JP4565071B2 - Surfactant, coating material containing the same, and method for producing the surfactant - Google Patents

Description

  The present invention relates to a surfactant, a coating material containing the same, and a method for producing the surfactant. More specifically, the present invention relates to an optimum surfactant for water-based paints, paper coating paints and water-based inks, a paint containing the same, and a method for producing the surfactant.

There is no known surfactant including a polyoxyalkylene compound having a structure that can be produced by a chemical reaction of a non-reducing di- or trisaccharide with an alkylene oxide and an α-olefin oxide.
Conventionally, surfactants used in water-based paints, paper coating paints, water-based inks and the like are predominantly anionic surfactants, such as dialkyl sulfosuccinates, alkyl sulfonates, and ether carboxylates (Patent Document 1). Etc. are known. Further, acetylene glycol (Non-patent Document 1) manufactured by Air Products is known.

Japanese Unexamined Patent Publication No. 5-051900 Surfactor for water-based paint “Surfinol” Ichiro Yamazaki, Paint and Paint August 2000 (No. 607) p. 77, Paint Publisher

  The surfactant described in Patent Document 1 has a problem that foaming is severe. In addition, since the acetylene glycol described in Patent Document 2 has low solubility or dispersibility in water, it must be added in advance when preparing paints, inks, etc., and can be added in any manufacturing process. There are no major restrictions on usage. That is, an object of the present invention is to provide a surfactant excellent in surface tension lowering ability (including foam suppressing property, foam breaking property, foam stabilizing property and defoaming property) and water solubility.

The present inventors have reached the present invention result of extensive studies to solve the above problems. That is, the present invention is Ri Do as an essential component a polyoxyalkylene compound represented by the general formula (1),
In the presence of an amide, the polyoxyalkylene compound is a non-reducing di- or trisaccharide (a1) 1 mole part, a C2-C4 alkylene oxide (a2) 2-46 mole part, and a C6-C18 produced by the chemical reaction of the α- olefin oxide (a3) of {except styrene oxide} 1.2-3 mole parts is a surface active agent characterized Rukoto.

{H- (OA ¹ ) _n -} _t-m Q {-[(OA ¹ ) _n / (OA ² )]-H} _m        (1)

  However, in the general formula (1), Q is a reaction residue obtained by removing a hydrogen atom from t (integer of 2 to 4) primary hydroxyl groups of a non-reducing di- or trisaccharide, OA ¹ Is an oxyalkylene group having 2 to 4 carbon atoms, OA ² Is an oxyalkylene group derived from an α-olefin oxide having 6 to 18 carbon atoms (excluding styrene oxide), H is a hydrogen atom, t n may be the same or different, an integer of 1 to 20, m Represents an integer of 1 to 3 and OA in one molecule ¹ Is 2 to 40 when t = 2, and 5 to 46 when t = 3 to 4, and t−m {H− (OA ¹ ) _n -} And m {-[(OA ¹ ) _n / (OA ² )]-H} may be the same or different.

The surfactant of the present invention has extremely excellent surface tension reducing ability (including foam suppression and antifoaming ability) and water solubility. Therefore, it is possible to drastically improve the familiarity to the surface to be coated, the wettability, and the like, which are disadvantages of the water-based paint, the handleability is excellent (there is no restriction on the addition timing, etc.), and there are no harmful effects of repelling or foaming.

The general formula (1) will be described.
Examples of di- or trisaccharides that can constitute a reaction residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of non-reducing di- or trisaccharides include sucrose, trehalose, isotrehalose, Examples include isosaccharose, gentianose, raffinose, meretitol and planteose. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of surface tension lowering ability and water solubility, and more preferably trehalose and sucrose, and particularly preferable from the viewpoint of supply ability and cost. Sucrose. These may be used alone or in combination.
t is an integer of 2 to 4 representing the number of primary hydroxyl groups of the non-reducing di- or trisaccharide, and is preferably 3. Within this range, surface tension reducing ability and water solubility tend to be further improved.

Examples of the oxyalkylene group having 2 to 4 carbon atoms (OA ¹ ) include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Among these, from the viewpoints of surface tension reducing ability and water solubility, a mixture containing oxyethylene, oxypropylene and oxyethylene is preferable, and more preferably a mixture containing oxyethylene and oxyethylene.
The n OA ¹ may be the same or different, and t (OA ¹ ) n may be the same or different.

