JP2018051513A - Oil-in-water type emulsion defoaming agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a higher alcohol-based emulsion-type defoaming agent having higher defoaming power than hitherto even in a system containing a paper-making additive or an agent derived from used paper in large quantities, and excellent in defoaming persistence.SOLUTION: An oil-in-water type emulsion defoaming agent contains, in an oil phase component, (A) a higher alcohol having the number of carbon atoms of 12 to 30, and (B) hydroxy acid esters having one hydroxy group in a molecule, shown by formula (1) (Ris a (m+n+1) valent residue obtained by removing a hydroxy group and a carboxyl group from hydroxy acid; Ris an acyl group having C2 to 30; Ris an alkyl group or an alkenyl group having C12 to 30; m is an integer of 0 to 3; and n is an integer of 1 to 3).SELECTED DRAWING: None

Description

  The present invention relates to an antifoaming agent, and more specifically, has an excellent antifoaming effect on bubbles generated in various manufacturing processes such as paper pulp manufacturing processes, foods, fibers, building materials, paints, and wastewater treatment processes. The present invention relates to an oil-in-water emulsion antifoaming agent.

  Conventionally, typical examples of the oil-in-water emulsion defoamer include emulsion defoamers mainly composed of higher alcohols (see Patent Documents 1 to 4). Higher alcohol emulsion-type antifoaming agent has a good antifoaming effect on fine bubbles intervening in the pulp slurry, and has excellent effects such as little influence on the size effect. It is expanding.

  In recent years, the recycling rate of used paper has increased, and when used as a raw material, in order to maintain product quality, the amount of additives such as paper strength agents and retention agents tends to increase. These additives are known to have the effect of stabilizing the foam. Further, there are chemicals derived from waste paper, and defoaming in the paper making process using waste paper as a raw material becomes even more difficult. Furthermore, waste paper is a generated product, and the quality of the waste paper varies from time to time. Therefore, the foam generated for each used paper is different, and the conventional antifoaming agent sometimes lacks the defoaming effect. Therefore, there is a demand for an antifoaming agent having a higher defoaming power than conventional antifoaming agents.

JP 2001-113104 A Japanese Patent Laying-Open No. 2015-54259 Japanese Patent No. 3690773 Japanese Patent No. 3964965

  The present invention has been made in consideration of such a situation, and has a higher defoaming power than conventional ones even in a system containing a large amount of papermaking additives and used paper-derived chemicals, and has a defoaming sustainability. An object of the present invention is to provide an improved higher alcohol emulsion defoamer.

（式中、Ｒ^１はヒドロキシ酸からヒドロキシ基とカルボキシル基を除いた（ｍ＋ｎ＋１）価の残基、Ｒ^２は炭素原子数２〜３０のアシル基、Ｒ^３は炭素原子数１２〜３０のアルキル基又はアルケニル基を表し、ｍは０〜３の整数、ｎは１〜３の整数を示す。） As a result of intensive studies to solve the above problems, the present inventor has found that the defoaming sustainability is remarkably improved by combining a specific raw material with the oil phase component and has led to the present invention. . That is, the present invention relates to (A) a higher alcohol having 12 to 30 carbon atoms as an oil phase component, and (B) a hydroxy acid ester having one hydroxy group in the molecule represented by the following general formula (1). And an oil-in-water emulsion antifoaming agent characterized in that

(Wherein R ¹ is a (m + n + 1) -valent residue obtained by removing a hydroxy group and a carboxyl group from a hydroxy acid, R ² is an acyl group having 2 to 30 carbon atoms, and R ³ is an alkyl having 12 to 30 carbon atoms. A group or an alkenyl group, m represents an integer of 0 to 3, and n represents an integer of 1 to 3)

  According to the present invention, a higher alcohol and a specific hydroxy acid ester are contained in the oil phase component of the antifoaming agent, so that the conventional higher alcohol can be used even in a system containing a large amount of papermaking additives and waste paper-derived chemicals. Compared with the system emulsion type antifoaming agent, it has a high defoaming power and can greatly improve the defoaming sustainability.

