JP5934855B2 - Surfactant, pigment composition and coating composition containing the same - Google Patents

Description

  The present invention relates to a surfactant, a pigment composition containing the surfactant, and a coating composition.

  In recent years, the demand for water-based paints has increased rapidly from the viewpoint of work safety and pollution-free. However, since the main component of the solvent for water-based paints is water, there is a problem in toning properties when using pigments, particularly when a plurality of pigments are used, and the development of a surfactant capable of improving toning properties has been desired. .

  Examples of pigment dispersants that improve the toning properties of water-based paints include polystyrene sulfonate (Patent Document 1) and a method using a pigment composition in which a colored pigment and a polymer are deposited on an inorganic pigment (Patent Document 2). Are known.

JP 2000-248211 A Japanese Patent Application Laid-Open No. 5-59318

The pigment dispersant described in Patent Document 1 has a problem that the water resistance of the coating film is remarkably lowered when an amount necessary and sufficient for improving the toning property is used.
In order to obtain the pigment composition described in Patent Document 2, it is necessary to go through complicated steps such as alkali dissolution and acid deposition, which is not practical.
That is, an object of the present invention is to provide a surfactant that can easily provide a coating composition capable of forming a coating film excellent in toning properties (improvement of color floating, color separation, color unevenness, etc.) and water resistance. Is to provide.

The surfactant of the present invention is obtained by reacting 1 mol of the polyoxyalkylene compound (Y) represented by the general formula (1) with 1 to 5 mol of an alkyl glycidyl ether having 6 to 21 carbon atoms. The gist is that the polyoxyalkylene compound (YG) is contained.

However, S is the general formula (2) a group represented by, U is 2-hydroxypropylene group _{{-CH 2 -CH (OH) -CH} 2 -} or hydroxymethyl ethylene group _{-CH 2 -CH (CH ₂ OH)-}, m represents 3 or 4, and S and U may be the same or different.

{H (OA) _n −} _t−2 Q {− (OA) _n −} ₂ (2)

  Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, OA is an oxyalkylene group having 2 to 4 carbon atoms, H is a hydrogen atom, and t is an integer of 2 to 4 , N represents an integer of 5-30, the total number of OA is an integer of 20-60, and Q, OA, t, n may be the same or different.

  The feature of the pigment composition of the present invention is that it contains a pigment and the above-mentioned surfactant, and the surfactant is contained in an amount of 10 to 100% by weight based on the weight of the pigment.

  The gist of the coating composition of the present invention is that it contains the coating agent and the above-described pigment composition, and contains 1 to 20% by weight of this pigment composition based on the weight of the coating agent. .

  The feature of the coating composition of the present invention is that it contains a coating agent and the above-mentioned surfactant, and contains 0.5 to 5% by weight of this surfactant based on the weight of the coating agent. And

A feature of the method for producing a surfactant of the present invention is a method for producing a surfactant containing a polyoxyalkylene compound,
Step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of the non-reducing di- or trisaccharide (a1) and 20 to 60 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. ;
A step (2) of obtaining a monoglycidyl ether compound (MG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 1.2 to 2 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (4) of obtaining a dimer (DM) by reacting 1 mol part of the polyoxyalkylene compound (a12) with 0.95 to 1.15 mol part of a monoglycidyl ether compound (MG); and dimer (DM) 1 A method (1) comprising a step (5) of reacting a mole part with 0.95 to 1.15 mole part of a diglycidyl ether compound (DG) to obtain a polyoxyalkylene compound (Y1); or non-reducing A step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of a di- or trisaccharide (a1) with 20 to 60 mol part of an alkylene oxide (a2) having 2 to 4 carbon atoms;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (6) of obtaining a trimer (TM) by reacting 2 mol parts of the polyoxyalkylene compound (a12) with 1 to 1.2 mol parts of the diglycidyl ether compound (DG);
From the method (2) including the step (7) of reacting 1 mol part of the trimer (TM) and 0.95 to 1.2 mol part of the diglycidyl ether compound (DG) to obtain the polyoxyalkylene compound (Y2). This is the gist.

  When the surfactant of the present invention is used, a coating composition capable of forming a coating film excellent in toning properties (improvement of color floating, color separation, color unevenness, etc.) and water resistance can be easily obtained. Moreover, the pigment composition for this coating composition can be obtained easily.

  Since the pigment composition of this invention contains said surfactant, the coating composition excellent in toning property can be obtained.

  Since the coating composition of the present invention contains the above-described surfactant, a coating film having excellent toning properties can be easily formed.

In the general formula (1), U is a 2-hydroxypropylene group {—CH ₂ —CH (OH) —CH ₂ —} or a hydroxymethylethylene group {—CH ₂ —CH (CH ₂ OH) —}.

  In the general formula (1), m represents an integer of 3 or 4, and 4 is preferable. Within this range, the toning property is further improved.

  In the general formula (2), as the non-reducing di- or trisaccharide that can constitute the residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of the non-reducing di- or trisaccharide, Examples include sucrose, isosaccharose, trehalose, isotrehalose, gentianose, raffinose, meretitol, planteose and the like. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of toning properties and water resistance, more preferably sucrose and trehalose, and sucrose is particularly preferable from the viewpoint of availability.

  Among the oxyalkylene groups (OA) having 2 to 4 carbon atoms, from the viewpoint of toning and water resistance, when the total number of OA is 30 to 50, oxypropylene alone is preferable, and the total number of OA is 20 to 30 In this case, a mixture of oxypropylene and oxybutylene is preferable. When the total number of OA is 50 to 60, a mixture of oxypropylene and oxyethylene is preferable.

  When plural kinds of oxyalkylene groups are contained in OA, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and content ratio of these oxyalkylene groups, but the block shape or block shape and random shape It is preferable that the combination of these is included.

  When the mixture of oxypropylene and / or oxybutylene and oxyethylene is included, the content ratio (mol%) of oxyethylene is preferably 2 to 10, more preferably 2 to 2, based on the total number of moles of oxyalkylene groups. 8, particularly preferably 3-8. Further, it is preferable that oxypropylene and / or oxybutylene is located at the end away from the reaction residue (Q). That is, when OA contains an oxyethylene group, it is preferable that the oxyethylene group is directly bonded to the reaction residue (Q). Further, when the OA includes a plurality of types of oxyalkylene groups, it is preferable to include a block shape.

  The total number of oxyalkylene groups (OA) contained in the group (S) represented by the general formula (2) is preferably an integer of 20 to 60, more preferably an integer of 30 to 60, particularly preferably 30 to 50. It is an integer. In this range, the toning property and water resistance are further improved.

  n is preferably an integer of 5 to 30, more preferably an integer of 8 to 30, and particularly preferably an integer of 8 to 25. Within this range, the toning property and water resistance are further improved.

  t is preferably an integer of 2 to 4, more preferably 3. Within this range, the toning property and water resistance are further improved.

  Surfactants containing a polyoxyalkylene compound (YG) obtained by reacting 1 mol of a polyoxyalkylene compound (Y) with 1 to 5 mol of an alkyl glycidyl ether having 6 to 21 carbon atoms include polyoxyalkylene compound (YG). The oxyalkylene compound (Y) may be contained.

  The number of moles of the alkyl glycidyl ether having 3 to 18 carbon atoms is preferably an integer of 1 to 5, more preferably an integer of 1 to 4, particularly preferably 2 or 3 with respect to 1 mole of the polyoxyalkylene compound (Y). It is. Within this range, the toning property is further improved.

