JP2006068678A - Antifoaming agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an antifoaming agent which exhibits an excellent anti-foaming property even at a low temperature, and has an excellent dynamic surface tension reduction ability. <P>SOLUTION: This antifoaming agent is the one in which a polyoxyalkylene compound represented by formula (1) is an essential ingredient, wherein, R is an 8-18C acyl group, N is nitrogen atom, H is hydrogen atom, AO is a 2-3C oxyalkylene group, M is a 1-2C hydrocarbon group, (q) represents an integer of 0-6, (m) is an integer of 1-30, (n) is an integer of 1-3, and the total number of AOs is 20-70. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an antifoaming agent. More particularly, the present invention relates to an antifoaming agent particularly suitable for water-based paints.

  Antifoaming agents for cationic electrodeposition coatings include polypropylene glycol having a number average molecular weight of 500 to 1500 (Patent Document 1), alkylated at both ends of a polyether (Patent Document 2), and Air Products Co., Ltd. Acetylene glycol (Non-patent Document 1) and the like are known.

JP-A-64-069678 Japanese Patent Publication No. 6-45772 (USP 4891111) Surfactant for water-based paints “Surfinol” by Ichiro Yamazaki, magazine “Painting and paints”, August 2000 (No. 607) p. 77, paint publisher

The antifoaming agent described in Patent Document 1 or 2 has inferior defoaming performance, and has a problem that it tends to foam particularly at low temperatures. In addition, the acetylene glycol described in Non-Patent Document 1 needs to be added in advance when preparing paints, inks, and the like. If added in a subsequent process, there is a problem that repellency and the like are caused.
That is, an object of the present invention is to provide an antifoaming agent that is excellent in antifoaming properties and has no harmful effects such as repelling.

なお、Ｒは炭素数８〜１８のアシル基、Ｎは窒素原子、Ｈは水素原子、ＡＯは炭素数２〜３のオキシアルキレン基、Ｍは炭素数１〜２の炭化水素基、ｑは０〜６の整数、ｍは１〜３０の整数、ｎは１〜３の整数を表し、ＡＯの合計数は２０〜７０である。 The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems. That is, the feature of the antifoaming agent of the present invention is that the polyoxyalkylene compound represented by the general formula (1) is an essential component.

R is an acyl group having 8 to 18 carbon atoms, N is a nitrogen atom, H is a hydrogen atom, AO is an oxyalkylene group having 2 to 3 carbon atoms, M is a hydrocarbon group having 1 to 2 carbon atoms, and q is 0 The integer of -6, m represents the integer of 1-30, n represents the integer of 1-3, and the total number of AO is 20-70.

  The antifoaming agent of the present invention has extremely excellent antifoaming properties. Furthermore, there is no harmful effect such as repellency even when used in paints and inks. In particular, the problem of easy foaming even at low temperatures can be solved.

The general formula (1) will be described.
Examples of the acyl group (R) having 8 to 18 carbon atoms include n-caproyl, 2-ethylhexoyl, lauroyl, myristaroyl, palmitoyl, stearoyl, oleoyl, and isostearoyl. A plurality of R may be all the same or a part or all of them may be different.

  Examples of the oxyalkylene group having 2 to 3 carbon atoms (AO) include oxyethylene and oxypropylene. The plurality of AOs may all be the same, or some or all of them may be different. In particular, from the viewpoint of defoaming properties, it is preferable to contain oxypropylene, and more preferably a mixture of oxypropylene and oxyethylene. In the case of a mixture of oxyethylene and oxypropylene, the content ratio (% by weight) of oxypropylene is preferably 50 to 90, more preferably 53 to 86, based on the total weight of AO (total weight of oxyalkylene groups). Especially preferably, it is 56-83, Most preferably, it is 60-80.

  When (AO) n or (AO) m contains a plurality of types of oxyalkylene groups, the bonding order of these oxyalkylene groups (block, random, and combinations thereof) is not limited, but is block or block It is preferable to include a combination of a shape and a random shape.

Examples of the hydrocarbon group having 1 to 2 carbon atoms (M) include methylene, ethylene, ethylenylene (—CH═CH—), ethylidene (CH ₃ CH <), vinylidene (CH ₂ ═C <) and acetylene (—C≡). C-) is included. The plurality of M may all be the same, or some or all of them may be different. From the viewpoint of harmful effects such as repelling, it is preferable to contain methylene.

  q is preferably an integer of 0 to 6, more preferably an integer of 1 to 5, particularly preferably an integer of 1 to 4, and most preferably an integer of 1 to 3. Within this range, bad effects such as repelling and antifoaming properties are further improved.

m is preferably an integer of 1 to 30, more preferably an integer of 2 to 28, particularly preferably an integer of 3 to 27, and most preferably an integer of 4 to 25. In this range, the defoaming property is further improved.
n is preferably an integer of 1 to 3, and more preferably 1 or 2. In this range, the defoaming property is further improved. Two (AO) m may be the same or different.
The plurality of (AO) n may be the same or different.
When q is 2 or more, a plurality of {-M- (AO) n-N (R)-(AO) n} may be the same or different.