When plural kinds of oxyalkylene groups are contained in OA ¹ , there is no limitation on the bonding order (block shape, random shape and combinations thereof) and the content ratio of these oxyalkylene groups, but block shape, block shape and random shape It is preferable that the combination of these is included. In this case, oxyethylene is preferably included, and the content ratio (% by weight) of oxyethylene is preferably 20 to 90, more preferably 25 to 85, particularly preferably based on the total weight of the oxyalkylene group. 30-80, most preferably 35-75. That is, in this case, the content ratio (% by weight) of oxyethylene is preferably 20 or more, more preferably 25 or more, particularly preferably 30 or more, most preferably 35 or more, based on the total weight of the oxyalkylene group. 90 or less, more preferably 85 or less, particularly preferably 80 or less, and most preferably 75 or less.
When OA ¹ contains an oxyethylene group and an oxypropylene group and / or oxybutylene group, it is preferable that oxypropylene and / or oxybutylene is located at a position away from the reaction residue (Q). That is, it is preferable that an oxyethylene group is directly bonded to the reaction residue (Q).

The total number of OA ^{1 in} one molecule is preferably 2 to 40, more preferably 5 to 38, particularly preferably 7 to 35, and most preferably 10 to 30, when t = 2. When t = 3-4, 5-46 is preferable, more preferably 7-43, particularly preferably 10-40, and most preferably 15-35. Within this range, the surface tension reducing ability and water solubility tend to be further improved. N is preferably an integer of 1 to 20, more preferably an integer of 2 to 18, particularly preferably an integer of 3 to 17, and most preferably an integer of 4 to 15. Within this range, the surface tension reducing ability and water solubility tend to be further improved. Further, t n may be the same value or different values.

As the oxyalkylene group (OA ² ), an oxyalkylene group derived from an α-olefin oxide having 6 to 18 carbon atoms can be used, and oxyhexylene, oxyhexenylene, oxyoctylene, oxydecylene, oxydecenylene, oxide Silene, oxiddecenylene, oxyoctadecylene, oxyoctadecenylene, and mixtures thereof are included. Of these, oxyoctylene, oxydecylene, oxydecenylene, oxide decylene, oxydecenylene, oxytetradecylene, oxytetradecenylene, and mixtures thereof are preferable from the viewpoint of surface activity.

The total number (pieces) of OA ^{2 in} one molecule is preferably 1 to 3, more preferably 2 to 3, particularly preferably 2. Within this range, the surface tension reducing ability and water solubility tend to be further improved.
m is preferably an integer of 1 to 3, more preferably 2 or 3, and particularly preferably 2. Within this range, the surface tension reducing ability and water solubility tend to be further improved.

H represents a hydrogen atom. tm is preferably an integer of 0 to 3, more preferably 1 or 2, and particularly preferably 1.
The tm {H- (OA ¹ ) _n- } and the m {-[(OA ¹ ) _n / (OA ² )]-H} may be the same or different.
[(OA ¹ ) n / (OA ² )] represents that (OA ² ) may exist at any position in relation to (OA ¹ ).

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, Q ¹ represents a sucrose reaction residue, Q ² represents a trehalose reaction residue, and Q ³ represents a meletitose reaction residue (the same applies hereinafter). ).
Of these, polyoxyalkylene compounds represented by formula (2), (3), (5), (8), (10) or (13) are preferred, and more preferred are formulas (2) and (5). , (10) or a polyoxyalkylene compound represented by (13).

Examples of the polyoxyalkylene compound represented by the general formula (1) include non-reducing disaccharides or trisaccharides (a1), alkylene oxides having 2 to 4 carbon atoms (a2), and α-olefin oxides having 6 to 18 carbon atoms. Those having a structure that can be produced by the chemical reaction of (a3) 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), 2-46 are preferable with respect to 1 mol part of non-reducing disaccharide or trisaccharide (a1), More preferably, it is 5-43, Especially preferably. Is 7-40, most preferably 10-35. That is, the amount (mole part) of the alkylene oxide (a2) used is preferably 2 or more, more preferably 5 or more, particularly preferably 7 or more, and most preferably with respect to 1 mol part of the non-reducing di- or trisaccharide. Is 10 or more, preferably 46 or less, more preferably 43 or less, particularly preferably 40 or less, and most preferably 35 or less. Within this range, the surface tension reducing ability and water solubility tend to be further improved.