  Examples of the alkyl glycidyl ether having 6 to 21 carbon atoms include compounds represented by the general formula (3).

  R is an alkyl group having 3 to 18 carbon atoms (propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and Octadecyl, etc.}, O represents an oxygen atom, C represents a carbon atom, and H represents a hydrogen atom.

  That is, as the alkyl glycidyl ether having 6 to 21 carbon atoms, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, nonyl glycidyl ether Examples include ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, heptadecyl glycidyl ether, and octadecyl glycidyl ether. Of these, butyl glycidyl ether, 2-ethylhexyl glycidyl ether and dodecyl glycidyl ether are preferred, and butyl glycidyl ether and 2-ethylhexyl glycidyl ether are more preferred.

An alkyl glycidyl ether having 6 to 21 carbon atoms undergoes an addition reaction with a hydroxyl group of “Q- (OA) _n H” in the general formula (2) and an addition reaction with a hydroxyl group of “U” in the general formula (1). In some cases, it may react with either one, may react with both, may react with all of these, or may react with some of these.

  The polyalkylene compound (YG) is obtained by reacting 1 mol of the polyoxyalkylene compound (Y) represented by the general formula (1) with 1 to 5 mol of an alkyl glycidyl ether having 6 to 21 carbon atoms. “Polyoxyalkylene compound (a12) obtained by chemically reacting 1 mol part of non-reducing disaccharide or trisaccharide (a1) and 20 to 60 mol part of alkylene oxide (a2) having 2 to 4 carbon atoms” described later, You may manufacture, after making it react with C6-C21 alkyl glycidyl ether (it mentions later for details).

  The polyoxyalkylene compound (Y) represented by the general formula (1) can be produced by a production method comprising the following method (1) or (2).

<Method (1)>
Step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of the non-reducing di- or trisaccharide (a1) and 20 to 60 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. ;
A step (2) of obtaining a monoglycidyl ether compound (MG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 1.2 to 2 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (4) of obtaining a dimer (DM) by reacting 1 mol part of the polyoxyalkylene compound (a12) with 0.95 to 1.15 mol part of a monoglycidyl ether compound (MG); and dimer (DM) 1 A method (1) comprising a step (5) of obtaining a polyoxyalkylene compound (Y1) by reacting a mole part with 0.95 to 1.15 mole part of a diglycidyl ether compound (DG).

Step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of the non-reducing di- or trisaccharide (a1) and 20 to 60 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. ;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (6) of obtaining a trimer (TM) by reacting 2 mol parts of the polyoxyalkylene compound (a12) with 1 to 1.2 mol parts of the diglycidyl ether compound (DG);
A method (2) comprising a step (7) of reacting 1 mol part of trimer (TM) with 0.95 to 1.2 mol part of a diglycidyl ether compound (DG) to obtain a polyoxyalkylene compound (Y2).

  The polyoxyalkylene compounds (Y1) and (Y2) produced by these chemical reactions may have a distribution in the oxyalkylene group, the number of m and n, and the like. It becomes a mixture of alkylene compounds, and the polyoxyalkylene compound (Y) represented by the general formula (1) is contained in this mixture.

  In the step (1), the usage amount (mole part) of the alkylene oxide (a2) is preferably 20 to 60, more preferably 30 to 1 mole part of the non-reducing di- or trisaccharide (a1). 60, particularly preferably 30-50. In this range, the toning property and water resistance are further improved.

  In the step (2), the use amount (mol part) of the epihalohydrin (a3) is preferably 1.2 to 2 and more preferably 1.2 to 1 with respect to 1 mol part of the polyoxyalkylene compound (a12). .8, particularly preferably 1.3 to 1.5. Within this range, the yield of the monoglycidyl ether compound (MG) is further improved.

  In the step (3), the usage amount (mol part) of the epihalohydrin (a3) is preferably 2.5 to 4, more preferably 2.5 to 3 with respect to 1 mole part of the polyoxyalkylene compound (a12). .5, particularly preferably 2.5 to 3. Within this range, the yield of the diglycidyl ether compound (DG) is further improved.

  In the step (4), the usage amount (mole part) of the monoglycidyl ether compound (MG) is preferably 0.95 to 1.15, more preferably 1 mol part of the polyoxyalkylene compound (a12). 1 to 1.1, particularly preferably 1 to 1.05. Within this range, the yield of dimer (DM) is further improved.

  In the step (5), the amount (mole part) of the diglycidyl ether compound (DG) used is preferably 0.95 to 1.15, more preferably 1 to 1 part per 1 part by mole of the dimer (DM). .15, particularly preferably 1 to 1.1. Within this range, the yield of the polyoxyalkylene compound (Y1) is further improved.

  In the step (6), the usage amount (mole part) of the diglycidyl ether compound (DG) is preferably 1 to 1.2, more preferably 1 to 2 parts by mole with respect to the polyoxyalkylene compound (a12). 1.15, particularly preferably 1 to 1.1. Within this range, the trimer (TM) yield is further improved.

  In the step (7), the amount (mole part) of the diglycidyl ether compound (DG) used is preferably 0.95 to 1.2, more preferably 1 to 1, with respect to 1 mole part of the trimer (TM). .15, particularly preferably 1 to 1.1. Within this range, the yield of the polyoxyalkylene compound (Y2) is further improved.

  As the non-reducing di- or trisaccharide (a1), the same disaccharide or trisaccharide that can constitute the reaction residue (Q) in the general formula (2) 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 ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter referred to as BO). And a mixture thereof. Among these, from the viewpoint of toning properties and water resistance, when the amount of alkylene oxide (a2) used is 30 to 50 parts by mole with respect to 1 mole of the non-reducing di- or trisaccharide (a1), PO alone is preferable. Moreover, when the same usage-amount is 20-30 mol part, mixing of PO and BO is preferable, and when the same usage-amount is 50-60 mol part, mixing of PO and EO is preferable.

  Epihalohydrin (a3) includes epichlorohydrin and epibromohydrin. Of these, epichlorohydrin is preferred.

  In the step (1), when a plurality of types of alkylene oxide are used, the reaction order (block, random and combinations thereof) and the use ratio are not limited, but include block or a combination of block and random. It is preferable. Moreover, when it contains EO, the usage-amount (mol%) of EO is based on the total number of moles of alkylene oxide, 1-10 are preferable, More preferably, it is 1-8, Most preferably, it is 3-8. When EO and PO or / and BO are included, it is preferable to react PO and / or BO in a block form after the reaction of EO to the di- or trisaccharide (a1).

  The chemical reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2) may be carried out in any form such as 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 chemical reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). 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 based on the total weight of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). Is 0.1 to 1, particularly preferably 0.2 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. "Kyoward" is a registered trademark of the company. } (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).

  The end point of removal of the reaction catalyst is preferably a CPR (Controlled Polymerization Rate) value of 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. CPR is measured in accordance with JIS K1557-4: 2007.

  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 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.

  It is preferable to use a reaction solvent for the chemical reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). As the reaction solvent, those having no active hydrogen are preferable, and more preferably, non-reducing disaccharides or trisaccharides (a1), alkylene oxides (a2), and polyoxyalkylene products (a12) generated by these reactions are used. Those that dissolve are preferred.

