JP5786336B2 - Antifoaming agent and method for producing antifoaming agent - Google Patents

Description

  The present invention relates to an antifoaming agent containing a higher alcohol and a method for producing the antifoaming agent.

  Conventionally, a wax-type antifoaming agent is an O / W emulsion type containing an active ingredient that is solid or liquid at room temperature, such as higher alcohols, hydrocarbons, and fatty acid esters (for example, see Patent Documents 1 to 3). However, there is a growing demand for improved performance of wax-based antifoaming agents, and improvement of conventional wax-based antifoaming agents is necessary.

JP 11-276805 A JP 2000-288308 A JP 2000-300909 A

  By the way, the defoaming effect by the defoaming agent is mainly determined by the performance of the active ingredient itself and the particle diameter of the dispersed oil phase. For this reason, in order to improve the defoaming effect by the antifoaming agent, it is necessary to optimize the particle diameter of the dispersed oil phase while improving the performance of the active ingredient. However, the oil phase easily aggregates, It was difficult to achieve both.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an antifoaming agent that suppresses aggregation of an oil phase and is excellent in an antifoaming effect, and a method for producing such an antifoaming agent. And

  The present inventor has found that the antifoaming ability by the active ingredient is improved by blending microcrystalline wax and / or petrolatum, and the accompanying oil phase aggregation is suppressed by using a polyhydric alcohol together, The present invention has been completed. Specifically, the present invention provides the following.

  (1) An antifoaming agent having an O / W emulsion structure, in which a higher alcohol, microcrystalline wax and / or petrolatum, and a polyhydric alcohol are blended.

  (2) An antifoaming agent having an emulsifying step of emulsifying a liquid oil containing a higher alcohol and microcrystalline wax and / or petrolatum into water in the presence of a polyhydric alcohol to produce an O / W emulsion. Production method.

(3) After the emulsification step,
A first cooling step in which the O / W emulsion is cooled to a predetermined temperature higher than room temperature without gentle stirring or stirring than the emulsification step;
Then, the 2nd cooling process of cooling the said O / W emulsion to normal temperature, stirring more intensely than a 1st cooling process, The manufacturing method of (2) description.

  According to the present invention, the defoaming ability of the active ingredient is improved by blending microcrystalline wax and / or petrolatum, and the accompanying aggregation of the oil phase is suppressed by using a polyhydric alcohol together. Thereby, the aggregation of an oil phase is suppressed and the antifoamer which is excellent in the defoaming effect can be manufactured.

  Hereinafter, although embodiment of this invention is described, these do not limit this invention.

  The antifoaming agent according to the present invention contains a higher alcohol, microcrystalline wax and / or petrolatum, and a polyhydric alcohol, and has an O / W emulsion structure. Microcrystalline wax and / or petrolatum improve the defoaming ability of the active ingredient, and the polyhydric alcohol suppresses the accompanying oil phase aggregation. Thereby, the aggregation of an oil phase is suppressed and the antifoamer which is excellent in the defoaming effect can be manufactured.

  The higher alcohol may be a higher alcohol conventionally used in an antifoaming agent, for example, one or more of natural alcohols and / or synthetic alcohols having 12 to 30, preferably 18 to 30 carbon atoms. It's okay. Examples of the natural alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol and unsaturated alcohol such as oleyl alcohol. Synthetic alcohols include linear, unbranched saturated alcohols synthesized by the Ziegler method, linear primary alcohols or branched primary alcohols synthesized by the oxo method, or mixtures of these alcohols having different carbon numbers, Examples include linear secondary alcohols obtained by air oxidation of paraffin. The blending amount of the higher alcohol is not particularly limited, and may be about 30 to 90% by mass with respect to the solid component in the antifoaming agent.

The microcrystalline wax and petrolatum may be blended alone or in combination. Microcrystalline wax and petrolatum belong to petroleum wax together with paraffin wax. In the present invention, petroleum wax is classified as follows in accordance with JIS.
Paraffin wax is a wax that is separated and refined from reduced-pressure distilled spilled oil and is solid (melting point: about 50 to 70 ° C.) at room temperature, and is composed of saturated hydrocarbons mainly composed of linear hydrocarbons, and has an oil content of Less (1% or less).
Microcrystalline wax is separated and purified from vacuum distillation residue oil or heavy spilled oil, is a solid wax at normal temperature, has a boiling point higher than that of paraffin wax (melting point is about 60 to 90 ° C.), and has an oil content of 2 to 2. 5%.
Petrolatum is separated and purified from a vacuum distillation residue, is a semi-solid wax at room temperature, and has about 10% more oil than microcrystalline wax.

