JP2001129307A - Defoaming agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyether type defoaming agent excellent in initial defoaming capacity, capable of maintaining defoaming capacity retention property, and causing no deterioration of water resistance of a finally to obtained product. SOLUTION: The defoaming agent composition contains a compound A produced by addition polymerization of 10-60 mole of 2-4C alkylene oxide to an ester of an aliphatic monocarboxylic acid containing 30 mole % or more of ricinoleic acid and having 16C or a higher average number of carbons and polyalcohol or the defoaming agent composition contains the compound A and a metal salt B composed of an aliphatic monocarboxylic acid having 12C or a higher average number of carbons and 46 deg.C or a lower melting point and a metal selected from sodium, potassium, cesium, magnesium, and aluminum.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyether-based antifoaming agent. More specifically, various industries handling foaming aqueous solutions, such as the paper pulp manufacturing industry and its papermaking process, the construction industry and its papermaking process, the dyeing and dyeing industries, the fermentation industry, the synthetic resin manufacturing industry, the synthetic rubber manufacturing industry, the ink,
Exhibits excellent defoaming properties against air bubbles generated in the paint industry and textile processing industry, as well as in the wastewater treatment process, and is used for paper, which is the final product obtained through processes such as papermaking. The present invention relates to a novel antifoaming composition capable of maintaining water resistance.

[0002]

2. Description of the Related Art Conventionally, for these industrial uses, water dispersibility is good, and the final product has few adverse effects such as oil spots, pinholes, repelling, and oil floating, and almost no scum or sediment is generated. Non-polyether-based defoamers are preferred. For example, mono- to polyhydric alcohols such as stearyl alcohol, dipropylene glycol, glycerin and sorbitan to which an alkylene oxide has been added (JP-B-45-30189, JP-B-49-3)
No. 8923, JP-A-54-133484, JP-B-61-7847, and the like wherein an alkylphenol is added to an alkylene oxide (JP-B-47-3).
No. 2511) or those obtained by esterifying these terminal hydroxyl groups (JP-A-52-97385, JP-A-5-97385).
No. 6,482,210).

[0003] Paper obtained by using the above-mentioned polyether-based antifoaming agent in the papermaking process has a problem that the water resistance is significantly inferior to, for example, the case where an emulsion-based antifoaming agent in which a higher alcohol is emulsified is used. there were. Conventionally, an organic solid such as an alkaline earth metal salt of a long-chain fatty acid is added to a polyether-based antifoaming agent (Japanese Patent Application Laid-Open No. 10-323505),
A higher fatty acid was added (for example, JP-A-9-308804) to improve the defoaming property, or a fatty acid ammonium salt was added (for example, JP-A-9-117608) to improve the water dilution stability of the defoamer. Although there are examples, in any case, the effect of improving the water resistance is not seen.

[0004]

As described above, the polyether-based defoamer has a disadvantage that the water resistance of the final product is reduced. Accordingly, an object of the present invention is to provide a polyether-based defoaming agent which maintains excellent defoaming properties, that is, maintains initial defoaming properties and defoaming continuity, and does not reduce water resistance of a finally obtained product. is there.

[0005]

Means for Solving the Problems The present inventors have made intensive studies and arrived at the present invention. That is, the present invention relates to an ester of an aliphatic monocarboxylic acid having an average carbon number of 16 or more and containing 30 mol% or more of ricinoleic acid and a polyhydric alcohol, and addition-polymerizing 10 to 60 mol of an alkylene oxide having 2 to 4 carbon atoms. A defoaming agent composition comprising

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, ricinoleic acid means a carboxyl group at C1 position, a hydroxyl group at C12 position, C9
It is a C18 aliphatic monocarboxylic acid having a double bond at the 10th to 10th positions. The aliphatic monocarboxylic acids having an average carbon number of 16 or more and containing ricinoleic acid of 30 mol% or more include ricinoleic acid and ricinoleic acid and other aliphatic monocarboxylic acids such as lauric acid, stearic acid, behenic acid and It is a mixture with oleic acid and the like.
The proportion of ricinoleic acid in the total carboxylic acid is preferably at least 30 mol%, more preferably at least 50 mol%.