  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 20 to 200 based on the weight of the polyoxyalkylene compound (a12) produced by the reaction between the di- or trisaccharide (a1) and the alkylene oxide (a2). Is more preferable, 40 to 180 is more preferable, and 60 to 150 is particularly preferable.

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, and particularly preferably 0.01 or less, based on the weight of the produced polymer. 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 distilling off at 100 to 150 ° C. under reduced pressure of 0.6 to 27 kPa can be applied.

  As the adsorption removal, a method of treatment using an alkali adsorbent {eg, trade name: Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd.} such as synthetic aluminosilicate 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 (a12), and the processing temperature is about 60 to 120 ° C. The processing time is about 0.5 to 5 hours. Subsequently, the residual amount of the reaction solvent can be reduced by removing the alkali adsorbent by filtration using filter paper or filter cloth.

  In the reaction of the polyoxyalkylene compound (a12) and the epihalohydrin (a3), an ether bond is formed by dehydrohalogenation from the hydrogen atom of the hydroxyl group of the polyoxyalkylene compound (a12) and the halogen atom of the epihalohydrin (a3). (Williamson synthesis method) can be applied.

  In the ether bond reaction (Williamson synthesis method) between the polyoxyalkylene compound (a12) and the epihalohydrin (a3), a vessel that can be heated, cooled, and stirred can be used, and is almost the same as the hydrogen halide generated by desorption. It is preferred to react in the presence of an amount of base.

  As the base, alkali metal or alkaline earth metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, etc.) and the like are used. Of these, alkali metal hydroxides are preferable, sodium hydroxide and potassium hydroxide are more preferable, and sodium hydroxide is particularly preferable.

  The amount of base used can be determined by the amount of epihalohydrin (a3) used (the amount actually designed for reaction). For example, when the amount of the epihalohydrin (a3) used is 1 mol part relative to 1 mol part of the polyoxyalkylene compound (a12), the amount of base used is 1 mol part per 1 mol part of the polyoxyalkylene compound (a12). It is. In this way, the step of neutralizing and removing excess base can be omitted, and the reaction is carried out in an excess of epihalohydrin (a3), but the excess is removed in a dehydration step under reduced pressure, etc. it can.

  Prior to the start of the chemical reaction between the polyoxyalkylene compound (a12) and the epihalohydrin (a3), the water content (wt%) is determined based on the weight of the polyoxyalkylene compound (a12), epihalohydrin (a3) and base. It is preferable to adjust to 2-5, More preferably, it is 2.5-4.5, Especially preferably, it is adjusting to 3-4. Within this range, the produced neutralized salt crystallizes greatly and can be easily removed by a desalting filtration step (for example, filter paper No. 2: manufactured by ADVANTEC, reserved particle diameter: 5 μm).

  The reaction temperature (° C.) between the polyoxyalkylene compound (a12) and the epihalohydrin (a3) is preferably 40 to 80, more preferably 50 to 70. As the reaction atmosphere, it is preferable to make the inside of the reaction apparatus an atmosphere of inert gas (argon, nitrogen, carbon dioxide, etc.) before introducing epihalohydrin into the reaction system.

  The end point of the reaction between the polyoxyalkylene compound (a12) and the epihalohydrin (a3) can be confirmed by the following method or the like. That is, when the pH of the reaction solution is measured and becomes 6 to 8, the reaction is terminated. The required reaction time is usually 3 to 12 hours. In addition, pH can be measured by attaching a reaction liquid directly to a litmus paper and observing a color change (20-30 degreeC).

  Subsequently, the monoglycidyl ether compound (MG) or the diglycidyl ether compound (DG) is isolated and purified through desalting (removal of neutralized salt), dehydration and the like by a conventional method (filtration or the like).

A known method can be applied for desalting (filtration), and normal natural filtration or vacuum filtration (suction filtration) may be used. Known filter media and filtration devices can be applied as they are.
As filtration temperature (degreeC), about 50-80 are preferable, More preferably, it is 60-70.

The method for dehydration is not limited, but a method of distilling under reduced pressure (dehydration under reduced pressure) is preferred. Distillation under reduced pressure (dehydration under reduced pressure) can be removed together with water even if excess epihalohydrin (a3) remains.
When distilling off under reduced pressure, the pressure {gauge pressure (hereinafter the same)} is preferably about -0.05 to -0.098 MPa, and the temperature is preferably about 60 to 80 ° C.

The water content (% by weight) after dehydration is preferably 0.2 or less, more preferably 0.1 or less, particularly preferably 0.1 or less, based on the weight of the monoglycidyl ether compound (MG) or diglycidyl ether compound (DG). Preferably it is 0.05 or less.
The water content (% by weight) can be measured by a known method, for example, by the Karl Fischer method (JIS K0113: 2005, coulometric titration method).

  After obtaining the monoglycidyl ether compound (MG) or the diglycidyl ether compound (DG), when an excess base remains in these, it is preferable to remove this. As the removal method, the removal method of “reaction catalyst that can be used for addition reaction of alkylene oxide (a2)” described in the production method of the polyoxyalkylene compound (a12) can be applied. Among these, a method of filtering a neutralized salt (hydrochloride, sulfate, carbonate, etc.) generated by neutralizing a base with an acid (mineral acid, carbon dioxide, etc.) is preferable. Applying the method of filtration is efficient because it can be filtered with the neutralized salt by-produced in the chemical reaction (2). The remaining amount may be further reduced by treating the base with an alkali adsorbent instead of or together with the filtration method.

  When the base is neutralized with an acid, the acids include mineral acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.), organic acids (formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, terephthalic acid, oxalic acid, malon Acid, adipic acid, succinic acid, lactic acid, etc.) can be used.

  The remaining amount of the base can be managed by a CPR (Controlled Polymerization Rate) value described in JIS K1557-4: 2007. The CPR value is preferably 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less.

  The epoxy equivalent (g / eq.) Of the monoglycidyl ether compound (MG) and the diglycidyl ether compound (DG) can be measured according to JIS K7236: 1995 (epoxy equivalent test method for epoxy resin).

  Reaction of polyoxyalkylene compound (a12) with monoglycidyl ether compound (MG) or diglycidyl ether compound (DG), reaction of dimer (DM) with diglycidyl ether compound (DG), and trimer (TM) with dimer The reaction with the glycidyl ether compound (DG) includes “reaction catalyst, reaction vessel, reaction conditions that can be used for the addition reaction of alkylene oxide (a2)” described in the method for producing the polyoxyalkylene compound (a12). Applicable.

  The end point of these reactions can be performed by the disappearance of the epoxy group. The epoxy group is quantified by cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and reacted with the epoxy group. : Conforming to ISO3001: 1999) is applicable.

  The polyalkylene compound (YG) is obtained by reacting 1 mol of the polyoxyalkylene compound (Y) represented by the general formula (1) with 1 to 5 mol of an alkyl glycidyl ether having 6 to 21 carbon atoms. The polyoxyalkylene compound (a12) and the carbon number alkyl glycidyl ether are reacted to prepare a polyoxyalkylene compound (a12) ′, and then the polyoxyalkylene compound (a12) is converted into the polyoxyalkylene compound (a12). It can be produced by the above method (1) or (2) other than changing to ')'.

