JP6298948B2 - Antifoam - Google Patents

Description

  The present invention relates to an antifoaming agent.

  “Mixing ratio of natural fats and oils and fatty acids having 8 to 22 carbon atoms or salts thereof is 1/3 to 1 / 0.1 in molar ratio, and a mixture of natural fats and oils and fatty acids having 8 to 22 carbon atoms or salts thereof An antifoaming agent characterized in that it contains a reaction product obtained by addition reaction of 5 moles or more of an alkylene oxide having 2 to 8 carbon atoms with ethylene oxide as an essential component per 1 mole of (Patent Document 1).

Japanese Patent Laid-Open No. 11-19407

  The conventional antifoaming agent has a problem that the antifoaming property may be low. An object of this invention is to provide the antifoamer which has the outstanding defoaming property.

The antifoaming agent of the present invention (first invention) is characterized by comprising only animal and vegetable oils (A) and animal and plant waxes (B), or animal and vegetable oils (A) and animal and plant waxes (B), water and / or products. Consisting only of stabilizers,
The melting point of animal and vegetable oil (A) is -17 to 0 ° C, and the melting point of animal and plant wax (B) is 53 to 83 ° C.
Based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B), the content of the animal and vegetable oil (A) is 92 to 99.9% by weight, and the content of the animal and vegetable oil (B) is 0.1 to 8% by weight. The point is the percentage.

The antifoaming agent of the present invention (second invention) is characterized by comprising only animal and vegetable oil (A), animal and vegetable wax (B) and natural surfactant (C), or animal and vegetable oil (A) and animal and vegetable wax (B ) And natural surfactant (C) and water and / or product stabilizer,
The melting point of animal and vegetable oil (A) is -17 to 0 ° C, and the melting point of animal and plant wax (B) is 53 to 83 ° C.
The natural surfactant (C) is lecithin or saponin,
Based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B), the content of the animal and vegetable oil (A) is 92 to 99.9% by weight, and the content of the animal and vegetable oil (B) is 0.1 to 8% by weight. The point is the percentage.

  The antifoaming agent of the present invention exhibits excellent antifoaming properties.

  Animal and vegetable oils (A) are not limited as long as they are oils obtained from animals and plants. For example, vegetable oils include rapeseed oil, soybean oil, corn oil, palm oil, palm oil, ben flower oil, olive oil, sesame oil, linseed oil, Cottonseed oil, sunflower oil, peanut oil, and the like are exemplified, and animal oils include beef tallow, pig oil, and whale oil. Of these, vegetable oils are preferred from the viewpoint of defoaming properties, more preferably rapeseed oil, soybean oil, corn oil, bean flower oil, olive oil, sesame oil, linseed oil, cottonseed oil, sunflower oil and peanut oil, particularly preferably rapeseed oil, Soybean oil, corn oil, bean flower oil, cottonseed oil, sunflower oil and peanut oil, most preferably rapeseed oil, soybean oil, corn oil and sunflower oil.

   The content (% by weight) of the animal and vegetable oil (A) is preferably 85 to 99.9, more preferably 90 to 99, particularly preferably based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B). 92-98. In this range, the defoaming property is further improved.

As for melting | fusing point of animal and vegetable oil (A), -20-37 degreeC is preferable, More preferably, it is -17-0 degreeC.
The melting point is JIS K7121-1987 {particularly 3. (2) and 8.6 (1)} are measured (the same applies hereinafter). That is, a measurement sample is put in a container (for example, 560-002, Seiko Instruments Inc.) of a differential scanning calorimetry (DSC) apparatus (for example, DSC-6200, Seiko Instruments Inc.), and nitrogen gas is 40 mL / min. While flowing, heat melt at a heating rate of 10 ° C./min to a temperature about 30 ° C. higher than the end of the melting peak, hold at that temperature for 10 minutes, and then cool to 5 ° C./min to a temperature about 100 ° C. lower than the melting temperature. Then, the melting point is the melting peak observed at the heating rate of 10 ° C./min.

  The animal and plant wax (B) is not particularly limited as long as it is a wax obtained from animals and plants. Examples thereof include wax, whale wax, shellac wax and lanolin wax. Of these, carnauba wax, candelilla wax, rice wax, wood wax, beeswax and lanolin wax are preferred, and carnauba wax, candelilla wax, wood wax and beeswax are particularly preferred from the viewpoint of defoaming properties. Are carnauba wax and candelilla wax.