In the present invention, the polyhydric alcohol is an alcohol having two or more hydroxyl groups such as ethylene glycol, propylene glycol, 1,4-butanediol, cyclohexanedimethanol, glycerin, polyglycerin, trimethylolpropane and pentaerythritol. It is. Of these, alcohols containing three or more hydroxyl groups are preferred, and glycerin is more preferred.

In the present invention, an ester is an esterified product of an aliphatic monocarboxylic acid containing 30% by mole or more of ricinoleic acid and a polyhydric alcohol, and the reaction ratio between the acid and the alcohol is not particularly limited. It is preferred that 70% or more of the hydroxyl groups of the dihydric alcohol are esterified.

In the present invention, castor oil is particularly preferred as an ester of an aliphatic monocarboxylic acid having an average carbon number of 16 or more and containing at least 30 mol% of ricinoleic acid with a polyhydric alcohol. Castor oil is a normal temperature liquid oil obtained from sesame seeds by squeezing. The composition is fatty acid triglyceride having 18 carbon atoms as a main component, and about 90% of the constituent fatty acids is ricinoleic acid.

In the present invention, the alkylene oxide having 2 to 4 carbon atoms includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO),
2-butylene oxide (hereinafter abbreviated as BO) and the like. Regarding the number of moles added to the ester of an aliphatic monocarboxylic acid containing ricinoleic acid of 30 mol% or more and a polyhydric alcohol having 3 or more carbon atoms, EO is preferably 3 to 15, preferably 4 to 14, and PO is preferably 7 to 45. 10-40, BO
Is 0-3, preferably 0-2. If the EO is less than 3 mol, dispersibility in water cannot be obtained, and if it exceeds 15 mol, dissolution into water starts, so that defoaming properties cannot be obtained. When the amount of PO is less than 7 mol or more than 45 mol, the defoaming property cannot be obtained. On the other hand, if BO exceeds 3 mol, the dispersibility in water decreases, so that both the defoaming property and the water resistance decrease. The order of addition polymerization of the alkylene oxide is not particularly limited, and the polymerization mode may be block or random.

In the present invention, an aliphatic monocarboxylic acid having an average carbon number of 12 or more and a melting point of 46 ° C. or less includes, for example, saturated fatty acids such as lauric acid, unsaturated fatty acids such as oleic acid and linoleic acid, branched alkyl groups and the like. Examples thereof include carboxylic acids having an unsaturated alicyclic group and the like, and mixtures thereof, and mixed fatty acids obtained from animal and vegetable oils. Of these, oleic acid is particularly preferred. When a carboxylic acid having a melting point of more than 46 ° C., such as stearic acid, is used, the defoamer composition may be solidified or pasted at room temperature or may form a coagulated material, resulting in non-uniformity.
Further, the improvement of the defoaming property and the water resistance is inferior to the case of oleic acid or the like. Further, when a carboxylic acid having an average carbon number of less than 12 such as 2-ethylhexylic acid is used, the defoaming property is obtained.
No improvement in water resistance is observed.

In the present invention, sodium, potassium, cesium, magnesium and aluminum can be used as the metal forming the neutralized salt of [B], of which potassium and magnesium are preferred, and potassium is particularly preferred. If a metal such as lithium or barium is used, the antifoaming composition may solidify or become cloudy at room temperature or may become non-uniform due to precipitation, so that sufficient antifoaming properties and water resistance cannot be obtained.

In the present invention, the weight ratio of [A] to [B] is 100: 0.5 to 5, preferably 100: 0.8 to 4. If [B] exceeds 5, the viscosity of the antifoaming agent composition increases, so that the handleability decreases and the antifoaming property also decreases. If it is less than 0.5, no improvement in defoaming property and water resistance is observed.

The present antifoaming composition may be obtained by adding a hydroxide such as potassium or magnesium or an alcoholate to [A] and then adding the carboxylic acid to form a metal salt in [A]. The metal salt may be directly added to [A]. [A] using potassium hydroxide or the like as a catalyst;
When the above is polymerized, the antifoaming composition can be prepared by adding the carboxylic acid as it is.