Moreover, as usage-amount (mol part) of C6-C18 alpha olefin oxide (a3), 1-3 are preferable with respect to 1 mol part of non-reducing di- or trisaccharide units, More preferably It is 1.2 to 2.8, particularly preferably 1.5 to 2.5, and most preferably 1.7 to 2.3. That is, the amount (mole part) used of (a3) is preferably 1 or more, more preferably 1.2 or more, particularly preferably 1.5 or more, most preferably 1 mol part of the non-reducing di- or trisaccharide. It is preferably 1.7 or more, and preferably 3 or less, more preferably 2.8 or less, particularly preferably 2.5 or less, and most preferably 2.3 or less. Within this range, the surface tension reducing ability and water solubility tend to be further improved.
The chemical reaction usually involves reacting a reactive product (a12) of a non-reducing di- or trisaccharide (a1) and an alkylene oxide (a2) with an α-olefin oxide (a3). And (a3) are reacted with (a13) and (a2), and (a1) and (a2) are reactive with (a12) and (a3). The product (a123) may be further reacted with (a2), or (a1), (a2) and (a3) may be reacted at once.

As the non-reducing di- or trisaccharide (a1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (1) can be used, and the preferred range is also the same.

As the alkylene oxide (a2), an alkylene oxide having 2 to 4 carbon atoms can be used, and examples thereof include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. Among these, from the viewpoints of surface tension reducing ability and water solubility, EO, a mixture containing EO and PO are preferable, and a mixture containing EO and EO is more preferable.
Multiple types of alkylene oxides may be used. In this case, the order of reaction (block, random, and combinations thereof) and the use ratio are not limited, but include block or a combination of block and random. Is preferable. Further, in this case, it is preferable to contain EO, and the use ratio (% by weight) of EO is preferably 20 to 90, more preferably 25 to 85, particularly preferably 30 to based on the total weight of the alkylene oxide. 80, most preferably 35-75. That is, in this case, the use ratio (% by weight) of EO is preferably 20 or more, more preferably 25 or more, particularly preferably 30 or more, and most preferably 35 or more, based on the total weight of the alkylene oxide. 90 or less, more preferably 85 or less, particularly preferably 80 or less, and most preferably 75 or less.
When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of EO.

  As the α-olefin oxide (a3), an α-olefin oxide having 6 to 18 carbon atoms can be used, and 1,2-epoxyhexane, 1,2-epoxy-5-hexene, 1,2-epoxyoctane, , 2-epoxy-7-octene, 1,2-epoxydecane, 1,2-epoxy-9-decene, 1,2-epoxydodecane, 1,2-epoxy-11-dodecene, 1,2-epoxytetradecane, Examples include 1,2-epoxy-13-tetradecene, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, and 1,2-epoxy-17-octadecene. Of these, 1,2-epoxyoctane, 1,2-epoxy-7-octene, 1,2-epoxydecane, 1,2-epoxy-9-decene, 1,2-epoxydodecane, 1,2-epoxy -11-dodecene, 1,2-epoxytetradecane and 1,2-epoxy-17-octadecene are preferred, more preferably 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1, 2-epoxy-11-dodecene and 1,2-epoxytetradecane. These may be used alone or in combination.

The cloud point (° C.) of the polyoxyalkylene compound is preferably 30 to 60, more preferably 32 to 58, particularly preferably 34 to 56, and most preferably 35 to 55. That is, the cloud point (° C.) of the polyoxyalkylene compound is preferably 30 or more, more preferably 32 or more, particularly preferably 34 or more, most preferably 35 or more, and preferably 60 or less, more preferably 58 or less. Particularly preferably, it is 56 or less, and most preferably 55 or less. Within this range, the surface tension reducing ability and water solubility tend to be even better.

  The cloud point means a physical property value that is a measure of the hydrophilicity / hydrophobicity of a 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-clouding 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 1.0 ± 0.2 ° C./min. Thereafter, while stirring, the sample solution is cooled at 1.0 ± 0.5 ° 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 (mN / m) of the 0.5 wt% aqueous solution of the polyoxyalkylene compound at 25 ± 0.2 ° C. and 20 Hz is preferably 45 to 25, more preferably 44 to 28, and particularly preferably 43 to 30. That is, the dynamic surface tension (mN / m) of the polyoxyalkylene compound is preferably 45 or less, more preferably 44 or less, particularly preferably 43 or less, and preferably 25 or more, more preferably 28 or more. Especially preferably, it is 30 or more.
Further, the difference in dynamic surface tension (mN / m) between 20 Hz and 0.05 Hz is preferably 12 or less, more preferably 11 or less, and particularly preferably 10 or less.

