JP4565081B2 - Surfactant - Google Patents

Description

The present invention relates to a surfactant. More specifically, the present invention relates to a surfactant that is particularly suitable for water-based paints.

  Conventionally, surfactants used in water-based paints and the like are overwhelmingly anionic surfactants, and for example, dialkyl sulfosuccinates, alkyl sulfonates, ether carboxylates (Patent Document 1) and the like are known. Further, acetylene glycol (Non-patent Document 1) manufactured by Air Products is known.

JP-A-5-51900 Surfactant for water-based paint “Surfinol”, Ichiro Yamazaki, Painting and paint, August 2000 (No. 607), p. 77, Paint publisher

With conventional anionic surfactants, the dynamic surface tension at 50 Hz {0.1% by weight aqueous solution, 25 ° C} can only be reduced to about 50 to 70 mN / m, and acetylene glycol has solubility or dispersibility in water. Since it is low, it must be added in advance when preparing paints, inks, etc., so that it cannot be added in any manufacturing process, and there is a great limitation in terms of use.
That is, an object of the present invention is to provide a surfactant excellent in dynamic surface tension reducing ability and water solubility.

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１２〜３４の整数である。 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 surfactant 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 is an integer of 1-30, n represents the integer of 1-3, and the total number of AO is an integer of 12-34 .

  The surfactant of the present invention has extremely excellent dynamic surface tension reducing ability and water solubility. Therefore, when applied to water-based paints, it can drastically improve the drawbacks of water-based paints (familiarity with the coated surface during high-speed coating, wettability, etc.) and excellent handling (no restrictions on the timing of addition). ing. Further, even when applied to water-based paints, there are no harmful effects of repelling or foaming.

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.
From the viewpoint of dynamic surface tension lowering ability and water solubility, it is preferable to contain oxyethylene, and more preferably a mixture of oxyethylene and oxypropylene.
When oxyethylene is included, the content ratio (% by weight) of oxyethylene is preferably 50 to 100, more preferably 55 to 96, particularly preferably 60, based on the total weight of AO (total weight of oxyalkylene group). ~ 93, most preferably 65-90.

  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 dynamic surface tension lowering ability and water solubility, 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, the dynamic surface tension reducing ability and water solubility 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. Within this range, the dynamic surface tension reducing ability and water solubility are further improved.
n is preferably an integer of 1 to 3, and more preferably 1 or 2. Within this range, the dynamic surface tension reducing ability and water solubility are 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 4 to 70, more preferably 6 to 67, particularly preferably 8 to 63, and most preferably 10 to 60. Within this range, the dynamic surface tension reducing ability and water solubility tend to be further improved.

The clouding point (° C.) of the polyoxyalkylene compound represented by the general formula (1) is preferably 40 to 90, more preferably 42 to 88, particularly preferably 43 to 87, and most preferably 45 to 85. Within this range, the dynamic surface tension lowering ability and water solubility 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% by weight aqueous solution, 25 ° C.) (mN / m) of the polyoxyalkylene compound represented by the general formula (1) is preferably 30 to 50, more preferably 31 to 47, particularly Preferably it is 32-45.

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, 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 distribution in the oxyalkylene group. In this case, strictly speaking, a mixture of a plurality of types of polyoxyalkylene compounds is obtained. In this, the polyoxyalkylene compound represented by the general formula (1) is included. Even in this case, the manufacturing method is not limited.

  And as usage-amount (mol part) of alkylene oxide (a2), 2-30 are preferable with respect to 1 mol part of monoalkylamide (a1), More preferably, it is 3-27, Most preferably, it is 4-26, Most preferably, it is 5-25. Within this range, the dynamic surface tension lowering ability and water solubility are 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, the dynamic surface tension reducing ability and water solubility tend to be 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. Of these, EO and a mixture of EO and PO are preferable, and a mixture of EO and PO is more preferable from the viewpoint of dynamic surface tension reducing ability and water solubility.
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 is included, the use ratio (% by weight) of EO is preferably 50 to 100, more preferably 55 to 96, particularly preferably 60 to 93, and most preferably 65 to 90, based on the total weight of alkylene oxide. It is.

  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 surfactant of the present invention may contain other surfactant and / or other solvent, if necessary.
As other surfactants, known surfactants of nonionic type, cationic type, anionic type or amphoteric type 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 40 to 1, more preferably 30 to 5, based on the weight of the polyoxyalkylene compound represented by the general formula (1). Especially preferably, it is 25-10.

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.

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, after charging 586 parts (1 mole part) of laurylamide EO adduct dimer and 1 part of potassium hydroxide {reagent special grade, manufactured by Sigma) into the same reaction vessel, the temperature was raised to 120 ° C while stirring, It dehydrated under reduced pressure of 100-5 mmHg. Next, 440 parts (10 mole 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. After cooling to 90 ° C., 10 parts of ion-exchanged water was added, then 15 parts of Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at the same temperature for 1 hour. Next, at the same temperature, no. Filter with 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove Kyoward 700, and further dehydrate for 1 hour at 120 ° C. under a reduced pressure of 20 to 10 mmHg to obtain the surfactant (dilaurylamide compound) of the present invention. / EO 14 mol: A1) was obtained.
The cloud point of (A1) (according to measurement method B of ISO 1065-1975 (E); the same applies hereinafter) was 68.5 ° C.