The defoamer composition of the present invention contains 1 to 20% of water.
(% By weight, the same applies hereinafter) and the aqueous solution may be diluted to a concentration of 99 to 80%. When diluting with water,
First add [B] to [A] at room temperature or below 50 ° C,
Alternatively, [B] is formed in [A], and the mixture is sufficiently stirred, and then water is gradually added to adjust to a predetermined concentration. If water is added in an amount of about 8% or more, the flash point cannot be measured, and the substance is not a dangerous substance under the Fire Service Law. Regarding the defoaming property, when water is added in an amount of 1 to 20%, the dispersibility in water becomes good, and the initial defoaming property is improved. If water is added in excess of 20%, the viscosity will increase significantly and the handling properties may be poor. For example, when water is added at 10%, the pressure is about 300 mPa · s / 25 ° C.
When 0% is added, it may become a paste or precipitate with time.

In the present invention, examples of the polymerization system used for the reaction of the alkylene oxide include anionic polymerization, cationic polymerization and coordination anionic polymerization. These polymerization types may be used alone or in combination. Examples of the catalyst include hydroxides, alcoholates or carbonates of alkali or alkaline earth metals and trialkylamines, Lewis acid catalysts such as stannic chloride and boron trifluoride, and mineral acids. -277
For example, a composite metal cyano complex disclosed in JP-A No. 236 or an organic aluminum porphyrin complex disclosed in JP-B-5-14734 may be used. Of these, potassium hydroxide and cesium hydroxide are preferred. The amount of the catalyst used is 0.05 to the weight of the compound at the end of the polymerization.
To 1.0% by weight, preferably 0.1 to 0.1% by weight.
5% by weight. Further, the amount is in the range of 0.2 to 2% by weight, and preferably 0.3 to 1.5% by weight, based on the ester serving as an initiator at the start of polymerization.

In the present invention, the reaction of the alkylene oxide having 2 to 4 carbon atoms may be carried out under ordinary conditions, for example, at a temperature of 70 to 150 ° C., preferably 80 to 140 ° C.
It is. The pressure (gauge pressure) during polymerization is 8 kg / c.
m ² or less, preferably 6 kg / cm ² or less.

In the present invention, the catalyst of [A] obtained by reacting the ester with the alkylene oxide may be removed or used without removal. As a method for removing the catalyst, a method of neutralizing an alkaline catalyst with an acidic component and removing a generated salt by filtration, a method of using an alkali adsorbent or an acid adsorbent, a method of dissolving in a solvent and washing and removing, and an ion exchange resin are used. There are a method of using, a method of neutralizing an alkaline catalyst with carbon dioxide gas, a method of filtering a generated carbonate, and a method of neutralizing with various organic acids, inorganic acids or alkali components, and any of them may be used. .

The antifoaming composition of the present invention can be added to a foaming system in the form of an aqueous solution diluted with water to a concentration of about 90 to 10%, or can be added to the foaming system without dilution. Is also good. The amount of the antifoaming composition of the present invention to be added to the foaming aqueous solution is usually 0.1 to 1,000 ppm, preferably 0.5 to 500 ppm.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. The test results of the defoaming property and the water resistance are shown in Table 1. Parts in Examples and Comparative Examples mean parts by weight. Unless otherwise specified, all raw materials used were reagent grade products.

[Defoaming test method] 750 ml of foaming test water (newspaper paper white water) is placed in a glass cylinder (hereinafter referred to as a foam tube), and the temperature is adjusted to 45 ° C. Then, using a pump, 3,000 ml of test water was poured from the bottom of the foam tube.
While circulating in minutes, drop the test tube onto the test liquid surface 20 cm below the top of the foam tube. When the foam height reaches 10 cm, add 5.0 ppm of antifoamer (vs. test water) with a micropipette. The circulation is maintained and the changing foam height is followed for 5 minutes. The data 1 minute after the start of the test indicates the initial defoaming property, and the data 5 minutes after the test indicates the defoaming persistence.

[Water Resistance Test Method] A Stighit sizing test (JI) using paper obtained under the following test paper preparation conditions:
SP 8122), the water resistance was evaluated and compared based on the total average value (second, the higher the value, the better the water resistance). [Test paper preparation conditions] AL-120 in 1000 cc of tap water
[Sizing agent manufactured by Arakawa Chemical Co., Ltd.] 0.1 g of an 8% aluminum sulfate aqueous solution and 1.0 g of an aqueous solution are added to prepare a model white water. Next, an antifoaming agent is added to this so as to have a concentration of 5.0 PPM to prepare a test aqueous solution, and the temperature is adjusted to 45 ° C. PPC paper [made by Fuji Xerox Co., Ltd., weight 0.75 g] cut into a circle having a diameter of 12 cm is placed on a nutsche of the same diameter attached to a suction bottle, and 75 g of the above test aqueous solution is poured. The suction bottle is then evacuated and the test water poured over about 15 seconds is filtered. Round PP filtered with test water
C paper is dried with a drum dryer at 110 ° C. for 2 minutes.

