40 ° C. The amount of foaming was 22 mm after 1 minute, 25 mm after 2 minutes, 22 mm after 3 minutes, 25 mm after 4 minutes, and 25 mm after 5 minutes.

(Comparative Example 1)
(B) The same operation as in Example 1 except that polyoxyethylene sorbitan monooleate [Daiichi Kogyo Seiyaku Co., Ltd., Sorgen TW-80, HLB 15.0] was used instead of the nonionic surfactant as the component. Was repeated to prepare an antifoam composition of this example. The viscosity at 20 ° C. was 439 mPa · s.
The viscosity after 30 days was 522 mPa · s after standing at 5 ° C., and 952 mPa.s after standing at room temperature. It was 1560 mPa * s which left still at 40 degreeC. The amount of foaming was 24 mm after 1 minute, 30 mm after 2 minutes, 30 mm after 3 minutes, 30 mm after 4 minutes, and 30 mm after 5 minutes.

(Comparative Example 2)
The same operation as in Example 1 except that polyoxyethylene alkyl ether [Kao Corporation, Emulgen 1135S-70, HLB 17.9, concentration 70% by mass] was used instead of the nonionic surfactant (B). Was repeated to prepare an antifoam composition of this example. The viscosity at 20 ° C. was 793 mPa · s.
The viscosity after 30 days was 3430 mPa · s after standing at 5 ° C., 8030 mPa · s after standing at room temperature, and 3640 mPa · s after standing at 40 ° C. The amount of foaming was 25 mm after 1 minute, 30 mm after 2 minutes, 30 mm after 3 minutes, 30 mm after 4 minutes, and 32 mm after 5 minutes.

(Comparative Example 3)
The antifoaming effect was tested without adding the antifoam composition to the foaming test water.
The amount of foaming was 33 mm after 1 minute, 35 mm after 2 minutes, 35 mm after 3 minutes, 35 mm after 4 minutes, and 35 mm after 5 minutes.

  Table 1 shows the results of changes in viscosity over time in Examples 1 to 4 and Comparative Examples 1 and 2, and Table 2 shows the results of defoaming effect tests in Examples 1 to 4 and Comparative Examples 1 to 3.

  As shown in Table 1, nonionic surfactant obtained by adding 40 mol of ethylene oxide to lanolin alcohol [Nikko Chemicals, NIKKOL BWA-40, HLB17.0] and / or nonionic surfactant obtained by adding 30 mol of ethylene oxide to phytosterol. The antifoaming compositions of Examples 1 to 4 using the agent [Nikko Chemicals Co., Ltd., NIKKOL BPS-30, HLB18.0] as an emulsifier have significantly increased viscosity at each standing temperature, and after 30 days. Viscosity and fluidity that are practically unproblematic to handle were exhibited.

On the other hand, the antifoamer composition of Comparative Example 1 using polyoxyethylene sorbitan monooleate [Daiichi Kogyo Seiyaku Co., Ltd., Sorgen TW-80, HLB 15.0] as an emulsifier was 40 ° C. after 30 days. Those that were allowed to stand increased in viscosity to about 4 times the viscosity immediately after preparation, and polyoxyethylene alkyl ether [Kao Corporation, Emulgen 1135S-70, HLB 17.9, concentration 70 mass%] was used as an emulsifier. The antifoam composition of Comparative Example 2 had a viscosity of 3,000 mPa · s or higher under any condition after 30 days, and became a cream with no fluidity.
Moreover, as shown in Table 2, the antifoamer composition of Examples 1-4 exhibits sufficient defoaming, and the effect continues. The defoamer compositions of Comparative Examples 1 and 2 had a larger amount of foaming than the defoamer compositions of Examples 1 to 4, resulting in poor defoaming effect.

  As mentioned above, although this invention was demonstrated with some embodiment and an Example, this invention is not limited to these, A various deformation | transformation is possible within the range of the summary of this invention.

1 Cylindrical container 2 Circulating pump 3 Flow meter

Claims (5)

(A) 5 to 50% by mass of an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms,
(B) 0.05 to 5% by mass of a nonionic surfactant having an HLB having a sterol skeleton of 12 to 19, and
(C) An oil-in-water emulsion defoamer composition comprising water as a remaining amount.   The oil-in-water emulsion antifoaming composition according to claim 1, wherein the nonionic surfactant (B) is polyoxyethylene lanolin alcohol and / or polyoxyethylene phytosterol.   The oil-in-water emulsion antifoam composition according to claim 1 or 2, wherein the content of the higher aliphatic alcohol having 12 to 30 carbon atoms in the oil phase component (A) is 50 to 100% by mass. object.   The oil-in-water emulsion antifoaming composition according to any one of claims 1 to 3, wherein the nonionic surfactant (B) has an HLB of 15 to 18.   The content of the nonionic surfactant (B) is 0.5 to 10 parts by weight per 100 parts by weight of the oil phase component, according to any one of claims 1 to 4. Oil-in-water emulsion antifoam composition.

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