<Example 2>
Into a reaction vessel similar to that in Example 1, 586 parts (1 mole part) of laurylamide EO adduct dimer and 2 parts of potassium hydroxide {reagent special grade, manufactured by Sigma Co.} were added, and the mixture was stirred up to 120 ° C. The temperature was raised and dehydration was performed under a reduced pressure of 100 to 5 mmHg. Subsequently, 528 parts (12 mole 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. Subsequently, 232 parts (4 mole parts) of PO was added dropwise at 100 to 120 ° C. over 4 hours, and then stirring was continued for 2 hours at the same temperature to react with the remaining PO. Then, in the same manner as in Example 1, decatalysis and dehydration were carried out using Kyoward 700 to obtain the surfactant of the present invention (dilaurylamide compound / EO 16 mol / PO 4 mol: A2). The cloud point of (A2) was 60.0 ° 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, after adding 176 parts (4 mol parts) of EO dropwise at 140 to 170 ° C. over 2 hours, stirring was continued for 30 minutes at the same temperature, and the remaining EO was reacted 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 755 parts (1 mole part) of stearylamide EO adduct dimer and 2 parts of potassium hydroxide to the same reaction vessel, the temperature was raised to 120 ° C. while stirring, and dehydration was performed at a reduced pressure of 100 to 5 mmHg. did. Next, 352 parts (8 mol parts) of EO was dropped over 3 hours at the same temperature, and then stirring was continued for 30 minutes at the same temperature to react with the remaining EO. Then, in the same manner as in Example 1, decatalysis and dehydration were carried out using Kyoward 700 to obtain a surfactant of the present invention (distearylamide compound / EO 12 mol: A3). The cloud point of (A3) was 56.0 ° C.

<Example 4>
755 parts (1 mol part) of stearylamide EO adduct dimer and 3 parts of potassium hydroxide were added to the same reaction vessel as in Example 1, and then the temperature was raised to 120 ° C. while stirring, and 100 to 5 mmHg. Dehydrated under reduced pressure. Next, 232 parts (4 mole parts) of PO was added dropwise at 100 to 120 ° C. over 1 hour, and then stirring was continued for 30 minutes at the same temperature to react with the remaining PO. Subsequently, 264 parts (6 mole parts) of EO was added dropwise at 140 to 170 ° C. over 2 hours, and then stirring was continued for 1 hour at the same temperature to react with the remaining EO. Subsequently, decatalysis and dehydration were carried out using Kyoward 700 in the same manner as in Example 1 to obtain the surfactant of the present invention (distearylamide compound / EO 12 mol / PO 4 mol / EO 6 mol: A4). The cloud point of (A4) was 65.0 ° C.

<Example 5>
After charging 1126 parts (4 mole parts) of oleylamide {special reagent grade, 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, 352 parts (8 parts by mole) 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 an oleylamide EO adduct.
Thereafter, an aqueous solution consisting of 256 parts (6.4 mole parts) of sodium hydroxide and 320 parts of water was added to the oleylamide EO 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 put into a separatory funnel, 800 parts of ion-exchanged water and 1000 parts of n-hexane were added, shaken and 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 an oleylamide EO adduct tetramer.
Next, 1514 parts (1 mole part) of oleylamide EO adduct tetramer and 3 parts of potassium hydroxide were added to the same reaction vessel, and then the temperature was raised to 120 ° C. with stirring, under a reduced pressure of 100 to 5 mmHg. Dehydrated. Next, 352 parts (8 parts by mole) of EO were 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. Then, in the same manner as in Example 1, decatalysis and dehydration were carried out using Kyoward 700 to obtain a surfactant of the present invention (tetraoleylamide compound / EO 16 mol: A5). The cloud point of (A5) was 43.0 ° C.

<Example 6>
Into the same reaction vessel as in Example 1, 1514 parts (1 mole part) of oleamide EO adduct tetramer and 4 parts of potassium hydroxide were added, and then the temperature was raised to 120 ° C. while stirring, and 100 to 5 mmHg. Dehydrated under reduced pressure. Next, a mixture of 232 parts (4 mole parts) of PO and 176 parts (4 mole parts) of EO was dropped over 120 hours at 120 to 140 ° C., and then stirred for 30 minutes at the same temperature to react the remaining EO and PO. I let you. Next, after 440 parts (10 parts by mole) of EO was added dropwise at 140 to 170 ° C. over 2 hours, stirring was continued for 1 hour at the same temperature to react with the remaining EO. Subsequently, decatalysis and dehydration were carried out using Kyoward 700 in the same manner as in Example 1 to obtain a surfactant of the present invention (tetraoleylamide compound / EO 16 mol / EO, PO 4 mol / EO 10 mol: A6). The cloud point of (A6) was 55.0 ° C.