  For the reaction of the polyoxyalkylene compound (Y1) or (Y2) with an alkyl glycidyl ether having 6 to 21 carbon atoms and the reaction of the polyoxyalkylene compound (a12) with an alkyl glycidyl ether having carbon atoms, a polyoxyalkylene compound ( The “reaction catalyst, reaction vessel, reaction conditions that can be used for the addition reaction of alkylene oxide (a2)” described in the production method of a12) can be applied.

  The end point of these reactions can be performed by the disappearance of the epoxy group. The epoxy group is quantified by cetyltrimethylammonium bromide (CTAB) method (JIS K7236) in which hydrogen halide (HB) is generated from perchloric acid and a quaternary ammonium salt (CTAB) and reacted with the epoxy group. : Conforming to ISO3001: 1999) is applicable.

  Examples of the polyoxyalkylene compound (Y1) prepared by the method (1) include those exemplified in Table 1, and examples of the polyoxyalkylene compound (Y2) prepared by the method (2) include those exemplified in Table 2. Can be mentioned.

In the column of non-reducing disaccharide or trisaccharide (a1), Q1 represents sucrose, Q2 represents trehalose, and Q3 represents raffinose. In the column of alkylene oxide (a2), P represents propylene oxide, E represents ethylene oxide, and B represents butylene oxide, and these subscripts represent moles per mole of the non-reducing di- or trisaccharide (a1), respectively. Represents a number, / represents a block shape, and • represents a random shape.
In the column of the polyoxyalkylene compound (a12), being written in two steps means that two types of polyoxyalkylene compounds (a12) were used, and the upper row was used in steps (1) and (3). The raw material represents the raw material used in the steps (1), (3), (6) or the raw material used in the steps (1), (3), (6). Moreover, epichlorohydrin is used as epihalohydrin (a3). Moreover, about the polyoxyalkylene compound (Y), the value corresponding to t and m of General formula (1), (2) is shown in the table | surface.

  Examples of the polyoxyalkylene compound (YG) obtained by reacting the polyoxyalkylene compound (Y) with an alkyl glycidyl ether having 6 to 21 carbon atoms include those exemplified in Table 3. In the column (Y), the polyoxyalkylene compound (Y) to be reacted and the number of the polyoxyalkylene compound (Y) exemplified in Table 1 or 2 is shown. In the column of alkyl glycidyl ether, BUG represents butyl glycidyl ether, EHG represents 2-ethylhexyl glycidyl ether, DDG represents dodecyl glycidyl ether, HDG represents hexadecyl glycidyl ether, and these suffixes are polyoxyalkylenes. The number of moles relative to 1 mole of compound (Y) is represented.

  Among these polyoxyalkylene compounds (Y1, Y2, YG), No. 1, 2, 6, 7, 8, 10, 12, 13, 16, 19, 21, 22, 24, 27, 28, 29, 30, 30, 32, 33, 34, 36, 39 and 40 Of the polyoxyalkylene compound represented by formula (I) is preferred, and more preferably 7, 8, 10, 12, 13, 16, 23, 24, 28, 30, 32, 33, 36 and 39, particularly preferably 10, 13, 28, 33 and 39 is a polyoxyalkylene compound represented by any one of 39.

  In addition to the polyoxyalkylene compounds (Y) and (YG), other additives (viscosity modifiers, antifoaming agents, wetting agents, dispersants, etc.) are used in combination with the surfactant of the present invention, if necessary. It can be included.

  As the viscosity modifier, SN thickener 601 and 612 (manufactured by San Nopco Co., Ltd.) and the like, as the antifoaming agent, SN deformer 180 and 184 (manufactured by San Nopco Co., Ltd.), etc., as the wetting agent, SN wet 125 and 126 ( Examples of the dispersant include Nop Cosperth 6100 and 6110, SN Dispersant 2060 and 5041 (San Nopco Co., Ltd.), and the like. In addition, when using or containing an additive together, as these usage-amounts or content, all are 0.1-100 weight% based on the weight of a polyoxyalkylene compound (Y) and (YG).

  When the surfactant of the present invention contains other additives as required, there are no restrictions on the polyoxyalkylene compounds (Y) and (YG) and their blending methods as long as they can be mixed uniformly. Examples include a method in which each necessary amount is put into a container and sealed, and then uniformly stirred and mixed at room temperature (10 to 30 ° C.) or heated (30 to 70 ° C.).

  The surfactant of the present invention is suitable as an additive for a coating composition containing a pigment, for example, a toning improver, a hydrophilicity imparting agent, a stain reducing agent, an antifogging agent for a coating composition containing a pigment. Besides emulsifying agents, surface tension reducing agents (including curtain flow coatability improving agents and spraying optimization agents), and anti-skinning agents (a phenomenon in which the surface of a paint solidifies during storage of water-based paint in a container) Can be used widely as a raw material for these materials.

  Examples of pigments include various natural pigments and synthetic pigments (synthetic organic pigments, synthetic inorganic pigments, etc.), in addition to titanium white, cadmium yellow, chrome yellow, iron yellow, ultramarine blue, bengara, and carbon black. Examples thereof include phthalocyanine-based, quinoline-based, azo-based and anthraquinone-based pigments. These pigments are used alone or as a mixed pigment of at least two kinds (two products). Furthermore, various extender pigments such as calcium carbonate, talc and mica can be used.

  When the surfactant of the present invention is used as an additive for a coating composition containing a pigment, the surfactant of the present invention is added when preparing a pigment dispersion (pigment composition) (pigment dispersion step). Or after adding to the finished pigment dispersion), it may be added to any of the coating processes, and added to the finished coating composition (paint). You can also. In any of these cases, excellent toning properties and water resistance can be exhibited.

  The pigment composition (pigment paste) of the present invention can contain a dispersant, a dispersion medium (water, etc.) and the like in addition to the pigment and the surfactant, as long as the surfactant and the pigment are contained.

  The content (% by weight) of the surfactant is preferably 10 to 100, more preferably 10 to 90, and particularly preferably 20 to 80, based on the weight of the pigment. When a dispersing agent or a dispersion medium is contained, these contents can be contained within a normal range.

  The pigment composition (pigment paste) of the present invention is not limited in the production method as long as the pigment, the surfactant and the like can be uniformly dispersed and mixed. For example, it can be prepared by uniformly dispersing and mixing using a mixer such as a ball mill, an Excel auto homogenizer, or a disper. The pigment composition may be defoamed.

The coating composition of the present invention contains a coating agent and the above surfactant, or contains a coating agent and the above pigment composition.
As the coating agent, both an aqueous coating agent and a non-aqueous coating agent can be applied, and among these, an aqueous coating agent is preferable, an aqueous emulsion coating agent is more preferable, an acrylic type, a vinyl acetate type are particularly preferable. , Styrene-based, halogenated olefin-based, urethane-based, acrylic-silicon-based or fluorine-based aqueous emulsion coating agent.

  When the coating composition of the present invention contains a coating agent and the above pigment composition, the content (% by weight) of the pigment composition is preferably 1 to 20, more preferably based on the weight of the coating agent. Is from 2 to 15, particularly preferably from 2 to 10.

  When the coating composition of the present invention contains a coating agent and the above-described surfactant, the content (% by weight) of the surfactant is appropriately determined according to the use. For example, the coating composition is aqueous. When used in paints (including paper coating paints and various inks), 0.5 to 5 is preferable, 1 to 5 is more preferable, and 1 to 4 is particularly preferable based on the weight of the coating agent.