  The total number of oxyalkylene groups AO is preferably 20 to 70, more preferably 22 to 65, particularly preferably 23 to 60, and most preferably 25 to 55. If it is within this range, there is a tendency that adverse effects such as antifoaming properties and repelling are further improved.

The clouding point (° C.) of the polyoxyalkylene compound represented by the general formula (1) is preferably 20 to 60, more preferably 22 to 58, particularly preferably 23 to 57, and most preferably 25 to 50. Within this range, adverse effects such as defoaming and repelling are further improved.
The cloud point means a physical property value that is a measure of the hydrophilicity / hydrophobicity of the surfactant. The higher the cloud point, the higher the hydrophilicity. ISO 1065-1975 (E), “ethylene oxide non-ion It is measured according to “Measurement Method B” in “Surfactant-Cloud Point Measurement Method”. That is, a sample is put into a 25% by weight aqueous solution of butyl diglycol (3,6-oxadecyl alcohol: butanol EO2 molar adduct) so as to have a concentration of 10% by weight and dissolved uniformly (usually at 25 ° C. Dissolve, but if not, cool until clear liquid). Next, about 5 cc of this sample solution is taken into a test tube having an outer diameter of 18 mm, a total length of 165 mm, and a wall thickness of about 1 mm, and a thermometer with a diameter of about 6 mm, a length of about 250 mm, and a half degree scale is placed in the sample solution. While stirring, the sample solution is made cloudy by raising the temperature at 1.5 ± 0.5 ° C./min. Thereafter, while stirring, the sample solution is cooled at 1.0 ± 0.2 ° C./min to read the temperature at which the sample solution becomes completely transparent, and this is taken as the cloud point.

  The dynamic surface tension (0.1 wt% aqueous solution, 20 Hz, 25 ° C.) (mN / m) (mN / m) of the polyoxyalkylene compound represented by the general formula (1) is preferably 30 to 50, more preferably 31 to 47. Especially preferably, it is 32-45. Within this range, adverse effects such as defoaming and repelling are further improved.

Here, the dynamic surface tension will be briefly described.
When a new interface is formed with an aqueous solution containing a surfactant or the like, it takes time for the surface tension to reach equilibrium. The ring method and the plate method are well known as surface tension measurement methods, but these measure the surface tension that reaches equilibrium (static surface tension). On the other hand, what is dynamic surface tension? It is the surface tension at the gas-liquid interface in the process of reaching equilibrium, and is measured by a method called the Maximum Bubble Pressure Method or the Differential Maximum Bubble Pressure Method, etc. {Reference: Journal of Chemical Society of 121, p858 (1922); Journal of Colloid and Interface Science, 166, p6 (1944); ASTM D3825-90, etc.}, when a new interface (surface) is formed, the surface tension at the interface ( mN / m) in milliseconds. For example, a dynamic surface tension of 20 Hz means a surface tension after 1/20 (50 milliseconds) after a new interface is formed. Currently, automatic surface tension automatic measuring machines based on the maximum bubble pressure method have been developed. Kyowa Interface Science Co., Ltd. (automatic / dynamic surface tension meter BP-D3, etc.), KRUSS (bubble pressure type dynamic surface tension meter Cruz BP-2 etc.).

  In the present invention, the dynamic surface tension is as follows: sample concentration: 0.1% by weight, dilution medium: ion exchange water, gas for generating bubbles: dry air, measurement time interval: 500 milliseconds, measurement temperature; 25.0 ± 0 Measured by the maximum bubble pressure method at 2 ° C. Note that the dynamic surface tension of deionized water was measured under the same conditions as a blank, and the diameter of the capillary (dry air discharge pipe) was in the range of 73.0 to 72.0 mN / m at 20 to 0.05 Hz. Select a value.

  Examples of the polyoxyalkylene compound represented by the general formula (1) include compounds represented by the following chemical formulas. Here, po represents an oxypropylene group, eo represents an oxyethylene group, me represents a methylene group, and et represents an ethylene group.

  Among these, the polyoxyalkylene compound represented by the formula (2), (3), (5) or (6) is preferable, and the polyoxyalkylene represented by the formula (3) or (5) is more preferable. A compound.

  The polyoxyalkylene compound represented by the general formula (1) includes the chemistry of a monoalkylamide (a1), a C2-C3 alkylene oxide (a2), and a C1-C2 dihalogenated hydrocarbon (a3). Those having structures that can be produced by reaction are included. That is, a polyoxyalkylene compound having a structure that can be produced by such a chemical reaction may cause a distribution in an oxyalkylene group or the like. In this case, strictly speaking, it becomes a mixture of a plurality of types of polyoxyalkylene compounds. A polyoxyalkylene compound represented by the general formula (1) is included in the mixture. Even in this case, the manufacturing method is not limited.

  And as usage-amount (mol part) of alkylene oxide (a2), 5-30 are preferable with respect to 1 mol part of monoalkylamide (a1), More preferably, it is 7-27, Most preferably, it is 8-26. Most preferably, it is 10-25. Within this range, the antifoaming property is further improved.

  Moreover, as usage-amount (mol part) of a C1-C2 dihalogenated hydrocarbon (a3), 0.5-0.9 are preferable with respect to 1 mol part of monoalkylamide (a1), More preferably Is 0.53 to 0.87, particularly preferably 0.57 to 0.83, and most preferably 0.6 to 0.8. Within this range, adverse effects such as defoaming and repelling are further improved.