   The content (% by weight) of the animal and plant wax (B) is preferably 0.1 to 15, more preferably 1 to 10, particularly preferably based on the total weight of the animal and vegetable oil (A) and the animal and plant wax (B). 2-8.

   40-90 degreeC is preferable and, as for melting | fusing point of animal and vegetable wax (B), More preferably, it is 53-83 degreeC.

  The natural surfactant (C) is not particularly limited as long as it is a naturally occurring surfactant. Viscosin, surfactin, emalzan and the like can be mentioned. Among these, lecithin, saponin and sodium caseinate are preferable from the viewpoint of antifoaming properties, and lecithin and saponin are more preferable.

   The content (% by weight) of the natural surfactant (C) is preferably from 0.9 to 10, more preferably from 1 to 9, based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B). Preferably it is 2-8.

  The antifoaming agent of the present invention includes animal and vegetable oil (A) and animal and vegetable wax (B) {first invention}, or animal and vegetable oil (A), animal and vegetable wax (B) and natural surfactant (C) {second invention }, It is preferable not to contain other components, but water and / or a product stabilizer {an antifungal agent, an antiseptic agent, an antirust agent and an antioxidant} may be contained.

  When water is contained, the content (% by weight) is preferably 0.1 to 55, more preferably 1 to 50, and particularly preferably based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B). Is 2-40.

  When the product stabilizer is contained, the content (% by weight) is preferably 0.01 to 20, more preferably 0.05 to, based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B). 15, particularly preferably 0.1-10.

  The form of the antifoaming agent of the present invention may be liquid or solid, and in the case of solid, it is preferable to use animal and vegetable oil (A) having a melting point of 23 to 37 ° C.

  The antifoaming agent of the present invention comprises animal and vegetable oil (A) and animal and vegetable wax (B) {first invention}, or animal and vegetable oil (A), animal and vegetable wax (B) and natural surfactant (C) {second invention}. In addition, the production method is not limited as long as it contains water and / or a product stabilizer as required, but it is preferable that these components are uniformly mixed.

  When uniformly mixing the components of the antifoaming agent of the present invention, it is preferable to mix at a temperature equal to or higher than the melting point of the animal and plant wax (B).

  The antifoaming agent of the present invention is effective for water-based foaming liquid {for example, drainage, white paper making process, water-based paint, etc.}, but particularly effective for water-based paint.

  The amount of the antifoaming agent of the present invention can be appropriately increased or decreased depending on the composition, temperature, concentration, etc. of the foaming liquid (additive), but is 0.01 based on the weight of the foaming liquid (additive). Is preferably 10 to 10% by weight, more preferably 0.05 to 5% by weight, and particularly preferably 0.1 to 2% by weight.

Unless otherwise specified, “parts” means parts by weight and “%” means percent by weight.
<Example 1>
In a container that can be heated, stirred and cooled, 98 parts of animal and vegetable oil (a1) {rapeseed oil, Nissin Oilio Group, melting point -6 ° C} and animal and plant wax (b1) {carnauba wax, refined fine-grain carnauba S Toa Kasei Co., Ltd., melting point 83 ° C.} 2 parts were stirred and mixed at 150 ° C., and then cooled to 30 ° C. with stirring to obtain a mixed solution. This mixed solution is transferred to a stainless steel container, and homogenized by stirring at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, Taitec Co., Ltd.). Obtained.

<Example 2>
"Animal and vegetable oil (a1) 98 parts" and "Animal and vegetable wax (b1) 2 parts" were replaced with "Animal and vegetable oil (a2) {Cotton seed oil, Nisshin Oillio Group, melting point 0 ° C} 92 parts" and "Animal and vegetable wax (b2). ) {Candelilla wax, refined candelilla wax MK-2, Yokoseki Yushi Co., Ltd., melting point 70 ° C} 8 parts ", except that the antifoaming agent (2) of the present invention was used in the same manner as in Example 1. Obtained.

<Example 3>
"Animal and vegetable oil (a1) 98 parts" and "Animal and vegetable wax (b1) 2 parts" were replaced with "Animal and vegetable oil (a3) {Sunflower oil, Nisshin Oillio Group, melting point -17 ° C} 95 parts" and "Animal and vegetable wax. (B3) The antifoaming agent (3) of the present invention was obtained in the same manner as in Example 1, except that it was changed to {part of wood wax, Sankei Industry Co., Ltd., melting point 53 ° C} 5 parts}.