  In addition to the coating agent, surfactant and pigment composition, the coating composition of the present invention may contain a film-forming regulator, extender pigment (clay, calcium carbonate, etc.), thickener and solvent (water, etc.).

  The coating composition of the present invention is not limited in the production method as long as the coating agent and the pigment composition or coating agent and the surfactant described above can be uniformly dispersed and mixed. For example, it can be prepared by uniformly dispersing and mixing using a mixer such as an Excel auto homogenizer or a disper. The coating composition may be defoamed.

  The coating composition of the present invention can be applied to an object to be coated by an ordinary method, such as brush coating, roller coating, bell coating, air spray coating, airless coating, roll coater coating, and flow coater coating. Is applicable. The drying method may be normal drying or baking drying, and baking drying is performed according to a conventional method, for example, using an electric hot air dryer, an indirect hot air oven, a direct hot air oven, a far infrared oven, etc. It can be carried out by holding the coating film at 260 ° C. for several tens of seconds to 30 minutes.

  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”.

<Production Example 1>
In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, pressurizing with nitrogen, and depressurization with a vacuum pump, 342 parts (1 mol part) of purified granulated sugar {sucrose made by Taiyo Co., Ltd., hereinafter the same} and DMF {Mitsubishi After the introduction of 1000 parts by Gas Chemical Co., Ltd., the same applies hereinafter, the operation of pressurizing to 0.1 MPa with nitrogen gas and discharging to 0.02 MPa was repeated three times (this Hereinafter, the operation using nitrogen gas is abbreviated as nitrogen substitution.) Thereafter, the temperature was raised to 100 ° C. while stirring, 360 parts (5 parts by mole) of butylene oxide (BO) was added dropwise over 2 hours at the same temperature, and stirring was further continued for 2 hours at the same temperature. Next, 870 parts (15 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 4 hours, and stirring was further continued at the same temperature for 4 hours. Subsequently, DMF was removed at 120 ° C. under reduced pressure of 1.3 to 13 kPa (hereinafter simply referred to as “removing DMF”) to obtain an adduct (S1) of sucrose / BO 5 mol / PO 15 mol.

<Production Example 2>
In the same reaction vessel as in Production Example 1, after adding 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF and replacing with nitrogen, the temperature was raised to 100 ° C. with stirring, and then propylene oxide (PO) at the same temperature. 1160 parts (20 mol parts) was added dropwise over 6 hours, and stirring was further continued at the same temperature for 4 hours. Next, DMF was removed to obtain a sucrose / PO20 molar adduct (S2Be).

  In the same reaction vessel as in Production Example 1, sucrose / PO 20 mol adduct (S2Be) 1502 parts (1 mol part) and potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. Displayed in minutes equivalent. same as below. } 5 parts were added and “dehydrated at 120 ° C. under reduced pressure of 0.6 to 1.3 kPa” (the operation in the “” is hereinafter referred to as dehydration). Subsequently, 580 parts (10 mol parts) of propylene oxide (PO) was added dropwise over 4 hours at 100 ° C. with reduced pressure, and stirring was further continued for 4 hours at 120 ° C. Next, after adding 40 parts of deionized water at 80 ° C., 80 parts of an inorganic adsorbent {Kyoward 700, manufactured by Kyowa Chemical Industry Co., Ltd., hereinafter the same} is added and stirred at the same temperature for 2 hours. The inorganic adsorbent was removed by filtration using No. 2 filter paper (manufactured by Toyo Filter Paper Co., Ltd., retained particle diameter: 5 μm, the same shall apply hereinafter) at the same temperature, and further at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa. 1 hour dehydration ”(the operation in“ ”is hereinafter abbreviated as purification treatment) to obtain a sucrose / PO 30 molar adduct (S2).

<Production Example 3>
In the same reaction vessel as in Production Example 1, 1502 parts (1 mole part) of sucrose / PO 20 mole adduct (S2Be) and 6 parts of potassium hydroxide were added for dehydration. Next, 1100 parts (20 mole parts) of propylene oxide (PO) was added dropwise over 5 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Subsequently, purification was performed to obtain a sucrose / PO 40 molar adduct (S3).

<Production Example 4>
In the same reaction vessel as in Production Example 1, 1502 parts (1 mole part) of sucrose / PO 20 mole adduct (S2Be) and 7 parts of potassium hydroxide were added for dehydration. Subsequently, 1740 parts (30 mole parts) of propylene oxide (PO) was added dropwise over 5 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, purification was performed to obtain a sucrose / PO 50 mol adduct (S4).

<Production Example 5>
In the same reaction vessel as in Production Example 1, 342 parts (1 mole part) of purified granulated sugar and 1500 parts of DMF were added and purged with nitrogen, and then the temperature was raised to 100 ° C. while stirring and 220 parts of ethylene oxide (EO) at the same temperature ( 5 mol parts) and 290 parts (5 mol parts) of propylene oxide (PO) are added dropwise over 3 hours, and then 580 parts (10 mol parts) of propylene oxide (PO) are added over 5 hours at the same temperature. The solution was added dropwise, and stirring was further continued at the same temperature for 4 hours. Next, DMF was removed to obtain an adduct (S5Be) of sucrose / EO 5 mol · PO 5 mol / PO 10 mol.

  To the same reaction vessel as in Production Example 1, sucrose / EO 5 mol / PO 5 mol / PO 10 mol adduct (S5Be) 1432 parts (1 mol part) and potassium hydroxide 8 parts were added and dehydrated. Next, 23100 parts (40 mole parts) of propylene oxide (PO) was added dropwise over 5 hours at 100 ° C. with reduced pressure, and stirring was further continued for 4 hours at 120 ° C. Next, purification treatment was performed to obtain an adduct (S5) of sucrose EO 5 mol · PO 5 mol / PO 50 mol.

<Production Example 6>
In the same reaction vessel as in Production Example 1, 342 parts (1 mole part) of trehalose {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} and 1200 parts of DMF were purged with nitrogen, and the temperature was raised to 100 ° C. while stirring. Subsequently, 1740 parts (30 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 7 hours, and stirring was further continued at the same temperature for 4 hours. Next, DMF was removed to obtain a trehalose / PO 30 molar adduct (S6).

<Production Example 7>
In the same reaction vessel as in Production Example 1, 2082 parts (1 mol part) of trehalose / PO 30 mol adduct (S6) and 3 parts of potassium hydroxide were added for dehydration. Subsequently, 580 parts (10 mol parts) of propylene oxide (PO) was added dropwise over 3 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 2 hours. Next, purification was performed to obtain a trehalose / PO40 molar adduct (S7).

<Production Example 8>
In the same reaction vessel as in Production Example 1, 504 parts (1 mole part) of raffinose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 800 parts of DMF were added and purged with nitrogen, and then the temperature was raised to 100 ° C while stirring. Then, 870 parts (15 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 5 hours, and stirring was further continued at the same temperature for 4 hours. DMF was then removed to obtain a raffinose / PO15 molar adduct (S8Be).

  In the same reaction vessel as in Production Example 1, 1374 parts (1 mole part) of raffinose / PO 15 mole adduct (S8Be) and 4 parts of potassium hydroxide were added for dehydration. Next, 870 parts (15 parts by mole) of propylene oxide (PO) was added dropwise over 6 hours at 100 ° C. with reduced pressure, and stirring was further continued at 120 ° C. for 4 hours. Next, purification was performed to obtain a raffinose / PO 30 molar adduct (S8).