  As the monoalkylamide (a1), an amide having 8 to 18 carbon atoms can be used, and n-caprylamide, 2-ethylhexylamide, laurylamide, myristylamide, palmitylamide, stearylamide, isostearylamide and oleylamide Etc.

As alkylene oxide (a2), C2-C3 alkylene oxide etc. can be used, and ethylene oxide (EO) and propylene oxide (PO) are mentioned. Among these, from the viewpoint of defoaming property and the like, a mixture of PO and PO and EO is preferable, and a mixture of PO and EO is more preferable.
Moreover, when using multiple types of alkylene oxide, there is no restriction | limiting in the order (block shape, random shape, and these combination) made to react, However, It is preferable that the combination of block shape or block shape and random shape is included.
When EO and PO are used, the use ratio (% by weight) of PO is preferably 50 to 90, more preferably 53 to 86, particularly preferably 56 to 83, and most preferably 60, based on the total weight of alkylene oxide. ~ 80.

  As the dihalogenated hydrocarbon (a3), a dihalogenated alkyl having 1 to 2 carbon atoms or the like can be used. Examples of the dihalogenated alkyl include dichloromethane, dibromomethane, 1,2-dichloroethane, 1,2-dibromoethane, 1,1-dichloroethane, 1,1-dibromoethane, 1,2-dichloroethylene, 1,2-dibromoethylene, Examples include 1,1-dichloroethylene, 1,1-dibromoethylene, dichloroacetylene, and dibromoacetylene. These may be used alone or in combination.

The polyoxyalkylene compound represented by the general formula (1) can be obtained by reacting a monoalkylamide (a1), an alkylene oxide (a2) and a dihalogenated hydrocarbon (a3). As the reaction method, the following method can be applied.
That is, (a1) and (a2) are first reacted to obtain a reaction product (a12). Next, (a12) and (a3) are reacted to obtain a reaction product (a123). Next, this is a method of further reacting with (a2) to obtain the polyoxyalkylene compound represented by the general formula (1).

  Reaction of monoalkylamide (a1) with alkylene oxide (a2) and reaction product (a123) with (a2) (hereinafter abbreviated as reaction with alkylene oxide (a2)). } May be carried out in any form such as non-catalytic polymerization, anionic polymerization, cationic polymerization or coordination anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.

  A reaction catalyst can be used for the reaction with the alkylene oxide (a2). As the reaction catalyst, a conventionally used alkylene oxide addition reaction catalyst or the like can be used. Alkali metal or alkaline earth metal hydroxides (potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (Potassium methylate and cesium ethylate), alkali metal or alkaline earth metal carbonates (potassium carbonate, cesium carbonate, barium carbonate, etc.), tertiary amines having 3 to 24 carbon atoms (trimethylamine, trioctylamine, trimethylamine) Ethylenediamine and tetramethylethylenediamine) and Lewis acids (such as stannic chloride and boron trifluoride) are used. Of these, alkali metal hydroxides and tertiary amine compounds are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.

  When a reaction catalyst is used, the amount used (% by weight) is 0.01 to 2 based on the total weight of the monoalkylamide (a1) or reaction product (a123) and the alkylene oxide (a2). Preferably, it is 0.05 to 1, particularly preferably 0.1 to 0.6.

When using a reaction catalyst, it is preferable to remove the reaction catalyst from the reaction product. As the method, an alkali adsorbent such as a synthetic aluminosilicate {for example, trade name: Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd. } (JP-A-53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (JP-B-49-14359, etc.), a method using an ion exchange resin (JP-A-51 No. 23211, etc.) and a method of filtering a carbonate formed by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).
As the end point of the removal of the reaction catalyst, the CPR (Controlled Polymerization Rate) value described in JIS K1557-1970 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. is there.

As the reaction vessel, it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. The reaction atmosphere is preferably an atmosphere of inert gas (such as argon, nitrogen and carbon dioxide) in which the inside of the reaction apparatus is vacuumed or dried before introducing the alkylene oxide (a2) into the reaction system. Moreover, as reaction temperature (degreeC), 80-150 are preferable, More preferably, it is 90-130. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.
The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 5 minutes, the reaction end point is set when the decrease in the reaction pressure (gauge pressure) is 0.001 MPa or less. The required reaction time is usually 2 to 8 hours.

  Reaction of reaction product (a12) of monoalkylamide (a1) and alkylene oxide (a2) with dinohalogenated hydrocarbon (a3) (hereinafter abbreviated as reaction with halide). } Is a dehydrohalogenation reaction with a basic substance (Williamson synthesis reaction: the reaction is driven by neutralizing the hydrogen halide sequentially generated during the reaction with a basic substance). Basic substances that can be used for this reaction include alkali metal or alkaline earth metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, water Calcium oxide, barium hydroxide, etc.), alkali metal alcoholates (C 1-2: sodium methylate, potassium ethylate, etc.), alkali metal or alkaline earth metal carbonates (sodium carbonate, potassium carbonate, barium carbonate, etc.) ) And the like. Of these, alkali metal hydroxides are preferred, sodium hydroxide and potassium hydroxide are more preferred, and sodium hydroxide is particularly preferred.