  The present invention will be described in detail below, but the present invention is not limited thereto.

  (A) The higher alcohol having 12 to 30 carbon atoms used in the present invention may be used in a conventional higher alcohol emulsion-type antifoaming agent. For example, natural alcohol or synthetic alcohol having 12 to 30 carbon atoms. 1 type (s) or 2 or more types can be used. Specific examples include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol, triacontanol and the like. Among these, a higher alcohol having 18 to 22 carbon atoms is preferable in terms of the defoaming effect.

  (A) Although the compounding quantity of a higher alcohol is not specifically limited, It may be 20-80 mass% with respect to the oil-phase component whole quantity. Preferably it is about 40-60 mass% from the surface of a defoaming effect.

  (B) The hydroxy acid esters represented by the general formula (1) used in the present invention are esterified by reacting all carboxyl groups of the hydroxy acid with higher alcohols having 12 to 30 carbon atoms. And having one hydroxy group in the molecule.

Examples of the hydroxy acid include lactic acid, tartaric acid, malic acid, citric acid, isocitric acid, hydroxybutyric acid, mevalonic acid, pantoic acid, ricinoleic acid, quinic acid, shikimic acid, salicylic acid, vanillic acid, syringic acid, and orthoric acid. . Among these, hydroxy acids having one hydroxy group such as malic acid and citric acid are preferable from the viewpoint of the defoaming effect.
As the hydroxy acid having two or more hydroxy groups, one obtained by reacting with a carboxylic acid to form one hydroxy group can be used.
As the higher alcohol having 12 to 30 carbon atoms, those mentioned as the component (A) can be used.

  The (B) hydroxy acid esters may be used alone or in combination of two or more, and among them, dialkyl malate and trialkyl citrate are particularly preferably used.

  (B) Although the compounding quantity of hydroxy acid ester is not specifically limited, You may be 20-80 mass% with respect to the oil-phase component whole quantity. Preferably it is about 40-60 mass% from the surface of a defoaming effect.

  The antifoaming agent according to the present invention may further contain a compound generally used as an antifoaming agent. For example, fatty acid esters, natural fats and oils, mineral oils, hydrocarbons and the like can be mentioned.

  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 2 to 30 carbon atoms. Examples of the monohydric alcohol having 1 to 30 carbon atoms used for the ester include methanol, ethanol, hexanol, decanol, palmityl alcohol, stearyl alcohol and the like. Examples of the dihydric alcohol include ethylene glycol, butanediol, hexanediol and the like. Examples of the trihydric alcohol include glycerin, trimethylolpropane, pentanetriol and the like. Examples of the tetrahydric alcohol include pentaerythritol, diglycerin, sorbitan and the like. Examples of pentavalent alcohol include arabit, and examples of hexavalent alcohol include sorbit and tetraglycerin. Examples of the carboxylic acid having 2 to 30 carbon atoms include acetic acid, hexanoic acid, lauric acid, stearic acid, and oleic acid.

  Examples of natural fats and oils include vegetable oils and fats such as soybean oil, palm oil, coconut oil, linseed oil, rapeseed oil and cacao fat, animal fats and oils such as beef tallow, pork fat and fish oil, and hydrogenated hydrogenated fats and the like.

  Examples of the hydrocarbon include paraffin wax, polyethylene wax, liquid paraffin, α-olefin, and mineral oil.

  The antifoaming agent according to the present invention is an oil-in-water emulsion in which an oil phase containing the above components is emulsified and dispersed in an aqueous phase. The mixing ratio of the oil phase and the water phase is not particularly limited as long as an oil-in-water emulsion is obtained, and the oil phase is generally about 10 to 50% by mass with respect to the antifoaming agent.

  In the present invention, a known water-soluble polymer may be used as an emulsion separation inhibitor. Examples of water-soluble polymers include starch, mannagalactan, sodium alginate, xanthan gum, welan gum, diyutan gum, tragacanth gum, arabic gum, dextrin, gelatin, casein, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, carboxymethyl starch, polyvinyl alcohol , Sodium polyacrylate, polyethylene oxide and the like.