<Production Example 9>
In the same reaction vessel as in Production Example 1, sucrose / BO 5 mol / PO 15 mol adduct (S1) 1572 parts (1 mol part) obtained in Production Example 1 and sodium hydroxide {reagent special grade, Wako Pure Chemical Industries, Ltd. Manufactured, purity is about 97% by weight, and the amount used is expressed in terms of pure content excluding moisture. same as below. } 40.4 parts (1.01 mol part) and 70 parts of water were charged and stirred at 60 ° C., and epichlorohydrin {manufactured by Daiso Co., Ltd., hereinafter the same} 130 parts (1.4 mol parts) was added for 4 hours. It was dripped at. Subsequently, stirring is continued at 60 ° C. for 5 hours, and the pH of the reaction solution is 7 to 8 {Litmus test paper (manufactured by TOYO ROSHI CO. LTD, product name: UNIV PH 1-11). same as below. } Was confirmed. Next, after “dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.03% by weight), suction filtration with No. 2 filter paper” was performed (for operations in this “”, Hereinafter, simply abbreviated as dehydration / filtration), a monoglycidyl ether compound (S1-MG) was obtained. This epoxy equivalent is 1650 g / eq. Met. The epoxy equivalent was measured according to JIS K7236: 1995, (Epoxy equivalent test method of epoxy resin) (hereinafter the same).

<Production Example 10>
In the same reaction vessel as in Production Example 1, 1572 parts (1 mole part) of sucrose / BO 5 mole / PO15 mole adduct (S1) obtained in Production Example 1 and 80.8 parts (2.02 mole part) of sodium hydroxide Then, 80 parts of water was charged, and 260 parts (2.8 parts by mole) of epichlorohydrin was added dropwise over 6 hours while stirring at 60 ° C. Subsequently, stirring was continued at 60 ° C. for 5 hours, and it was confirmed that the pH of the reaction system became 7-8. Subsequently, dehydration and filtration were performed to obtain a diglycidyl ether compound (S1-DG). Epoxy equivalent is 840 g / eq. Met.

<Production Examples 11-18>
“Adduct obtained in Production Example 1 / BO 5 mol / PO 15 mol adduct (S1) (1 mol part)” as “addition obtained in Production Example 2, 3, 6 or 8 {(S2), (S3), Monoglycidyl ether compound {(S1-MG), (S2-MG), in the same manner as in Production Examples 9 and 10, except that (S6) or (S8) (one mole part)} (S3-MG), (S6-MG), (S8-MG)} and diglycidyl ether compounds {(S1-DG), (S2-DG), (S3-DG), (S6-DG), (S8 -DG)}. These epoxy equivalents are listed in Table 4.

<Example 1>
The same reaction vessel as in Production Example 1 was charged with 2082 parts (1 mol part) of sucrose / PO 30 mol mol adduct (S2) obtained in Production Example 2 and 12 parts of potassium hydroxide, and then dehydrated. Next, at 80 ° C., 2150 parts (1 mole part) of the monoglycidyl ether compound (S2-MG) {(S2) -monoglycidyl ether, epoxy equivalent: 2150} obtained in Production Example 11 was added. After dehydration at a reduced pressure of 1.3 to 2.7 kPa for 1 hour ”(the operation of“ ”is hereinafter abbreviated as additional dehydration), stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. {Dimer (DM1)}. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 2200 parts (1 mole part) of the diglycidyl ether compound (S2-DG) {(S2) -diglycidyl ether, epoxy equivalent: 1100} obtained in Production Example 12 was added, and added at the same temperature. After dehydration, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant (polyoxyalkylene compound) (Y11) of the present invention.

The weight average molecular weight (Mw) of the surfactant (Y11) was 6300, and Mw / Mn was 2.4.
Further, from the molecular weight distribution chart, the main peak was about 65 area%, the high molecular weight portion was about 20 area% than the main, and the low molecular weight portion considered to be unreacted was about 15 area% (in the following examples) Was about the same).
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.
The weight average molecular weight was measured and calculated (hereinafter the same) under the following conditions using gel permeation chromatography (GPC) with polystyrene having a known molecular weight as a standard substance.

Apparatus: manufactured by Tosoh Corporation (model HLC-8120GPC)
Column: Toso-type SuperH-4000 × 2 and the same type SuperH-3000 × 1 column connected in series Detector: Differential refraction detector Data processor: Data processor manufactured by Tosoh Corporation SC-8020)
Column temperature: 40 ° C
Eluent: THF (reagent grade 1, manufactured by Katayama Chemical)
Flow rate: 0.5 ml / min.
Sample concentration: 1% by weight
Sample solution injection volume: 10 μl

<Example 2>
In the same reaction vessel as in Production Example 1, 18 parts of potassium hydroxide was added to 6432 parts (1 mol part) of the surfactant (Y11) obtained in Example 1, followed by dehydration. Next, at 80 ° C., butyl glycidyl ether {Epogosei BA, manufactured by Yokkaichi Gosei Co., Ltd., epoxy equivalent: 135, and so on. “Epo Gosei” is a registered trademark of the company. } After adding 270 parts (2 mole parts) and substituting with nitrogen, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG11) of the present invention. The weight average molecular weight of the surfactant (YG11) was 6560, and Mw / Mn was 2.5.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 3>
The same reaction vessel as in Production Example 1 was charged with 2662 parts (1 mol part) of trehalose / PO 40 mol adduct (S7) obtained in Production Example 7 and 12 parts of potassium hydroxide, and then dehydrated. Subsequently, at 80 ° C., the monoglycidyl ether compound (S1-MG) obtained in Production Example 9 {sucrose / BO 5 mol / PO 15 mol adduct-monoglycidyl ether, epoxy equivalent: 1650} 1650 parts (1 mol part) was added. After the additional dehydration, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 1680 parts (1 mole part) of the diglycidyl ether compound (S1-DG) {(S1) -diglycidyl ether, epoxy equivalent: 840} obtained in Production Example 10 was added, and after dehydration, Stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {dimer (DM2)}. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y12) of the present invention. The weight average molecular weight of the surfactant (Y12) was 5860, and Mw / Mn was 2.3.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 4>
In the same reaction vessel as in Production Example 1, 18 parts of potassium hydroxide was added to 5992 parts (1 mole part) of the surfactant (Y12) obtained in Example 3, followed by dehydration. Next, at 80 ° C., 680 parts (2 mole parts) of dodecyl glycidyl ether {CE-EP, Yokkaichi Synthesis Co., Ltd., epoxy equivalent: 340} is added, and after nitrogen substitution, stirring is continued at 140 ° C. for 12 hours. The disappearance of the epoxy group was confirmed. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG12) of the present invention. The weight average molecular weight of the surfactant (YG12) was 6620, and Mw / Mn was 2.4.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 5>
The same reaction vessel as in Production Example 1 was charged with 3242 parts (1 mol part) of sucrose / PO 50 mol adduct (S4) obtained in Production Example 4 and 16 parts of potassium hydroxide, and then dehydrated. Next, at 80 ° C., 2140 parts (1 mole part) of the monoglycidyl ether compound (S6-MG) {trehalose / PO 30 mole adduct-monoglycidyl ether, epoxy equivalent: 2140} obtained in Production Example 15 was added, followed by dehydration. Then, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 2200 parts (1 mole part) of the diglycidyl ether compound (S6-DG) {(S6) -diglycidyl ether, epoxy equivalent: 1100} obtained in Production Example 16 was added, and after dehydration, Stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {dimer (DM3)}. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y13) of the present invention. The weight average molecular weight of the surfactant (Y13) was 7160, and Mw / Mn was 2.6.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 6>
In the same reaction vessel as in Production Example 1, 20 parts of potassium hydroxide was added to 7582 parts (1 mol part) of the surfactant (Y13) obtained in Example 5, followed by dehydration. Next, at 80 ° C., 540 parts (4 mole parts) of butyl glycidyl ether was added, and after substitution with nitrogen, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG13) of the present invention. The weight average molecular weight of the surfactant (YG13) was 7320, and Mw / Mn was 2.7.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 7>
The same reaction vessel as in Production Example 1 was charged with 3752 parts (1 mole part) of sucrose / EO 5 mol / PO 5 mole / PO 50 mole adduct (S5) obtained in Production Example 5 and 16 parts of potassium hydroxide, followed by dehydration. . Subsequently, at 80 ° C., 2330 parts (1 mole part) of monoglycidyl ether compound (S8-MG) {raffinose / PO30 mole adduct-monoglycidyl ether, epoxy equivalent: 2330} obtained in Production Example 17 was added, followed by dehydration. Then, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., after adding the diglycidyl ether compound (S8-DG) {(S8) -diglycidyl ether, epoxy equivalent: 1190} 2380 parts (1 mol part) obtained in Production Example 18, followed by additional dehydration, Stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {dimer (DM4)}. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y14) of the present invention. The weight average molecular weight of the surfactant (Y14) was 7780, and Mw / Mn was 2.5.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 8>
In the same reaction vessel as in Production Example 1, 862 parts (1 mole part) of the surfactant (Y14) obtained in Example 7 was charged with 22 parts of potassium hydroxide and then dehydrated. Subsequently, 380 parts (2 mole parts) of 2-ethylhexyl glycidyl ether {Epogosei 2EH, Yokkaichi Gosei Co., Ltd., epoxy equivalent: 190, hereinafter the same} is added at 80 ° C. Stirring was continued for a while to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG14) of the present invention. The weight average molecular weight of the surfactant (YG14) was 8100, and Mw / Mn was 2.6.
From the above values, it was confirmed that the compound having a value of m of 3 in the general formula (1) is the main product.