The use amount (mol%) of the basic substance used for the reaction with the halide is preferably 200 to 250, more preferably 205 to 235, particularly preferably based on the use amount (mol) of the dihalide (a3). 210-220.
After completion of the reaction, it is preferable to remove the produced neutralized salt and the remaining basic substance. Examples of the method include (1) an extraction method using an organic solvent and (2) a salting out method using sodium chloride.

In the extraction method (1), water and an organic solvent (one that is not soluble in water such as hexane, toluene, xylene, etc.) are added to the reaction product, and the reaction product is shaken by shaking. And the basic substance is separated into an aqueous layer. The organic solvent layer is washed with deionized water or the like. A suitable volume ratio of reaction product: water: organic solvent is approximately 1: 1: 1.
In the salting-out method of (2), the reaction product is shaken by adding approximately the same volume of water and an appropriate amount (3 to 10% by weight of sodium chloride) of sodium chloride to the reaction product and shaking. In this method, the basic substance is separated into an aqueous layer by being precipitated from the layer.
In any case, it is preferable to finally remove the basic substance by using an alkali adsorbent such as synthetic aluminosilicate (for example, Kyoward 700).
As the end point of the removal of the basic substance, the CPR (Controlled Polymerization Rate) value described in JIS K1557-1970 is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. It is. It is also preferable to remove moisture. In this case, dehydration is performed at 100 to 130 ° C. under reduced pressure (100 to 1 mmHg) for 1 to 2 hours. The water content in the product is preferably 0.5% by weight or less, more preferably 0.05% by weight or less.

As the reaction vessel, it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. The reaction atmosphere is preferably an atmosphere of inert gas (argon, nitrogen, carbon dioxide, etc.) in which the inside of the reaction apparatus is vacuumed or dried before introducing the dihalogenated hydrocarbon (a3) into the reaction system. Moreover, as reaction temperature (degreeC), 60-120 are preferable, More preferably, it is 70-100. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.
The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 15 minutes, the reaction end point is set when the decrease in the reaction pressure (gauge pressure) is 0.001 MPa or less. The required reaction time is usually 2 to 10 hours.

In addition to the polyoxyalkylene compound represented by the general formula (1), the antifoaming agent of the present invention may contain a surfactant and / or other solvent, if necessary.
As the surfactant, nonionic, cationic, anionic or amphoteric surfactants can be used.
Nonionic surfactants include alkylphenol alkylene oxide adducts, alcohol alkylene oxide adducts, polyhydric alcohol fatty acid esters, alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and acetylene glycol alkylene oxide additions. Body and polyoxyalkylene-modified silicone.
Examples of the cationic surfactant include amine salts, quaternary ammonium salts, and alkylene oxide addition type ammonium salts.
Examples of the anionic surfactant include fatty acid salts, α-olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfates, N-acyl alkyl taurates, and alkyl sulfosuccinates. It is done.
Examples of amphoteric surfactants include alanine, imidazolinium betaine, amide betaine, and betaine acetate.

  Product names available from the market as surfactants include SN Wet 123 and 970 (San Nopco); Lionol TDL-30, 50 and 70 (Lion); Ionette T-80C, S-80 and DO-600, etc. (Sanyo Chemical Industry Co., Ltd.); Softanol 30, 30S, MES-5, etc. (Nippon Shokubai Co., Ltd.); Surfynol 104, 440, Emblem Gem AD01, etc. (Air Products), and the like.

  When other surfactant is contained, the content (% by weight) is preferably 20 to 1, more preferably 18 to 3, based on the weight of the polyoxyalkylene compound represented by the general formula (1). Especially preferably, it is 15-5.

As other solvents, water, water-soluble organic solvents, and the like can be used.
Examples of water include ion exchange water, distilled water, tap water, and industrial water.
Examples of the water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), and ethers having 4 to 6 carbon atoms (ethyl). Cellsolve and butylcellosolve) and ether esters having 4 to 8 carbon atoms (such as butylcellosolve acetate).
When other solvent is contained, the content (% by weight) is preferably 20 to 1, more preferably 17 to 3, particularly preferably based on the weight of the polyoxyalkylene compound represented by the general formula (1). Preferably it is 15-5.

The antifoaming agent of the present invention exhibits excellent antifoaming properties for aqueous liquids, but is particularly suitable for aqueous paints.
Examples of water-based paints include paper coating paints, architectural paints, building material paints, automobile paints, ship paints, and water-based inks.
Of these water-based paints, they are suitable for automobile paints, particularly cationic electrodeposition paints.