  For the antifoaming agent according to the present invention, known preservatives can be used for the purpose of preserving during storage, but the use of these preservatives is not limited.

  In producing the emulsion of the present invention, known nonionic surfactants and / or anionic surfactants can be used as emulsion emulsifiers. The amount of the emulsifier used is preferably 0.1 to 5% by weight in the emulsion.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester And sorbitan fatty acid esters.

  Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, alkyl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl sulfosuccinate and the like.

  The emulsion of the present invention can be easily obtained by a known emulsification method. For example, there is a method in which an oil phase component and an emulsifier are charged in a container, heated to a temperature equal to or higher than the melting point of the oil phase component and the emulsifier, and then hot water is added to phase-invert and emulsify into an O / W emulsion. There is no particular limitation. In emulsification, a disperser such as a homomixer, a high-pressure emulsifier, a colloid mill, or a disper mill may be used.

  The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In this example, “%” means “% by weight” unless otherwise specified.

<Examples and comparative examples>
Ingredients and emulsifiers shown in Table 1 were charged into a flask, heated to 85-95 ° C., hot water having the same temperature was added and mixed with stirring so as to form an oil-in-water emulsion. Thereafter, the mixture was passed through a disper mill, mixed with an aqueous solution containing a thickener, and cooled to obtain an antifoaming agent.

<Performance evaluation of antifoaming agent>
Place 1000 ml of the test solution prepared by the following method in a glass cylinder having an inner diameter of 80 mm and a height of 600 mm and hold at 40 ° C. Next, the liquid is circulated from the bottom of the cylinder to the top using a water flow pump at a flow rate of 10 L / min and foamed. When the foam height reaches 90 mm, 2 ppm of antifoam is added. The minimum value of the subsequent foam height (mm) was measured after 5 minutes and 10 minutes. The defoaming sustainability was evaluated from the difference between the numerical value after 5 minutes and 10 minutes after circulation and the minimum value of the foam height (the smaller the difference, the higher the defoaming sustainability).

<Method for preparing test solution>
Composite waste paper in which cardboard waste paper, magazine waste paper, and coated paper waste paper were mixed at a ratio of 4: 3: 3 was disaggregated with a desktop disintegrator to obtain a pulp slurry having a concentration of 5%. After adding 3% (for pulp) sulfate sulfate, 0.5% (for pulp) commercially available paper strength agent and 0.8% (for pulp) for commercially available rosin emulsion sizing agent, tap water, Was added to a concentration of 0.5%. Thereafter, a filtrate obtained by filtering the pulp using a 40-mesh wire mesh was used as a test solution.

表２に示したように、本発明による高級アルコール系エマルション型消泡剤は従来品及び比較例よりも優れた消泡性能を示し、実用上非常に有用である。また、従来品と比較し長時間での消泡効果が優れている（消泡持続性が良好）ことから、用水循環率が高まっている昨今の製紙工程においては、一層の効果が期待できると言える。

As shown in Table 2, the higher alcohol emulsion-type antifoaming agent according to the present invention exhibits defoaming performance superior to that of conventional products and comparative examples, and is very useful in practice. In addition, since the defoaming effect over a long period of time is superior compared to conventional products (good defoaming sustainability), a more effective effect can be expected in the recent papermaking process where the water circulation rate is increasing. I can say that.

Claims (2)

An oil phase component containing (A) a higher alcohol having 12 to 30 carbon atoms and (B) a hydroxy acid ester having one hydroxy group in the molecule represented by the following general formula (1) Oil type antifoaming agent.

(Wherein R ¹ is a (m + n + 1) -valent residue obtained by removing a hydroxy group and a carboxyl group from a hydroxy acid, R ² is an acyl group having 2 to 30 carbon atoms, and R ³ is an alkyl having 12 to 30 carbon atoms. A group or an alkenyl group, m represents an integer of 0 to 3, and n represents an integer of 1 to 3) The oil-in-water emulsion antifoaming agent according to claim 1, wherein the (B) hydroxy acid ester is a dialkyl malate or a trialkyl citrate.