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 plate method are well known as surface tension measurement methods, but these measure the surface tension that reaches equilibrium (static surface tension). It is the surface tension at the gas-liquid interface with a certain amount, and is measured by a method called a maximum bubble pressure method or a differential maximum bubble pressure method {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 (mN / m) at the interface is Expressed 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 measuring instruments 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 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. In addition, the dynamic surface tension of deionized water is measured on the same conditions as a blank, and it confirms for every measurement that it is 73.0-72.0mN / m in 20-0.05Hz.

The polyoxyalkylene compound can be obtained by reacting a non-reducing disaccharide or trisaccharide (a1), an alkylene oxide (a2) and an α-olefin oxide (a3). As the order of reaction,
(1) First, (a1) and (a2) are reacted to obtain a reaction product (a12). Next, (a12) and (a3) are reacted to obtain a reaction product (a123).
(2) First, (a1) and (a3) are reacted to obtain a reaction product (a13). Next, a reaction product (a13) is reacted with (a2) to obtain a reaction product (a123).
(3) First, (a1) and (a2) are reacted to obtain (a12), then (a3) is reacted to obtain (a123), and (a2) is further reacted to produce a reaction product (a1232 How to get).
(4) A method of obtaining a reaction product (a123) by reacting (a1) with a mixture of (a2) and (a3).
The above is possible. All of these are preferred methods, but (1) is particularly preferred.

The reaction of the non-reducing di- or trisaccharide (a1) with the alkylene oxide (a2) and / or the α-olefin oxide (a3) is carried out in any form such as anionic polymerization, cationic polymerization or coordination anionic polymerization. May be. 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 of the non-reducing disaccharide or trisaccharide (a1) with the alkylene oxide (a2) and / or the α-olefin oxide (a3). In addition, when using the amide demonstrated below as a reaction solvent, it is not necessary to use a reaction catalyst.
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 preferably 0.05 to 2, more preferably 0.1 based on the total weight of (a1) and (a2) and / or (a3). To 1, particularly preferably 0.2 to 0.6. That is, in this case, the use amount (% by weight) of the reaction catalyst is preferably 0.05 or more, more preferably 0.1 or more, particularly based on the weight of (a1) and (a2) and / or (a3). Preferably it is 0.2 or more, 2 or less is preferable, More preferably, it is 1 or less, Most preferably, it is 0.6 or less.
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 an inert gas atmosphere (such as argon, nitrogen and carbon dioxide) in which the inside of the reaction apparatus is evacuated or dried before introducing the alkylene oxide (a2) and / or the α-olefin oxide (a3) into the reaction system. It is preferable that 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 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 4 to 12 hours.

In the reaction step of the non-reducing di- or trisaccharide (a1) with the alkylene oxide (a2) and / or the α-olefin oxide (a3), it is preferable to use a reaction solvent.
The reaction solvent includes (1) no active hydrogen, (2) non-reducing di- or trisaccharide (a1), alkylene oxide (a2), α-olefin oxide (a3), (a1) and (a2) The reaction product (a12) and the reaction product (a13) of (a1) and (a3) can be used.

  As such a reaction solvent, alkyl amides having 3 to 8 carbon atoms and heterocyclic amides having 5 to 7 carbon atoms can be used. Examples of the alkylamide include N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-N-propylacetamide, 2-dimethylaminoacetaldehyde dimethylacetal and the like. Examples of the heterocyclic amide include N-methylpyrrolidone, N-methyl-ε-caprolactam, and N, N-dimethylpyrrolecarboxylic acid amide.

Of these, alkylamide and N-methylpyrrolidone are preferred, DMF, N, N-dimethylacetamide and N-methylpyrrolidone are more preferred, DMF and N-methylpyrrolidone are most preferred, and DMF is most preferred.
When a reaction solvent is used, the amount used (% by weight) is preferably 20 to 200, more preferably 40 to 180, particularly preferably 60 to 150, based on the weight of the reaction product. That is, in this case, the use amount (% by weight) of the reaction solvent is preferably 20 or more, more preferably 40 or more, particularly preferably 60 or more, and preferably 200 or less, based on the weight of the reaction product. More preferably, it is 180 or less, Especially preferably, it is 150 or less.