Depending on the type of cationic resin used as the main raw material, cationic electrodeposition paints include epoxy-based, acrylic-based and polybutadiene-based coatings. The antifoaming agent of the present invention has excellent antifoaming properties for all types. To demonstrate.
The cationic electrodeposition paint consists of 1) a cationic resin emulsion, 2) a pigment paste, and 3) an aqueous medium. The three are mixed immediately before being put into the electrodeposition coating bath, and are mixed uniformly for coating. Is done.
1) Cationic resin emulsion is obtained by (1) cationically modified resin, (2) its curing agent (such as blocked isocyanate), (3) neutralizing agent {inorganic acid (such as hydrochloric acid and phosphoric acid nitrate) or Organic acids (formic acid, acetic acid, lactic acid, etc.)}, (4) Dispersion aid {Organic solvents (ethylene glycol monobutyl ether, ethylene glycol mono 2-ethylhexyl ether, dipropylene glycol monobutyl ether, methanol, ethanol, etc.) and surfactants (Nonionic surfactant such as polyoxyethylene 2-ethylhexyl ether)} or the like is dispersed in distilled water or deionized water.
2) Pigment paste is made of cation-modified resin, dispersion aid and water and pigment (kaolin, talc, aluminum silicate, calcium carbonate, mica, clay, zinc oxide, iron phosphate, aluminum phosphate, zinc molybdate, Aluminum molybdate and zinc phosphomolybdate zinc).
3) The aqueous medium consists of water (such as deionized water) that may contain a dispersion aid if necessary.

The antifoaming agent of the present invention comprises (1) a cationic resin emulsion, (2) a pigment paste, (3) an electrodeposition paint, and (4) a filtrate obtained by ultrafiltration of the electrodeposition paint with an ultrafilter (hereinafter referred to as UF). It may be added to any of the abbreviations “filtrate”.
When added to (1) a cationic resin emulsion or (2) a pigment paste, the addition amount (% by weight) of the antifoaming agent of the present invention is preferably 0.01 to 5, based on the weight of the emulsion or paste, More preferably, it is 0.05-3, Most preferably, it is 0.1-2.
(3) When added to the electrodeposition paint, the addition amount (% by weight) of the antifoaming agent of the present invention is preferably 0.01 to 3, more preferably 0.03, based on the weight of the electrodeposition paint. 2.5, particularly preferably 0.05-2.
(4) When added to the UF filtrate, the addition amount (% by weight) of the present invention is preferably 0.001 to 0.3, more preferably 0.002 to 0.2, based on the weight of the UF filtrate. Most preferably, it is 0.003-0.15.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
<Example 1>
After charging 398 parts (2 mole parts) of lauryl amide {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} into a reaction vessel capable of heating, stirring, cooling, dropping, pressurization and decompression, nitrogen gas is used. The operation of pressurizing to a pressure of 0.4 MPa and discharging to 0.02 MPa (pressurized nitrogen substitution) was repeated three times. Next, the temperature was raised to 130 ° C. while stirring, and dehydration was performed under a reduced pressure of 100 to 5 mmHg. Next, 176 parts (4 mole parts) of EO was added dropwise at 140 to 170 ° C. over 2 hours, and then stirring was continued for 30 minutes at the same temperature to react with the remaining EO to obtain a laurylamide EO adduct.
Thereafter, 88 parts (2.2 mole parts) of water and sodium hydroxide {reagent special grade, manufactured by Sigma-Aldrich Japan Co., Ltd., hereinafter abbreviated as Sigma Corporation} at 50 ° C. or lower are added to the laurylamide EO adduct. An aqueous solution consisting of was added. The temperature was raised with stirring to 130 ° C., and then dehydrated under reduced pressure of 100 to 5 mmHg. Subsequently, the pressure reduction was stopped, and 89.3 parts (1.05 mole parts) of methyl dichloride {reagent special grade, manufactured by Sigma Co., Ltd.} was introduced over 2 hours at 100 to 120 ° C. with stirring. The mixture was further stirred at the same temperature for 2 hours and then cooled to 40 ° C. The obtained reaction mixture is taken into a separating funnel, 500 parts of ion-exchanged water and 500 parts of n-hexane {special grade reagent, manufactured by Sigma Co., Ltd.} are added and shaken, and then left to stand for separation. A hexane layer was obtained. From this n-hexane layer, n-hexane was distilled off at 100 ° C. under reduced pressure of 100 to 5 mmHg to obtain a laurylamide EO adduct dimer.
Next, 586 parts (1 mole part) of laurylamide EO adduct dimer and 3 parts of potassium hydroxide {reagent special grade, manufactured by Sigma Co., Ltd.) were charged into the same reaction vessel, and the temperature was raised to 120 ° C. while stirring. Dehydrated under reduced pressure of ˜5 mmHg. Next, 1160 parts (20 mole parts) of PO was added dropwise at 100 to 120 ° C. over 6 hours, and then stirring was continued at the same temperature for 2 hours to react the remaining EO.
Next, 264 parts (6 mole parts) of EO was added dropwise at 130 to 160 ° C. over 2 hours, and then stirring was continued at the same temperature for 0.5 hours to react the remaining EO.
After cooling to 90 ° C., 20 parts of ion-exchanged water was added, and 35 parts of Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) were added and stirred at the same temperature for 1 hour. Next, at the same temperature, no. Filtered using 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove Kyoward 700, and further dehydrated at 130 ° C. under reduced pressure of 20 to 10 mmHg for 1 hour, and the antifoaming agent of the present invention (dilaurylamide compound) / EO4 mol / PO20 mol / EO6 mol: A1) was obtained.
The cloud point of (A1) (based on measurement method B of ISO 1065-1975 (E); the same applies hereinafter) was 46.0 ° C.