  Since microcrystalline wax and petrolatum are both microcrystalline waxes and hydrocarbons having polyunsaturation, they are more hydrophilic than general waxes such as paraffin wax, and foam of antifoamer particles. It exhibits the effect of facilitating penetration into the membrane. For this reason, the defoaming ability by an active ingredient can be improved. The blending amount of the microcrystalline wax and petrolatum is not particularly limited, but may be 5 to 50% by mass with respect to the solid component in the antifoaming agent. Paraffin wax may or may not be included as long as microcrystalline wax and / or petrolatum are included.

  The polyhydric alcohol is a compound having two or more hydroxyl groups (—OH) in one molecule. Although not particularly limited, low molecular weight polyethylene glycols such as ethylene glycol and diethylene glycol, low molecular weight polypropylene glycols such as propylene glycol and dipropylene glycol, other glycols, glycerin and its multimers, 1,3-propanediol, 1,4- Examples include alkylene polyols such as butanediol. The molecular weight of the polyhydric alcohol is not particularly limited, and may be, for example, 500 or less.

  Although the compounding quantity of a polyhydric alcohol is not specifically limited, 0.5 mass% or more and 10 mass% or less may be sufficient with respect to an antifoamer. Moreover, since polyhydric alcohol has the effect | action which suppresses aggregation of the oil phase by microcrystalline wax and petrolatum, the compounding quantity of polyhydric alcohol may be prescribed | regulated by the relative amount with microcrystalline wax and petrolatum. That is, if the blending amount of the polyhydric alcohol is too small relative to the total amount of the microcrystalline wax and / or petrolatum, it is difficult to sufficiently suppress the aggregation of the oil phase, and even if it is excessive, the aggregation of the oil phase is suppressed. Saturated and not economical. Therefore, the lower limit of the blending amount of the polyhydric alcohol with respect to 100 parts by mass of the total amount of the microcrystalline wax and / or petrolatum is preferably 10 parts by mass, more preferably 50 parts by mass, and the upper limit is 200 parts by mass. It is preferably 100 parts by mass.

  The antifoaming agent according to the present invention may further contain an active ingredient that is solid or liquid at room temperature, such as hydrocarbon, fatty acid ester, aliphatic ketone, and aliphatic ether, if necessary.

  The hydrocarbon may be polyethylene wax, Fischer-Tropsch wax, paraffin wax, and the like, for example, a commercially available paraffin mixture called white oil.

  The fatty acid ester may be a fatty acid ester of a 1 to 6 carbon alcohol having 1 to 30 carbon atoms and a carboxylic acid having 12 to 30 carbon atoms. The fatty acid used in the ester may be, for example, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid, behenic acid, etc., preferably palmitic acid, oleic acid or stearic acid. Examples of the monovalent alcohol having 1 to 30 carbon atoms for esterifying the carboxylic acid include methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, and higher alcohol. Examples of the dihydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, cyclohexanediol, butanediol, pentanediol, hexanediol, trimethylene glycol, catechol, resorcin, and hydroquinone. Examples of the trihydric alcohol include glycerin, trimethylolpropane, trimethylolethane, butanetriol, pentanetriol and the like. Examples of the tetrahydric alcohol include pentaerythritol, diglycerin, sorbitan, mannitan and the like. Examples of the pentahydric alcohol include arabit, and examples of the hexavalent alcohol include tetraglycerin, sorbit, and mannitol. Fatty acid esters include animal fats such as beef tallow, pork oil, sardine oil, and whale oil, and natural fats such as vegetable oil such as soybean oil, corn oil, coconut oil, linseed oil, rapeseed oil, cottonseed oil, castor oil, and gill oil. Further, it may be a hardened oil obtained by hydrogenating them and subjected to a hardening treatment.