When a reaction solvent is used, it is preferable to remove the reaction solvent after the reaction.
The residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.01 or less, based on the weight of the polyoxyalkylene compound. The residual amount of the reaction solvent can be determined by gas chromatography using an internal standard substance.
As a method for removing the reaction solvent, vacuum distillation, adsorption removal and the like can be applied, and it is preferable to further remove by adsorption after vacuum distillation.
As conditions for distilling off under reduced pressure, conditions such as distillation at 100 to 150 ° C. under reduced pressure of 200 to 5 mmHg can be applied.
Furthermore, when removing by adsorption, a method of treating with an alkali adsorbent such as synthetic aluminosilicate {for example, trade name: Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.} can be applied. For example, when using KYOWARD 700, the addition amount (% by weight) of the alkali adsorbent is about 0.1 to 10 based on the weight of the polyoxyalkylene compound, the processing temperature is about 60 to 120 ° C., and the processing time is 0. About 5 to 5 hours. Subsequently, the remaining amount of the reaction solvent can be further reduced by removing the alkali adsorbent by filtration using filter paper or filter cloth.

If necessary, the surfactant of the present invention may contain other surfactants and / or other solvents as components other than the polyoxyalkylene compound.
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, particularly preferably 25 to 10, based on the weight of the polyoxyalkylene compound. . That is, in this case, the content (% by weight) of the other surfactant is preferably 1 or more, more preferably 5 or more, particularly preferably 10 or more, based on the weight of the polyoxyalkylene compound. The following is preferable, more preferably 30 or less, and particularly preferably 25 or less.

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 water-soluble organic solvents include alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ethers (ethyl cellosolve, butyl cellosolve, etc.), ether esters (butyl cellosolve acetate, etc.), etc. Is mentioned.
When other solvents are contained, the content (% by weight) is preferably 20 to 1, more preferably 17 to 3, particularly preferably 15 to 5, based on the weight of the polyoxyalkylene compound. That is, in this case, the content (% by weight) of the other solvent is preferably 1 or more, more preferably 3 or more, particularly preferably 5 or more, and 20 or less based on the weight of the polyoxyalkylene compound. More preferably, it is 17 or less, and particularly preferably 15 or less.

  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”.

<Evaluation of surface tension reducing ability (dynamic surface tension)>
At 25 ° C., the evaluation sample was dissolved in deionized water to prepare a 0.5% evaluation sample aqueous solution. At this time, solubility in water and foaming resistance were evaluated. Furthermore, at 25 degreeC, the surface tension (T1) of 20 Hz and the surface tension (T2) of 0.1 Hz were measured using the bubble pressure type | mold dynamic surface tension meter Cruz BP-2 by Cruz. And the difference (DELTA) T {(T1)-(T2)} of surface tension was computed. Table 1 shows the surface tension (T1) at 20 Hz, the difference in surface tension ΔT {(T1) − (T2)}, and the standard {surface tension only with deionized water}.

<Evaluation of water solubility>
The evaluation was made in the following three stages and shown in Table 1.
○: Dissolves uniformly.
Δ: White turbidity is observed, but no oil droplets or oil film is generated.
X: Generation | occurrence | production of an oil droplet and an oil film is seen.

<Foam resistance>
The evaluation was made in the following three stages and shown in Table 1.
○: Almost no foaming △: Slight bubbling ×: Strong foaming

<Example 1>
342 parts (1 mole part) of purified granulated sugar {sucrose, manufactured by Taiyo Co., Ltd.}, DMF {Mitsubishi Gas Chemical Co., Ltd. Content of 0.005%, the same shall apply hereinafter} After adding 1000 parts, an operation (pressurized nitrogen substitution) is performed using nitrogen gas until the gauge pressure is increased to 0.4 MPa and discharged to 0.02 MPa. Repeated 3 times. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 440 parts (10 parts by mole) of EO was added dropwise at the same temperature over 4 hours, followed by stirring at the same temperature for 30 minutes to react with the remaining EO. Next, after the temperature was raised to 110 ° C., 1160 parts (20 mole parts) of PO was added dropwise at this temperature over 6 hours, and stirring was continued for 2 hours at the same temperature to react with the remaining PO. Next, after raising the temperature to 120 ° C., 184 parts (1 mole part) of 1,2-epoxydodecane {special reagent grade, manufactured by Sigma Aldrich Japan Co., Ltd., hereinafter abbreviated as Sigma Corporation} was taken at 120 ° C. for 2 hours. The reaction was continued by stirring for 8 hours at the same temperature.
Thereafter, DMF was distilled off under reduced pressure at 120 ° C. and 100 to 10 mmHg, and then 20 parts of ion-exchanged water was added at 90 ° C., and then 100 parts of Kyoward 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added. Stir at the same temperature for 1 hour. Next, at the same temperature, no. Filter using 2 filter paper {manufactured by Toyo Filter Paper Co., Ltd.} to remove KYOWARD 700 and dehydrate for 1 hour at 120 ° C. under a reduced pressure of 20 to 10 mmHg to obtain sucrose / EO 10 mol / PO 20 mol / 1,2. -Epoxide decane 1 mol adduct (A1) was obtained.
The DMF content of (A1) (gas chromatography method using an internal standard substance; the same applies hereinafter) is 0.02%, and the cloud point (according to measurement method B of ISO 1065-1975 (E); the same applies hereinafter) is 45. 0 ° C.