<Example 2>
Into the same reaction vessel as in Example 1, 586 parts (1 mole part) of laurylamide EO adduct dimer obtained in Example 1 and 4 parts of potassium hydroxide {reagent special grade, manufactured by Sigma Co., Ltd.} were added and stirred. The temperature was raised to 120 ° C. while dehydrating under a reduced pressure of 100 to 5 mmHg. Subsequently, 264 parts (6 mol parts) of EO was added dropwise at 140 to 170 ° C. over 3 hours, and then stirring was continued for 30 minutes at the same temperature to react with the remaining EO. Next, 2030 parts (35 mole parts) of PO was added dropwise at 100 to 120 ° C. over 8 hours, and then stirring was continued for 3 hours at the same temperature to react with the remaining PO. Subsequently, decatalysis and dehydration were carried out by Kyoward 700 in the same manner as in Example 1 to obtain an antifoaming agent of the present invention (dilaurylamide compound / EO 10 mol / PO 35 mol: A2). The cloud point of (A2) was 30.0 ° C.

<Example 3>
After charging 567 parts (2 mole parts) of stearylamide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} into a reaction vessel similar to that in Example 1, nitrogen substitution was performed in the same manner as in Example 1, The temperature was raised to 120 ° C. while stirring, and dehydration was performed under a reduced pressure of 100 to 5 mmHg. Next, 264 parts (6 mole parts) of EO was added dropwise at 140 to 170 ° C. over 2 hours, and then stirring was continued for 30 minutes at the same temperature to react with the remaining EO to obtain a stearylamide EO adduct.
Thereafter, an aqueous solution comprising 88 parts (2.2 parts by mole) of sodium hydroxide and 120 parts of water was added to the stearylamide EO adduct at 50 ° C. or less. The temperature was raised while stirring to 120 ° C., and then dehydration was performed at a reduced pressure of 100 to 5 mmHg. Subsequently, the pressure reduction was stopped, and 89.3 parts (1.05 mol parts) of methyl dichloride was introduced over 2 hours at 100 to 120 ° C. with stirring. The mixture was further stirred at the same temperature for 2 hours and then cooled to 40 ° C. The obtained reaction mixture was taken in a separatory funnel, and 600 parts of ion exchange water and 600 parts of n-hexane were added and shaken, and then allowed to stand to obtain an n-hexane layer. From this n-hexane layer, n-hexane was distilled off under reduced pressure at 100 ° C. and 100 to 5 mmHg to obtain a stearylamide EO adduct dimer.
Next, after adding 855 parts (1 mole part) of stearylamide EO adduct dimer and 4 parts of potassium hydroxide to the same reaction vessel, the temperature was raised to 120 ° C. with stirring, and dehydration was performed at a reduced pressure of 100 to 5 mmHg. did. Next, after 2320 parts (40 mole parts) of PO was added dropwise at 100 to 120 ° C. over 7 hours, stirring was continued for 2 hours at the same temperature to react with the remaining PO. Subsequently, decatalysis and dehydration were carried out by Kyoward 700 in the same manner as in Example 1 to obtain an antifoaming agent (distearylamide compound / EO 6 mol / PO 40 mol: A3) of the present invention. The cloud point of (A3) was 27.0 ° C.

<Example 4>
(A3) 3175 parts (1 mol part) obtained in Example 3 and 3 parts of potassium hydroxide obtained in Example 3 and 3 parts of potassium hydroxide were added to a reaction vessel similar to Example 1, and the temperature was raised to 120 ° C. while stirring, and 100 to 5 mmHg. Dehydrated under reduced pressure. Next, 440 parts (10 parts by mole) of EO was added dropwise at 140 to 160 ° C. over 2 hours, and stirring was continued for 0.5 hours at the same temperature to react with the remaining EO. Subsequently, decatalysis and dehydration were carried out in the same manner as in Example 1 to obtain an antifoaming agent (distearylamide compound / EO 6 mol / PO 40 mol / EO 10 mol: A4) of the present invention. The cloud point of (A4) is 42. ° C.