<Example 4>
In a container that can be heated, stirred and cooled, 98 parts of animal and vegetable oil (a2), 2 parts of animal and vegetable wax (b1) and 2 parts of natural surfactant (c1) {lecithin, J-Oil Mills Co., Ltd.} After stirring and mixing at 150 ° C., the mixture was cooled to 30 ° C. with stirring to obtain a mixed solution. This mixed solution is transferred to a stainless steel container, and homogenized by stirring at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, Taitec Co., Ltd.). Obtained.

<Example 5>
"Animal and vegetable oil (a2) 98 parts", "Animal and vegetable wax (b1) 2 parts" and "Natural surfactant (c1) 2 parts" were combined with "Animal and vegetable oil (a3) 92 parts" and "Animal and vegetable wax (b2) 8". Part "and" natural surfactant (c2) {saponin, Kirayanin P-20, Maruzen Pharmaceutical Co., Ltd.} 8 parts ", in the same manner as in Example 4, the antifoaming agent (5) of the present invention Got.

<Example 6>
"Animal and vegetable oil (a2) 98 parts", "Animal and vegetable wax (b1) 2 parts" and "Natural surfactant (c1) 2 parts" were combined with "Animal and vegetable oil (a4) {Corn oil, Nisshin Oillio Group, Defoaming agent of the present invention in the same manner as in Example 4 except that the melting point was -17 ° C} 95 parts, 5 parts of animal and vegetable wax (b3) and 8 parts of natural surfactant (c1). (6) was obtained.

<Example 7>
"Animal and vegetable oil (a2) 98 parts", "Animal and vegetable wax (b1) 2 parts" and "Natural surfactant (c1) 2 parts" were combined with "Animal and vegetable oil (a5) {soybean oil, Nisshin Oillio Group, The antifoaming agent of the present invention was the same as in Example 4 except that the melting point was −96 ° C.} 96 parts ”,“ 4 parts of animal and plant wax (b1) ”and“ 8 parts of natural surfactant (c1) ”. (7) was obtained.

<Comparative example>
Based on the Example of patent document 1, the antifoamer for a comparison was obtained using animal and vegetable oil (a2) {soybean oil}, oleic acid, potassium hydroxide, ethylene oxide, and propylene oxide.

<Evaluation Example 1>
Using the antifoaming agents obtained in Examples 1 to 7 and Comparative Examples, the antifoaming property was evaluated by the following method.

1. Preparation of effervescent test solution Polyoxyethylene lauryl ether sulfate sodium salt {Calibon EN-200, Sanyo Chemical Industries, Ltd., "Caribbon" is a registered trademark of the company. } 5 parts and 95 parts of ion-exchanged water were uniformly stirred and mixed to obtain a foaming test solution 1.

2. Defoaming test method 750 ml of foaming test liquid 1 is placed in a glass cylinder (hereinafter referred to as a foam tube), and the temperature of the foaming test liquid is adjusted to 40 ° C. (foaming with reference to the liquid surface at 40 ° C.). Measure the height.) Then, using a pump, discharge the foaming aqueous solution from the bottom of the foaming tube at 3,000 ml / min and drop it from the top 150 mm of the foaming tube to the foaming test solution water surface. When the foam height reaches 100 mm, add 375 μl of sample (ie, antifoaming agent) with a micropipette and then continue to circulate the foaming test solution to start the foam height test. Measurements were taken after 15 seconds, 1 minute and 5 minutes later. The test results are shown in Table 1. A smaller numerical value means higher defoaming properties and is preferable.

−：１５秒後で試験を中止した。

-: The test was stopped after 15 seconds.

  The antifoaming agent of the present invention showed an excellent antifoaming property as compared with a comparative antifoaming agent.

<Evaluation Example 2>
Using the antifoaming agents obtained in Examples 1 to 7 and Comparative Examples, emulsion paints were prepared by the following method, and these emulsion paints were evaluated for antifoaming properties and repellency by the following methods. The test results are shown in Table 3.