Example 1 Castor oil [HIMASHU LAV manufactured by Ito Oil Co., Ltd.] was placed in a pressure-resistant reaction vessel capable of heating, cooling and stirring up to 250 ° C.
5.0 parts of potassium hydroxide (hereinafter, potassium hydroxide is added so as to be approximately 0.25% by weight with respect to the final polymer) is added to 932 parts of 1 mol, and after dehydration at 130 ° C. under reduced pressure, 870 parts of 15 moles of PO were reacted at 100-120 ° C for about 9 hours, and 176 parts of 4 moles of EO were reacted at 130 ° C for about 2 hours. Next, 12 parts of oleic acid (melting point: 16 ° C.) was added to 900 parts of the polymer obtained at 40 ° C., and the mixture was stirred for 0.5 hour. Next, 88 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Example 2 To 1000 parts of the polymer obtained in Example 1 was added 20 parts of water at 90 ° C. and the mixture was stirred for 30 minutes. Further, at the same temperature, 50 parts of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd., alkali adsorbent for removing catalyst) are added, and the mixture is stirred for 1 hour. Next, a liquid material (containing 1.5% water) obtained by filtration using No. 2 filter paper (manufactured by Toyo Roshi Kaisha, Ltd.) was subjected to a defoaming test and the like.

Example 3 To 820 parts of the compound obtained in Example 2, 20 parts of magnesium oleate and 160 parts of water were added, followed by stirring at 40 ° C. for 1 hour, followed by cooling to obtain a liquid composition and defoaming. It was subjected to sex tests and the like.

Example 4 In the same manner as in Example 1, 1 mol of castor oil / 25 mol of PO /
7 mol of EO polymer was obtained, and polymer 8 obtained at 40 ° C.
4 parts of potassium hydroxide and 38 parts of oleic acid were added to 60 parts and stirred for 0.5 hour. Next, 98 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Example 5 In the same manner as in Example 1, 1 mol of castor oil / 40 mol of PO /
10 mol of EO was obtained, and 1.0 part of potassium hydroxide and 20 parts of oleic acid were added to 890 parts of the obtained polymer at 40 ° C., and the mixture was stirred for 0.5 hour. Then at the same temperature 8
Nine parts of water was gradually added to obtain a liquid composition, which was subjected to a defoaming test and the like.

Example 6 In the same manner as in Example 1, 1 mol of castor oil / 15 mol of PO /
A polymer of 2 mol of BO / 6 mol of EO was obtained, and 1.2 parts of potassium hydroxide was added to 890 parts of the polymer obtained at 40 ° C.
Oleic acid (22 parts) was added and stirred for 0.5 hour. Next, 86.8 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Example 7 Ricinoleic acid / oleic acid / lauric acid = 3/1/1
Esters were synthesized from 3 moles of the mixed fatty acid (by mole) and 1 mole of pentaerythritol by a conventional method. Next, a polymer of 1 mol of this ester / 30 mol of PO / 8 mol of EO was obtained in the same manner as in Example 1, and 9 parts of lauric acid (melting point: 44 ° C.) was added to 900 parts of the polymer obtained at 40 ° C. Stirred for 0.5 hour. Next, 91 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Comparative Example 1 In the same manner as in Example 1, a polymer of 1 mol of linear primary alcohol having an average carbon number of 15/17 mol of PO / 5 mol of EO was obtained, and 900 parts of the polymer obtained at 40.degree. Then, 12 parts of oleic acid was added and the mixture was stirred for 0.5 hour. Next, 88 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Comparative Example 2 Ricinoleic acid / oleic acid / lauric acid = 1/1/2
An ester was synthesized from 3 moles of the mixed fatty acid (in a molar ratio) and 1 mole of pentaerythritol by a conventional method. Then, a polymer of 1 mol of this ester / 35 mol of PO / 10 mol of EO was obtained in the same manner as in Example 1, and 12 parts of oleic acid was added to 900 parts of the obtained polymer at 40 ° C., followed by stirring for 0.5 hour. . Next, 88 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Comparative Example 3 To 900 parts of the polymer obtained in Example 1, 10 parts of caprylic acid (melting point: 16 ° C.) was added at 40 ° C., followed by stirring for 0.5 hour. Next, 90 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