<Example 5>
After charging 1126 parts (4 mole parts) of oleylamide {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} into a reaction vessel similar to that in Example 1, and after substituting with nitrogen in the same manner as in Example 1, The temperature was raised to 110 ° C. while stirring, and dehydration was performed under a reduced pressure of 100 to 5 mmHg. Next, 464 parts (8 mole parts) of PO was added dropwise at 120 to 140 ° C. over 4 hours, and the remaining PO was allowed to react by continuing stirring for 1 hour at the same temperature to obtain an oleylamide PO adduct.
Thereafter, an aqueous solution composed of 256 parts (6.4 parts by mole) of sodium hydroxide and 320 parts of water was added to the oleylamide PO adduct at 50 ° C. or lower. The temperature was raised while stirring to 120 ° C., and then dehydration was performed at a reduced pressure of 100 to 5 mmHg. Subsequently, the pressure reduction was stopped, and 263.5 parts (3.1 mole parts) of methyl dichloride was introduced over 3 hours at 100 to 120 ° C. with stirring. The mixture was further stirred at the same temperature for 2 hours and then cooled to 40 ° C. The obtained reaction mixture was taken in a separatory funnel, and 800 parts of ion-exchanged water and 1000 parts of n-hexane were added and shaken, followed by separation to obtain an n-hexane layer. From this n-hexane layer, n-hexane was distilled off at 100 ° C. under reduced pressure of 100 to 5 mmHg to obtain an oleylamide PO adduct tetramer.
Next, 1626 parts (1 mole part) of oleylamide EO adduct tetramer and 5 parts of potassium hydroxide were added to the same reaction vessel, and then the temperature was raised to 120 ° C. with stirring, under reduced pressure of 100 to 5 mmHg. Dehydrated. Subsequently, 1740 parts (30 mole parts) of PO was added dropwise at 100 to 120 ° C. over 7 hours, and then stirring was continued at the same temperature for 2 hours to react the remaining PO. Subsequently, 176 parts (4 mole parts) of EO was added dropwise at 140 to 160 ° C. over 2 hours, and then stirring was continued at the same temperature for 0.5 hours to react the remaining EO. Next, decatalysis and dehydration were carried out using Kyoward 700 in the same manner as in Example 1 to obtain an antifoaming agent (tetraoleylamide compound / PO 36 mol / EO 4 mol: A5) of the present invention. The cloud point of (A5) was 35.0 ° C.

<Example 6>
(A5) 3542 parts (1 mole part) obtained in Example 5 in a reaction vessel similar to Example 1
After adding 4 parts of potassium hydroxide, the temperature was raised to 120 ° C. with stirring, and dehydration was performed under a reduced pressure of 100 to 5 mmHg. Next, a mixture of 232 parts (4 mole parts) of PO and 176 parts (4 mole parts) of EO was dropped over 140 hours at 140 to 160 ° C., and then the remaining EO and PO were reacted by continuing stirring at the same temperature for 1 hour. I let you. Subsequently, decatalysis and dehydration were carried out by Kyoward 700 in the same manner as in Example 1 to obtain an antifoaming agent of the present invention (tetraoleylamide compound / PO 36 mol / EO 4 mol / EO, PO 4 mol each: A6). The cloud point of (A6) was 43.0 ° C.

<Comparative Example 1>
After adding 134 parts (1 mol part) of dipropylene glycol and 3 parts of potassium hydroxide to the same reaction vessel as in Example 1, dehydration was performed at 80 ° C. under reduced pressure of 20 to 10 mmHg, and then 1160 parts of PO (20 Mol part) was added dropwise at 100 to 120 ° C. in about 7 hours. Further, the temperature was kept at the same temperature for about 3 hours to react the remaining PO. Subsequently, 220 parts (5 mol parts) of EO was added dropwise at 140 to 160 ° C. in about 2 hours. Further, the remaining EO was reacted for about 0.5 hours at the same temperature. According to Example 1, it was treated with 40 parts water / 150 parts Kyoward 700 and dehydrated to obtain a comparative antifoaming agent (dipropylene glycol / PO 20 mol / EO 5 mol: B1). The cloud point of (B1) was 40.0 ° C.

<Comparative example 2>
An aqueous solution consisting of 1514 parts (B1) (1 part by mole), 88 parts (2.2 parts by mole) sodium hydroxide and 120 parts of water was added to the same reaction vessel as in Example 1. The temperature was raised while stirring to 120 ° C., and then dehydration was performed at a reduced pressure of 100 to 5 mmHg. Subsequently, decompression was stopped, and 105 parts (2.04 mole parts) of methyl chloride was added dropwise over 2 hours at 100 to 120 ° C. with stirring. Furthermore, after making it react at the same temperature for 0.5 hour, the water washing of the reaction product was repeated 5 times using the separating funnel. Subsequently, the mixture was treated with 30 parts of Kyoward 700 in the same manner as in Example 1 to obtain a comparative antifoaming agent (dipropylene glycol / PO 20 mol / EO 5 mol / methyl chloride 2 mol: B2). The cloud point of (B3) was 29.5 ° C.

<Comparative Example 3>
Acetylene glycol {trade name: Surfynol-104, manufactured by Air Products Co., Ltd.} was used as a comparative surfactant (B2).

With respect to the antifoaming agents (A1) to (A6) of the present invention and the antifoaming agents (B1) to (B3) for comparison, the antifoaming properties of the UF filtrate obtained from the cationic electrodeposition coating and the cationic electrodeposition coating The solubility was evaluated, and the results are shown in Table 1.
The dynamic surface tension is also shown in Table 1.
<Surface tension reducing ability (dynamic surface tension)>
About measurement aqueous solution which weighed 0.20 g of evaluation sample and made 200.0 g with deionized water, at 25 ± 0.2 ° C., using a bubble pressure type dynamic surface tension meter Cruz BP-2 manufactured by Cruz, The surface tension at 20 Hz was measured (gas for generating bubbles: dry air, measurement time interval: 500 milliseconds). As a blank, the dynamic surface tension of deionized water without an antifoaming agent was measured under the same conditions, and a capillary (dry air discharge was used so that it was within a range of 73.0 to 72.0 mN / m at 20 to 0.05 Hz. The diameter value of the tube was selected.
The smaller the dynamic surface tension value at 50 Hz, the better the dynamic surface tension reducing ability.