  Aliphatic ketones are higher fatty acid ketones such as 16-hentriacontanone (palmitone), 18-pentatriacontanone (stearon), 20-nonatriacontanone (araquinone), and 22-triatetracontanone (behenone). It may be.

  The aliphatic ether may be an alkyl ether having 20 to 40 carbon atoms that is by-produced during Ziegler synthesis.

  The antifoaming agent according to the present invention may further contain a water-soluble polymer in order to prevent product separation and thickening during storage. Water-soluble polymers include cellulose, pullulan, sodium alginate, gum arabic, guar gum, glucomannan, xanthan gum, welan gum, rhamzan gum, tragacanth gum, locust bean gum, agarose, glycogen, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropyl Cellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, carboxymethylethylcellulose, cellulose acetate phthalate, polyvinyl alcohol, polyethylene oxide, polyacrylamide, polymethacrylamide, polyacrylic acid, polymethacrylic acid, copolymer of acrylamide and acrylic acid, acrylamide And methacrylic acid Things, a copolymer of methacrylamide and acrylamide, a copolymer such as of methacrylamide and methacrylic acid.

  In addition, the antifoaming agent according to the present invention may further contain a preservative, a fungicide, a bactericidal agent, a rust inhibitor, a skin prevention agent, and the like. Since these are conventionally well-known (see, for example, Japanese Patent Laid-Open No. 2000-300909), details thereof are omitted.

  The antifoaming agent according to the present invention is an oil phase containing the above components emulsified and dispersed in an aqueous phase. The mixing ratio of the oil phase and the aqueous phase is not particularly limited as long as an O / W emulsion structure is obtained, and generally the amount of the oil phase may be 50% by mass or less based on the antifoaming agent.

  The antifoaming agent according to the present invention is an emulsification step in which a liquid oil containing a higher alcohol and microcrystalline wax and / or petrolatum is emulsified in water in the presence of a polyhydric alcohol to produce an O / W emulsion. Have Thereby, aggregation of the oil phase in the cooling process after emulsification is suppressed, and an antifoaming agent having an excellent defoaming effect can be obtained.

  In the emulsification step, the polyhydric alcohol is preferably added to water after being mixed with a higher alcohol and an oil agent such as microcrystalline wax and / or petrolatum from the viewpoint of sufficiently suppressing aggregation of the oil phase. Alternatively, it may be added to water.

  As described above, the blending amount of the polyhydric alcohol is preferably 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the total amount of the microcrystalline wax and / or petrolatum, and the oil agent contains other components. Optionally included.

  In the emulsification step, in order to disperse the oil agent in water, the oil agent is heated to a temperature not lower than the melting point of the components contained in the oil agent (not particularly limited, but 90 ° C. or higher) so that the oil agent has fluidity. Stir. Since the operation and equipment itself are well known in the art (see Japanese Patent Application Laid-Open No. 11-276805), details are omitted.

  The emulsification step is followed by a step of cooling the O / W emulsion to room temperature. In this step, the first cooling step in which the O / W emulsion is cooled to a predetermined temperature higher than normal temperature without stirring, and then the stirring is performed more intensely than in the first cooling step. However, it is preferable to have the 2nd cooling process which cools O / W emulsion to normal temperature. Thereby, aggregation of the oil phase in the cooling process can be more sufficiently suppressed.

  The predetermined temperature may be appropriately determined according to the composition of the oil agent, the mixing ratio with water, and the like so as to be a temperature at which the particle surface of the antifoaming agent is solidified. Good. Note that the gentle or intense stirring is determined by the magnitude of the shearing force (for example, when the emulsification step, the first cooling step, and the second cooling step are performed in the same equipment, the rotation speed of the stirring member).

  However, in the cooling step, as is conventionally known, the O / W emulsion may be cooled to room temperature while continuing to stir.

  The antifoaming agent thus obtained can be widely used, for example, in the paper pulp industry, food industry, textile industry, building material board production, paint industry, chemical industry, etc. It is useful in wastewater treatment processes such as activated sludge.