Comparative Example 4 To 900 parts of the polymer obtained in Example 1 was added 12 parts of stearic acid (melting point: 71 ° C.) at 70 ° C., followed by stirring for 0.5 hour. Next, 88 parts of water was gradually added at 40 ° C., and a paste-like composition was obtained at room temperature and subjected to a defoaming test and the like.

Comparative Example 5 In the same manner as in Example 1, castor oil 1 mol / PO5 mol / E
O2 mol of polymer was obtained, and polymer 86 obtained at 40 ° C. was obtained.
5.0 parts potassium hydroxide and 50 parts oleic acid per 0 parts
And stirred for 0.5 hour. Next, 85 parts of water was gradually added at the same temperature to obtain a viscous liquid composition at room temperature, which was subjected to a defoaming test and the like.

Comparative Example 6 In the same manner as in Example 1, 1 mol of castor oil / 48 mol of PO /
20 parts of water are added at 90 ° C. to 1000 parts of a polymer having 16 moles of EO, and the mixture is stirred for 30 minutes. Further, at the same temperature, 50 parts of Kyoward 600 is added and stirred for 1 hour. Then, 4.0 parts of magnesium oleate was added to 920 parts of a liquid substance (containing 1.0% of water) obtained by filtration using No. 2 filter paper at 40 ° C, followed by stirring for 0.5 hour. Subsequently, 76 parts of water was gradually added at the same temperature to obtain a liquid composition, which was subjected to a defoaming test and the like.

[0036]

[Table 1]

[0037]

The antifoaming agent according to the present invention can be used in industries handling various foaming aqueous solutions, such as the paper pulp manufacturing industry and the paper making process.
Excellent against bubbles generated in the wastewater treatment process of the construction industry, its papermaking process, dye industry and dyeing industry, fermentation industry, synthetic resin manufacturing industry, synthetic rubber manufacturing industry, ink, paint industry, textile processing industry, etc. It shows the initial defoaming property and the defoaming durability. Also, when the antifoaming agent according to the present invention is used in a field where water resistance is required for the final product, for example, in the paper making process in the paper pulp manufacturing industry, it is useful because the obtained paper can retain excellent water resistance. It is.

Claims (7)

[Claims] 1. An ester of an aliphatic monocarboxylic acid having an average carbon number of 16 or more and containing 30 mol% or more of ricinoleic acid and a polyhydric alcohol is subjected to addition polymerization of 10 to 60 mol of an alkylene oxide having 2 to 4 carbon atoms. An antifoaming composition comprising the compound [A]. 2. An ester of an aliphatic monocarboxylic acid having an average carbon number of 16 or more and containing at least 30 mol% of ricinoleic acid and a polyhydric alcohol is subjected to addition polymerization of 10 to 60 mol of an alkylene oxide having 2 to 4 carbon atoms. Compound [A]
And a metal salt [B] of an aliphatic monocarboxylic acid having an average carbon number of 12 or more and a melting point of 46 ° C. or less selected from the group consisting of sodium, potassium, cesium, magnesium and aluminum. 3. The compound according to claim 1, wherein [A] is a compound obtained by subjecting 1 mol of castor oil to addition polymerization of 3 to 15 mol of ethylene oxide, 7 to 45 mol of propylene oxide and 0 to 3 mol of 1,2-butylene oxide. The antifoaming composition according to any one of the above. 4. The antifoaming composition according to claim 2, wherein [B] is potassium oleate. 5. The weight ratio of [A] to [B] is 100: 0.
The antifoaming composition according to any one of claims 2 to 4, which is 5 to 5. 6. The composition according to claim 1, which contains 1 to 20% by weight of water.
5. The antifoaming composition according to any one of the above items 5. 7. The antifoaming composition according to claim 1, which is an antifoaming agent for a papermaking process in the paper pulp manufacturing industry.