<Example 2>
After charging 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF into the same reaction vessel as in Example 1, the pressurized nitrogen substitution was repeated three times in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 660 parts (15 mole parts) of EO was added dropwise at the same temperature over 5 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. Subsequently, after heating up to 110 degreeC, PO870 part (15 mol part) was dripped at this temperature over 6 hours, and also stirring was continued for 3 hours at the same temperature, and the remaining PO was made to react. Next, 312 parts (2 mole parts) of 1,2-epoxydecane {special reagent grade, manufactured by Sigma Co., Ltd.} are added dropwise at 110 ° C. over 3 hours, and stirring is continued for 8 hours at the same temperature. I let you.
Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain an adduct (A2) of sucrose / EO 15 mol / PO 15 mol / 1,2-epoxydecane.
The DMF content of (A2) was 0.01%, and the cloud point was 40.5 ° C.

<Example 3>
342 parts (1 mole part) of purified granulated sugar, N-methylpyrrolidone {reagent grade, manufactured by Wako Pure Chemical Industries, Ltd., water content 0.007%, the same applies below} 1500 in the same reaction vessel as in Example 1 Then, nitrogen replacement was performed in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 572 parts (13 parts by mole) of EO were added dropwise at the same temperature over 4 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. Next, a mixture of PO986 parts (17 mol parts) and BO parts 222 parts (3 mol parts) was added dropwise at 100 ° C. over 8 hours, and stirring was continued at the same temperature for 4 hours to react the remaining PO and BO. . Next, 192 parts (1.5 mole parts) of 1,2-epoxyoctane {special grade reagent, manufactured by Sigma Co., Ltd.} was added dropwise at 100 ° C. over 3 hours, and stirring was continued for 8 hours at the same temperature. And reacted.
Thereafter, N-methylpyrrolidone distillation / Kyoward treatment was carried out in the same manner as in Example 1, and sucrose / EO 13 mol / (PO 17 mol / BO 3 mol) / 1,2-epoxyoctane 1.5 mol adduct (A3) Got.
The N-methylpyrrolidone content of (A3) was 0.02%, and the cloud point was 51.0 ° C.

<Example 4>
After charging 342 parts (1 mole part) of purified granulated sugar and 1250 parts of DMF in the same reaction vessel as in Example 1, pressurized nitrogen substitution was repeated three times in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 870 parts (15 mole parts) of EO was added dropwise at the same temperature over 4 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. Next, after raising the temperature to 110 ° C., 480 parts (2 mol parts) of 1,2-epoxyhexadecane {reagent special grade, manufactured by Sigma Co., Ltd.} are added dropwise at 110 ° C. over 3 hours, and the temperature is further increased. The reaction was continued for 8 hours.
Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain sucrose / EO 15 mol / 1,2-epoxyhexadecane 2-mol adduct (A4).
The DMF content of (A4) was 0.01%, and the cloud point was 35.5 ° C.

<Example 5>
Into a reaction vessel similar to that in Example 1, 342 parts (1 mole part) of trehalose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1500 parts of DMF were charged, and then the atmosphere was replaced with nitrogen in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then a mixed solution of EO 220 parts (5 mol parts) / PO 870 parts (15 mol parts) was added dropwise at the same temperature over 5 hours, followed by stirring at the same temperature for 3 hours. The remaining EO and PO were reacted. Thereafter, the temperature was raised to 110 ° C., and 256 parts (2 mol parts) of 1,2-epoxyoctane was added dropwise at 110 ° C. over 3 hours, followed by further stirring for 8 hours at the same temperature for reaction.
Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain an adduct (A5) of trehalose / (EO 5 mol / PO 15 mol) / 1,2-epoxyoctane 2 mol.
The DMF content of (A5) was 0.01%, and the cloud point was 43.5 ° C.