<Evaluation of antifoaming property of cation electrodeposition paint for UF filtrate>
Bowenix Excel 1100 {epoxy high corrosion resistance, lead-free type, manufactured by Nippon Paint Co., Ltd.}: deionized water = 2: 1 (weight ratio) was uniformly mixed to obtain an electrodeposition paint base for evaluation.
After adding 0.1 part of the evaluation sample to 100 parts of the electrodeposition paint base for evaluation and stirring uniformly to evaluate the solubility, the temperature of about 1 liter is adjusted to 28 to 20 ° C., manufactured by Asahi Kasei Corporation. About 0.2 liters of UF filtrate was obtained by ultrafiltration with a UF module, KCP-1010. This filtrate was used as a UF filtrate for evaluation.

注１；水に溶解しなかったため、測定できなかった。 The temperature of the evaluation UF filtrate was adjusted to 28 ° C. or 10 ° C. Put it in a 4 Ford cup (conforming to JIS K-5600-2-2) and drop it into a 500 mL glass graduated cylinder (inner diameter: 50.0 mm, cylinder length: 340 mm) placed under 1.0 m, The amount of foam generated (mL) was measured immediately after 2 minutes and 5 minutes after almost the entire amount of the UF filtrate for evaluation dropped on the measuring cylinder. In addition, the defoaming property test was implemented in the room | chamber interior adjusted to the same temperature as the temperature of each UF filtrate for evaluation. Moreover, the result of the blank (UF filtrate from the electrodeposition paint base for evaluation, no evaluation sample added) is also described.
<Evaluation of dispersibility for cationic electrodeposition coatings>
The evaluation was made in the following two stages at 25 ° C. and shown in Table 1.
○: Uniformly dispersed within a short time (within 5 minutes) Δ: It took a long time (30 minutes or more) to uniformly disperse ×: Difficult to disperse or generation of oil droplets and oil film was observed

Note 1: Measurement was not possible because it did not dissolve in water.

  In Table 1, the smaller the defoaming property (foam amount), the better the defoaming property. Therefore, the antifoaming agent (Examples 1-6) of this invention is excellent in the dispersibility to a cationic electrodeposition coating material, and the antifoaming property with respect to a UF filtration addition liquid in any temperature of 28 degreeC and 10 degreeC. It is clear. In the antifoaming agent of Comparative Example 3, an oil film and oil droplets were generated in the evaluation of dispersibility. The oil film and oil droplets can cause defects such as repellency and craters in the cationic electrodeposition coating film. In addition, since the antifoaming agent of Comparative Example 2 requires a long time to uniformly disperse, it tends to cause problems such as repellency depending on the place of addition.

The antifoaming agent of the present invention can be used for any application, but is particularly suitable for water-based paints. In addition, the ability to reduce dynamic surface tension is large, and surface tension can be reduced in a very short time (excellent ability to reduce dynamic surface tension). The wettability can be remarkably improved. Therefore, it is suitable for paints that are applied or printed at high speed (for example, curtain flow coat paints, paper paints and water-based inks), cationic electrodeposition paints, and the like.
Further, the antifoaming agent of the present invention includes, in addition to the antifoaming agent for water-based paints, an antifoaming agent for paper coating paints, an antifoaming agent for aqueous paints, an antifoaming agent for various inks, an antifoaming agent for papermaking processes, It can be used as an antifoaming agent for various synthesis processes (such as for monomer stripping).

Claims (8)

An antifoaming agent comprising a polyoxyalkylene compound represented by the general formula (1) as an essential component.

R is an acyl group having 8 to 18 carbon atoms, N is a nitrogen atom, H is a hydrogen atom, AO is an oxyalkylene group having 2 to 3 carbon atoms, M is a hydrocarbon group having 1 to 2 carbon atoms, and q is 0 The integer of -6, m represents the integer of 1-30, n represents the integer of 1-3, and the total number of AO is 20-70. The antifoaming agent according to claim 1, comprising an oxypropylene group as AO, wherein the content of the oxypropylene group is 50 to 90% by weight based on the total weight of AO. A polyoxyalkylene compound having a structure that can be produced by a chemical reaction of a monoalkylamide (a1), a C2-C3 alkylene oxide (a2), and a C1-C2 dihalogenated hydrocarbon (a3) as an essential component An antifoaming agent characterized by comprising: The antifoaming agent according to any one of claims 1 to 3, wherein the cloud point of the polyoxyalkylene compound {according to measurement method B of ISO 1065-1975 (E)} is 20 to 60 ° C. 5. The antifoaming agent according to claim 1, wherein the polyoxyalkylene compound has a dynamic surface tension {0.1 wt% aqueous solution, 25 ° C.} at 20 Hz of 30 to 50 mN / m. The antifoaming agent according to any one of claims 1 to 5, which is for water-based paints. The antifoaming agent according to any one of claims 1 to 5, which is used for cationic electrodeposition coatings. The antifoaming agent according to any one of claims 1 to 5, wherein the water-based paint is at least one selected from the group consisting of paper coating paint, building paint, building material paint, automobile paint, ship paint, and water-based ink.