<Example 9>
The same reaction vessel as in Production Example 1 was charged with 5324 parts (2 mol parts) of sucrose / PO 40 mol adduct (S3) obtained in Production Example 3 and 20 parts of potassium hydroxide, and then dehydrated. Next, at 80 ° C., 2780 parts (1 mole part) of the diglycidyl ether compound (S3-DG) {(sucrose / PO 40 mole adduct-diglycidyl ether, epoxy equivalent: 1390) obtained in Production Example 14 was added. After dehydration, stirring was continued for 12 hours at 140 ° C. to confirm the disappearance of the epoxy group, and then 8 parts of potassium hydroxide was added for dehydration, followed by diglycidyl ether compound (S3-DG) at 80 ° C. 2780 parts (1 mole part) was added, and after additional dehydration, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {trimer (TM1)}. The surfactant {polyoxyalkylene compound} (Y21) was obtained, and the surfactant (Y21) had a weight average molecular weight of 9700 and Mw / Mn of 2.5.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 10>
In the same reaction vessel as in Production Example 1, 26 parts of potassium hydroxide was added to 10884 parts (1 mol part) of the surfactant (Y21) obtained in Example 9, and then dehydrated. Next, at 80 ° C., 675 parts (5 mol parts) of butyl glycidyl ether was added, and after substitution with nitrogen, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG21) of the present invention. The weight average molecular weight of the surfactant (YG21) was 10400, and Mw / Mn was 2.5.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 11>
The same reaction vessel as in Production Example 1 was charged with 5324 parts (2 mole parts) of trehalose / PO 40 mol adduct (S7) obtained in Production Example 7 and 20 parts of potassium hydroxide, and then dehydrated. Next, at 80 ° C., 2200 parts (1 mol part) of the diglycidyl ether compound (S6-DG) {trehalose / PO 30 mol adduct-diglycidyl ether, epoxy equivalent: 1100} obtained in Production Example 16 was added, followed by dehydration. Then, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group {trimer (TM2)}. Thereafter, 7 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 2200 parts (1 mol part) of a diglycidyl ether compound (S6-DG) was added, and after additional dehydration, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y22) of the present invention. The weight average molecular weight of the surfactant (Y22) was 9040, and Mw / Mn was 2.3.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 12>
In the same reaction vessel as in Production Example 1, 25 parts of potassium hydroxide was added to 9724 parts (1 mol part) of the surfactant (Y22) obtained in Example 11, and then dehydrated. Next, at 80 ° C., 570 parts (3 mol parts) of 2-ethylhexyl glycidyl ether was added, and stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG22) of the present invention. The weight average molecular weight of the surfactant (YG22) was 9540, and Mw / Mn was 2.4.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 13>
The same reaction vessel as in Production Example 1 was charged with 7504 parts (2 mol parts) of sucrose / EO 5 mol / PO 5 mol / PO 50 mol adduct (S5) obtained in Production Example 5 and 28 parts of potassium hydroxide, followed by dehydration. . Next, at 80 ° C., 2200 parts (1 mole part) of the diglycidyl ether compound (S2-DG) {sucrose / PO 30 mole adduct-diglycidyl ether, epoxy equivalent: 1100} obtained in Production Example 12 was added, followed by dehydration. Then, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 2200 parts (1 mol part) of diglycidyl ether compound (S2-DG) was added, and after additional dehydration, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {trimer ( TM3)}. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y23) of the present invention. The weight average molecular weight of the surfactant (Y23) was 10500, and Mw / Mn was 2.8.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 14>
In the same reaction vessel as in Production Example 1, 28 parts of potassium hydroxide was added to 11904 parts (1 mol part) of the surfactant (Y23) obtained in Example 13, followed by dehydration. Next, at 80 ° C., 570 parts (3 mol parts) of 2-ethylhexyl glycidyl ether was added, and after substitution with nitrogen, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG23) of the present invention. The weight average molecular weight of the surfactant (YG23) was 11000, and Mw / Mn was 2.7.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 15>
The same reaction vessel as in Production Example 1 was charged with 3144 parts (2 mol parts) of sucrose / BO 5 mol / PO 15 mol adduct (S1) obtained in Production Example 1 and 15 parts of potassium hydroxide, and then dehydrated. Next, at 80 ° C., the diglycidyl ether compound (S1-DG) obtained in Production Example 10 {sucrose / BO 5 mol / PO 15 mol adduct-diglycidyl ether, epoxy equivalent: 840} 1680 parts (1 mol part) was added. After the additional dehydration, stirring was continued at 140 ° C. for 12 hours to confirm the disappearance of the epoxy group. Thereafter, 6 parts of potassium hydroxide was added for dehydration. Next, at 80 ° C., 1680 parts (1 mol part) of a diglycidyl ether compound (S1-DG) was added, and after additional dehydration, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group {trimer ( TM4)}. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (Y24) of the present invention. The weight average molecular weight of the surfactant (Y24) was 6240, and Mw / Mn was 2.2.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Example 16>
In the same reaction vessel as in Production Example 1, 20 parts of potassium hydroxide was added to 6504 parts (1 mol part) of the surfactant (Y24) obtained in Example 15, followed by dehydration. Next, at 80 ° C., cetyl glycidyl ether {CE-EP, manufactured by Yokkaichi Gosei Co., Ltd., epoxy equivalent: 350} 350 parts (1 mole part) and 405 parts (3 mole parts) butyl glycidyl ether were added, and nitrogen-substituted. Thereafter, stirring was continued at 140 ° C. for 15 hours to confirm the disappearance of the epoxy group. Thereafter, purification treatment was performed to obtain the surfactant {polyoxyalkylene compound} (YG24) of the present invention. The weight average molecular weight of the surfactant (YG24) was 6500, and Mw / Mn was 2.2.
From the above values, it was confirmed that the compound having a value of m of 4 in the general formula (1) was the main product.