<Comparative Example 1>
To a reaction vessel similar to Example 1, 76 parts of propylene glycol (1 mole part) and 4.0 parts of potassium hydroxide were added and dehydrated at 80 ° C. under a reduced pressure of 20 to 10 mmHg, and then 1450 parts of PO ( 25 mol parts) 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. Next, 660 parts (15 parts by mole) of EO was added dropwise at 140 to 170 ° C. in about 2 hours. Further, the remaining EO was reacted for about 0.5 hours at the same temperature. In accordance with Example 1, it was treated with 45 parts water / 250 parts Kyoward 700 and dehydrated to obtain a comparative surfactant (propylene glycol / PO 25 mol / EO 15 mol: B1). The cloud point of (B1) was 42.5 ° C.

<Comparative example 2>
Acetylene glycol {trade name: Surfynol-104, manufactured by Air Products Co., Ltd.} was used as a comparative surfactant (B2).

<Comparative Example 3>
Dialkylsulfosuccinate {trade name: Sanmorin OT-70, manufactured by Sanyo Chemical Industries Ltd.} was used as a comparative surfactant (B3).

The surfactants (A1) to (A6) of the present invention and the comparative surfactants (B1) to (B3) were evaluated for water solubility, surface tension reducing ability and foaming resistance, and are shown in Table 1. .
<Water solubility>
An evaluation sample of 0.150 g was taken in a glass beaker (300 mL), and deionized water at 25 ° C. was added to make 150.0 g (evaluation sample concentration of 0.1%). Next, a stirrer piece (30 mm long, 7 mm diameter cylindrical shape) was put in, stirred at 25 ° C. for 2 minutes at 100 rpm, allowed to stand for 1 minute, and then visually observed. And water solubility was evaluated by the following criteria.
○: uniformly dissolved (no cloudiness, oil droplets, oil film)
X: Oil droplets and oil film were observed

<Evaluation of surface tension reducing ability (dynamic surface tension)>
About the evaluation sample which completed evaluation of water solubility, the surface tension in 50 Hz was measured at 25 +/- 0.2 degreeC using the bubble pressure type | formula dynamic surface tension meter Cruz BP-2 made from Cruz (bubble) Gas for generation: dry air, measurement time interval: 500 milliseconds, dynamic surface tension of deionized water as a blank is measured under the same conditions, and within a range of 73.0-72.0 mN / m at 20-0.05 Hz The diameter of the capillary (dry air discharge pipe) was selected so that

<Foam resistance>
Simultaneously with the evaluation of the ability to lower the surface tension, the foaming resistance was visually observed and evaluated according to the following criteria.
○: Almost no foaming △: Slight bubbling ×: Strong foaming

標準：脱イオン水での測定結果
注１；比較例２の界面活性剤（Ｂ２）は水に溶解しなかったため、測定できなかった。

Standard: Measurement results with deionized water Note 1: The surfactant (B2) of Comparative Example 2 could not be measured because it did not dissolve in water.

  The smaller the dynamic surface tension value at 50 Hz, the better the dynamic surface tension reducing ability. Therefore, the surfactants of the present invention (Examples 1 to 6) were extremely excellent in dynamic surface tension lowering ability and water solubility, and further showed excellent results in foaming resistance.

The surfactant of the present invention can be used for any application, but is particularly suitable for water-based paints, and further suitable for paints that are coated or printed at high speed (for example, water-based paints for curtain flow coats). is there.
Examples of water-based paints include paper coating paints, architectural paints, building material paints, automobile paints, ship paints, and water-based inks.
The coating material to which the surfactant of the present invention is added can be applied to an object to be coated by an ordinary method, such as brush coating, roller coating, air spray coating, airless coating, roll coater coating, flow coater coating, and curtain flow coater. A painting method such as painting can be applied.

Claims (8)

A surfactant 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 is an integer of 1-30, n represents the integer of 1-3, and the total number of AO is an integer of 12-34 . The surfactant according to claim 1, comprising an oxyethylene group as AO, wherein the content ratio of the oxyethylene group is 50 to 100% by weight based on the total weight of AO. The polyoxyalkylene compound represented by the general formula (1) is a monoalkylamide (a1) having 8 to 18 carbon atoms, an alkylene oxide (a2) having 2 to 3 carbon atoms, or a dihalogenated hydrocarbon having 1 to 2 carbon atoms. The surfactant according to claim 1 or 2, which is a polyoxyalkylene compound having a structure that can be produced by the chemical reaction (a3). The surfactant 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 40 to 90 ° C. The surfactant according to any one of claims 1 to 4, wherein the dynamic surface tension {0.1 wt% aqueous solution, 25 ° C} of the polyoxyalkylene compound by a maximum bubble pressure method at 50 Hz is 30 to 50 mN / m. The surfactant according to any one of claims 1 to 5, which is used for water-based paints. The surfactant according to claim 6, which is used for curtain flow coat water-based paint. The surfactant according to claim 6 or 7, 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.