<Example 6>
Into a reaction vessel similar to that in Example 1, 504 parts (1 mole part) of Metetitos {special grade reagent, manufactured by Tokyo Chemical Industry Co., Ltd.} and 2500 parts of DMF were charged, and then nitrogen substitution was carried out in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 440 parts (10 mole parts) of EO was added dropwise at the same temperature over 4 hours, followed by stirring for 30 minutes at the same temperature to react with the remaining EO. PO580 part (10 mol part) was dripped over 7 hours. Stirring was continued for 4 hours at the same temperature to react with the remaining PO. Next, a mixture of 256 parts (2 mole parts) of 1,2-epoxyoctane and 156 parts (1 mole part) of 1,2-epoxydecane was dropped at the same temperature over 3 hours, and further at the same temperature for 8 hours. The reaction was continued with stirring. Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain an adduct (A6) of meletitol / EO 10 mol / PO 10 mol / (1,2-epoxyoctane 2 mol, 1,2-epoxydecane 1 mol). )
The DMF content of (A6) was 0.02%, and the cloud point was 34.0 ° C.

<Comparative Example 1>
After charging 342 parts (1 mole part) of purified granulated sugar and 1050 parts of DMF in the same reaction vessel as in Example 1, the pressurized nitrogen substitution was repeated three times in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 132 parts (3 mole parts) of EO was added dropwise at the same temperature over 4 hours, and then stirring was continued for 30 minutes at the same temperature to react with the remaining EO. Next, after the temperature was raised to 110 ° C., a mixed solution of PO 1160 parts (20 mol parts) and BO 370 parts (5 mol parts) was dropped at this temperature over 6 hours, and stirring was further continued at the same temperature for 3 hours. The remaining PO and BO were reacted.
Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain an adduct (B1) of sucrose / EO3 mol / (PO20 mol / BO5 mol).
The DMF content of (B1) was 0.01%, and the cloud point was 52.5 ° C.

<Comparative example 2>
After charging 342 parts (1 mole part) of purified granulated sugar and 1050 parts of DMF in the same reaction vessel as in Example 1, the pressurized nitrogen substitution was repeated three times in the same manner as in Example 1. Thereafter, the temperature was raised to 100 ° C. while stirring, 4060 parts (70 mole parts) of PO was added dropwise over 8 hours, and stirring was continued for 3 hours at the same temperature to react with the remaining PO.
Thereafter, DMF distillation / Kyoward treatment was carried out in the same manner as in Example 1 to obtain a sucrose / PO 70 mol adduct (B2).
The DMF content of (B2) was 0.01%, and the cloud point was 33.5 ° C.

<Comparative Example 3>
To a reaction vessel similar to that in 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 reduced pressure of 20 to 10 mmHg for 0.5 hours, and then PO2030 under the same reduced pressure. Parts (35 mol parts) were added dropwise at 100 to 120 ° C. over about 10 hours. Further, the remaining PO was kept at the same temperature for about 4 hours to react with the remaining PO. Subsequently, the mixture was treated with 45 parts water / 250 parts Kyoward 700 according to Example 1 to obtain a propylene glycol / PO35 molar adduct (B3). The cloud point of (B3) was 20.5 ° C.

<Comparative example 4>
Acetylene glycol {trade name: Surfynol-104, manufactured by Air Products Co., Ltd.} was used as the surfactant (B4) of Comparative Example 4.

<Comparative Example 5>
Dialkylsulfosuccinate {trade name: Sanmorin OT-70, manufactured by Sanyo Chemical Industries, Ltd.} was used as the surfactant (B5) of Comparative Example 5.

Note 1: The propylene glycol / PO35 molar adduct (B3) of Comparative Example 3 could not be measured because it did not dissolve in water.
Note 2: The surfactant (B4) of Comparative Example 4 was evaluated by using a filtrate that became transparent after being separated by No. 2 filter paper (JIS P3801) because an oil film and oil droplets were generated.