1. Preparation of Emulsion Base Paint Using an Excel Auto Homogenizer (Nippon Seiki Co., Ltd., Model ED) equipped with impeller blades with the raw material composition shown in Table 2, it was made into a paint by gliding and letting down. The obtained paint was confirmed to have no particles of 5 microns or more by a dispersity test [JIS K5600-2-5: 1999 (corresponding to ISO 1524: 1983)].
Next, this paint was diluted with water to obtain 77 KU (25 ° C.) with a Stormer viscometer [JIS K5600-2-2: 1999 (corresponding to ISO 2431: 1993)] to obtain an emulsion base paint.

「タイペーク」、「ボンコート」、「テキサノール」は登録商標である。

“Taipeke”, “Boncoat” and “Texanol” are registered trademarks.

2. Preparation of emulsion paint To 100 parts of emulsion base paint, add 1 part of sample (ie antifoaming agent) and stir and mix with Excel Auto Homogenizer equipped with impeller blades at 15-25 ° C, 2000 rpm for 3 minutes. An emulsion paint was obtained.
Moreover, the emulsion paint for evaluation (blank) was obtained like the above except not adding a sample (namely, antifoamer).

3. Evaluation of defoaming property and repellency After degreasing a tin plate (thickness 0.5 mm, 20 × 30 cm) with acetone / cloth, and applying an emulsion paint for evaluation with a roller so that the wet film thickness becomes 200 microns, It was dried for 1 day in a control room adjusted to 25 ° C. and 60% relative humidity, the surface of the coating film was observed, and defoaming properties and repellency were evaluated according to the following criteria (immediately after preparation).
The emulsion paint for evaluation was stored in an airtight container at 40 ° C. for one month (aging), and then stirred and mixed at 15 to 25 ° C. and 2000 rpm for 3 minutes with an Excel auto homogenizer equipped with impeller blades. Thus, an emulsion paint for aging evaluation was obtained, and the antifoaming property and repellency were similarly evaluated (after aging).

Defoaming property: The number of bubble marks was visually confirmed. (A smaller value means higher defoaming properties and is preferable)
Repelling: The number of repelling or cratering marks was confirmed visually. (A smaller number means less repelling and is preferable)

  When the antifoaming agent of the present invention was used, excellent antifoaming properties were exhibited as compared with a coating using a comparative antifoaming agent. Moreover, there was little occurrence of repelling.

The antifoaming agent of the present invention is suitable for processing and wastewater treatment in fields such as the chemical industry, food industry, petroleum industry, textile industry, pulp and paper industry, civil engineering / architecture industry, and pharmaceutical industry.

Claims (5)

Consisting only of animal and vegetable oil (A) and animal and plant wax (B), or consisting only of animal and vegetable oil (A) and animal and plant wax (B) and water and / or product stabilizers,
The melting point of animal and vegetable oil (A) is -17 to 0 ° C, and the melting point of animal and plant wax (B) is 53 to 83 ° C.
Based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B), the content of the animal and vegetable oil (A) is 92 to 99.9% by weight, and the content of the animal and vegetable oil (B) is 0.1 to 8% by weight. % Antifoaming agent characterized by being%. It consists only of animal and vegetable oil (A), animal and vegetable wax (B) and natural surfactant (C), or animal and vegetable oil (A), animal and vegetable wax (B) and natural surfactant (C), water and / or Consisting only of product stabilizers,
The melting point of animal and vegetable oil (A) is -17 to 0 ° C, and the melting point of animal and plant wax (B) is 53 to 83 ° C.
The natural surfactant (C) is lecithin or saponin,
Based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B), the content of the animal and vegetable oil (A) is 92 to 99.9% by weight, and the content of the animal and vegetable oil (B) is 0.1 to 8% by weight. % Antifoaming agent characterized by being%. The antifoaming agent according to claim 1 or 2 , wherein the content of the natural surfactant (C) is 0.9 to 10% based on the total weight of the animal and vegetable oil (A) and the animal and vegetable wax (B). Animal and vegetable oils (A) are, rapeseed oil, soybean oil, corn oil, safflower oil, olive oil, sesame oil, cottonseed oil, sunflower oil, claim 1-3 is at least one selected from the group consisting of peanut oil, and whale oil An antifoaming agent as described in 1. The animal and plant wax (B) is selected from the group consisting of carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, yellowfin wax, urushi wax, sugarcane wax, palm wax, beeswax, insect wax, whale wax, shellac wax and lanolin wax. The antifoaming agent according to any one of claims 1 to 4 , which is at least one kind.