<Examples 1-4, Comparative Examples 1-4>
The components shown in Table 1 were supplied into a jacket-type beaker, and heated and melted by passing hot water of 90 ° C. through a circulating constant temperature water s tank “Ecoline” (manufactured by LAUDA). The stirrer “Toornade (standard type)” (manufactured by ASONE) was rotated at 2000 rpm, and hot water was added to the molten oil while stirring to emulsify the oil into water to produce an O / W emulsion. . Then, 0.1 mass% of acrylic acid polymer “AQUALIC DL40S” (manufactured by Nippon Shokubai Co., Ltd.) was added to the O / W emulsion while continuing stirring.

  Stirring was stopped, the water passing through the circulation type thermostatic water tank was switched to cold water, and the O / W emulsion was cooled to about 60 ° C. Then, stirring was started again (rotation speed 500rpm), and the O / W emulsion was cooled to normal temperature (30 degrees C or less), stirring, and the antifoamer was obtained.

[Evaluation]
500 mL of newsprint paper white water to which each of the obtained antifoams was added in an amount of 4 mg / L was supplied to a glass cylindrical container with a caliber of 70 mm in inner diameter and 1 L in capacity, and at a flow rate of 1000 mL / min by a circulation pump. It was circulated and dropped onto the water surface from a height of 50 cm above the surface of the papermaking white water in the cylindrical container. The temperature was maintained at 45 ° C., and 5 minutes after the start of circulation, the thickness of the foam generated on the surface of the papermaking white water in the cylindrical container was read based on the scale. The results are shown in Table 1.

表中の成分：
マイクロクリスタリンワックス Ｈｉ−ｍｉｃ−１０９０（日本精蝋社製）
高級アルコール ＮＡＦＯＬ２０＋（サソールジャパン社製）
炭化水素 パラフィンワックス１５５（日本精蝋社製）
脂肪酸エステル ヒマシ硬化油（伊藤製油社製）
多価アルコール プロピレングリコール試薬１級（キシダ化学社製）

Ingredients in the table:
Microcrystalline wax Hi-mic-1090 (Nippon Seiwa Co., Ltd.)
Higher alcohol NAFOL20 + (manufactured by Sasol Japan)
Hydrocarbon paraffin wax 155 (Nippon Seiwa Co., Ltd.)
Fatty acid ester castor hydrogenated oil (Ito Oil Co., Ltd.)
Polyhydric alcohol Propylene glycol reagent grade 1 (Kishida Chemical Co., Ltd.)

  As shown in Table 1, it was found that Examples 1 to 4 had a smaller foaming amount than Comparative Examples 1 to 4 and were excellent in the defoaming effect. Further, from Examples 1 and 2, it was confirmed that in order to obtain an excellent defoaming effect, microcrystalline wax, higher alcohol and polyhydric alcohol are essential, but hydrocarbon and fatty acid ester are not necessarily required.

<Examples 5 to 13 and Comparative Examples 5 to 13>
An antifoaming agent was obtained in the same procedure as in Example 1 except that the type of polyhydric alcohol was changed to that shown in Table 2. About the obtained antifoamer, it filtered with the 100 mesh metal-mesh, and the presence or absence of aggregation of an oil phase was confirmed by measuring the quantity of the filtration residue. The results are shown in Table 2.

  In Table 2, without aggregation in Examples 5 to 13, the amount of the residue is less than 0.1% with respect to the blending amount of the oil agent, and with aggregation in Comparative Examples 5 to 13 the amount of the residue with respect to the blending amount of the oil agent It was 5% or more. Thereby, it turned out that aggregation of an oil phase can be suppressed by using all polyhydric alcohols together with microcrystalline wax and higher alcohol.

Claims (3)

An antifoaming agent having an O / W emulsion structure, comprising a higher alcohol having 12 to 30 carbon atoms , microcrystalline wax and / or petrolatum, and a polyhydric alcohol. An emulsification step of emulsifying a liquid oil containing a higher alcohol having 12 to 30 carbon atoms and microcrystalline wax and / or petrolatum into water in the presence of a polyhydric alcohol to produce an O / W emulsion. A method for producing an antifoaming agent. After the emulsification step,
A first cooling step in which the O / W emulsion is cooled to a predetermined temperature higher than room temperature without gentle stirring or stirring than the emulsification step;
Then, the manufacturing method of Claim 2 which further has a 2nd cooling process which cools the said O / W emulsion to normal temperature, stirring more intensely than a 1st cooling process.