The smaller the surface tension and surface tension difference ΔT at 20 Hz, the better the surface tension lowering ability, the better the water solubility and antifoaming ability, and then the better Δ. ing.
Therefore, it is clear that the surfactants of the present invention (Examples 1 to 6) are extremely excellent in surface tension reducing ability and water solubility, and also excellent in antifoaming properties.
In addition, in the surfactants according to the conventional technique as seen in Patent Document 1, a decrease in surface tension can be observed for the first time at about 0.05 Hz (20 seconds), and it is not active until about 20 seconds after a new surface is formed. It can be seen that it begins to exert its function as an agent (see Table 1, Comparative Examples).

The surfactant of the present invention can be used for any application, but is particularly suitable for water-based paints, and furthermore, paints that are coated or printed at high speed (for example, curtain flow coat paints, paper paints and paints). It is suitable for water-based inks and the like.
Further, the surfactant of the present invention can be used as an antifoaming agent (including a foam suppressor, a foam breaker, a foam stabilizer, etc.), an emulsifying dispersant, and raw materials thereof. Antifoaming agents for paper coating paints, defoaming agents for water-based paints, antifoaming agents for various inks, antifoaming agents for paper making processes, antifoaming agents for various synthetic processes (for monomer stripping, etc.) Moreover, as a dispersing agent, it can be used for paper coating paints, water-based paints, pigment dispersants for various inks, etc., and as an emulsifier for various water-based paint resins. When the surfactant of the present invention is used as a defoaming agent or dispersant for paper coatings, water-based coatings, and various inks, it is added during or after the production process. The addition amount is preferably 0.01 to 10% based on the weight of the finished paint and various inks. Moreover, as a defoaming agent in a papermaking process and various synthesis processes, it can be added to a process in which it is foamed directly as a stock solution or diluted with a solvent such as water. The addition amount is preferably 0.001 to 1.0% by weight with respect to the target foaming system. When used as an emulsifier for various water-based paint resins, it is added to the paint resin in the emulsification step, and the addition amount is preferably 0.1 to 10% based on the weight of the paint resin.
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 (9)

Ri Do as an essential component a polyoxyalkylene compound represented by the general formula (1),
In the presence of an amide, the polyoxyalkylene compound is a non-reducing di- or trisaccharide (a1) 1 mole part, a C2-C4 alkylene oxide (a2) 2-46 mole part, and a C6-C18 α- olefin oxide (a3) surfactant, wherein Rukoto produced by the chemical reaction of 1.2 to 3 parts by mole {except styrene oxide}.

{H- (OA _< ¹ _> ) _n- } _tm Q {-[(OA _< ¹ >) _n / (OA _< ² >)]-H} _m (1)

However, in the general formula (1), Q is a reaction residue obtained by removing a hydrogen atom from t (integer of 2 to 4) primary hydroxyl groups of a non-reducing di- or trisaccharide, and OA ¹ has 2 to 2 carbon atoms. 4 oxyalkylene groups, OA ² is an oxyalkylene group derived from an α-olefin oxide having 6 to 18 carbon atoms ( excluding styrene oxide) , H is a hydrogen atom, and t n may be the same or different. Good integer of 1-20, m represents an integer of 1-3, and the total number of OA ^{1 in} one molecule is 2-40 when t = 2, and 5-46 when t = 3-4 , Tm {H- (OA ¹ ) _n- } and m {-[(OA ¹ ) _n / (OA ² )]-H} may be the same or different. The surfactant according to claim 1, wherein the non-reducing di- or trisaccharide reactive residue (Q) is a sucrose reactive residue. The interface according to claim 1 or 2, wherein the amide is at least one selected from the group consisting of N, N-dimethylformamide, N, N-dimethylacetamide, 2- (dimethylamino) acetaldehyde dimethylacetal and N-methylpyrrolidone. Activator. 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 30 to 60 ° C. The polyoxyalkylene compound has a dynamic surface tension {0.5 wt% aqueous solution, 25 ° C.} of 45 to 25 mN / m at 20 Hz, and the difference in dynamic surface tension at 20 Hz and 0.05 Hz is 12 mN / m or less. The surfactant according to any one of claims 1 to 4. The surfactant according to any one of claims 1 to 5, which is used for water-based paints. The surfactant according to any one of claims 1 to 5, which is for paper coating paint. The surfactant according to any one of claims 1 to 5, which is for water-based ink. A paint comprising 0.1 to 5% by weight of the surfactant according to any one of claims 1 to 5 based on the weight of the paint.