<Comparative Example 1>
BLAUNON OT-21 {manufactured by Aoki Oil & Fat Co., Ltd., polyoxyethylene sorbitan monooleate} was used as a comparative surfactant (H1).

<Comparative Example 2>
BLAUNON GL-20 {manufactured by Aoki Yushi Kogyo Co., Ltd., polyoxyethylene glycerol ether, glycerin / EO 20 mol} was used as a comparative surfactant (H2).

<Comparative Example 3>
In the same reaction vessel as in Production Example 1, 6484 parts (2 mole parts) of sucrose / PO 50 mol adduct (S5) obtained in Production Example 5 was charged and dehydrated. Next, after cooling to 50 ° C., isophorone diisocyanate {Desmodule I, manufactured by Sumika Bayer Urethane Co., Ltd., “Desmodule” is a registered trademark of Bayer Aktiengesellschaft. } After adding 222 parts (1 mole part), the temperature was raised to 100 ° C. over 1 hour with stirring, and stirring was continued at the same temperature for 8 hours to confirm the disappearance of the isocyanate group. The polyoxyalkylene compound thus obtained was used as a comparative surfactant (H3).

  Using the surfactants obtained in Examples and Comparative Examples, a pigment composition (pigment paste) was prepared as follows, and these were then converted into a commercially available coating agent {normally dry water-based paint (white)}. The coating composition {paint} was prepared by addition. Also, a commercially available coating agent {normally dry aqueous paint (white)} was added with any of the commercially available pigment pastes and the surfactants obtained in Examples and Comparative Examples to prepare a coating composition {paint}. Using these coating compositions {paints}, gloss, toning (color unevenness, floating mottle, etc.), hydrophilicity, water resistance and the like were evaluated, and the results are shown in Tables 8-10.

Preparation of pigment composition (1) Preparation of pigment composition for evaluation-1
Using an Excel auto homogenizer equipped with impeller blades (Nippon Seiki Co., Ltd., Model ED, the same applies hereinafter), pigments and surfactants (Y11-14, YG11-14, Y21-24) with the blending ratios in Table 5 , YG21 to 24 and any one of H1 to H3) are dispersed until uniform, and defoamed for 3 minutes with a defoamer {Model AR-250, manufactured by Awatori Nertaro Co., Ltd.) Thus, a pigment composition of the present invention (pigment pastes 1 to 16) and a comparative pigment composition (pigment pastes H1 to H3) were obtained. In addition, it was confirmed that all of the pigment compositions (pigment pastes 1 to 16 and H1 to H3) were free of particles of 5 microns or more by the crush gauge method (based on JIS K5600-2-5: 1999).
Further, a comparative pigment composition (pigment paste H4) was obtained in the same manner as described above except that the surfactant was not used.

* 1 Sannopco Co., Ltd. pigment dispersant (amine salt of special polycarboxylic acid, active ingredient 70%)
* 2 San Nopco Co., Ltd. wetting agent * 3 San Nopco Co., Ltd. defoaming agent * 4 San Nopco Co., Ltd. viscoelasticity modifier * 5 Color pigment (anthraquinone) manufactured by Dainichi Seika Kogyo Co., Ltd. "Is a registered trademark of the company.
* 6 Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. and “Taipeke” are registered trademarks of the same company.

(2) Preparation of pigment composition for evaluation-2
Using an Excel auto homogenizer equipped with impeller type blades, from an aqueous color base and a surfactant (any one of Y11-14, YG11-14, Y21-24, YG21-24, H1-21) The resulting mixture is dispersed until uniform and defoamed for 3 minutes with a defoamer, and the pigment composition of the present invention (pigment pastes 17 to 32) and the comparative pigment composition (pigment paste H5 to 5). 7) was obtained. It was confirmed by the crush gauge method that all the pigment pastes were free of particles of 5 microns or more.
Further, a comparative pigment composition (pigment paste H8) was obtained in the same manner as above except that no surfactant was used.

* 7 Water color base (monoazo) manufactured by Dainichi Seika Kogyo Co., Ltd.
* 8 Water color base {Copper phthalocyanine blue (β)} manufactured by Dainichi Seika Kogyo Co.

<Preparation of paint and test piece>
(1) Preparation of coating composition-1
10 parts of a pigment composition (pigment paste 1 to 32, H1 to H8) is added to 100 parts of a coating agent {please coat (white), manufactured by SK Kaken Co., Ltd., water-based building material paint}, and an impeller It mixed with the Excel auto homogenizer provided with the type | mold blade | wing, and the coating composition (1-32, H1-H8) was obtained.

(2) Preparation of coating composition-2
Using an Excel auto homogenizer equipped with impeller blades, the coating agent {please coat (white)} and surfactants (Y11-14, YG11-14, Y21-24, YG21-24, and Any one of H1 to H3) and a commercially available aqueous color base (pigment paste) are dispersed until uniform, and then defoamed with a defoamer for 3 minutes to form a coating composition (33 to 48, H9 to H11). ) It was confirmed by the crush gauge method that the coating composition was free of particles of 5 microns or more.
Further, a comparative coating composition (H12) was obtained in the same manner as described above except that the surfactant was not used.

  * 9 Water color base manufactured by Dainichi Seika Kogyo Co., Ltd. (Naphthol AS series)

<Preparation of test paint pieces>
Using the coating composition obtained above, a coated piece was prepared under the following conditions and tested for gloss, toning and water resistance. These results are shown in Tables 8-10.

[Glossy]
Polyester film (length: 150 mm, width: 150 mm, thickness: 0.10 mm, Toll Lermiller L-) diluted with acetone after being diluted with ion-exchanged water so that the coating composition has a 85 KU value (25 ° C.) 100T60 (manufactured by Toray Industries, Inc.) using an applicator (wet film thickness: 0.3 mm), dried for 7 days in a temperature-controlled room (25 ° C., 60% relative humidity, the same shall apply hereinafter) Got. Gloss (gross) at an incident angle of 60 ° was measured with a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., VGS-300A) at six places, and the arithmetic average value of these test pieces was calculated. With gloss.

[Hydrophilicity, contact angle with water (initial)]
Cut a 1 × 5 cm test piece from the test piece, drop 0.04 ± 0.005 mL of deionized water onto the surface of the coating, and measure the contact angle of the water drop after 1 minute. The initial contact angle was used. In addition, the measurement of the contact angle was implemented in the temperature control room using Kyowa Chemical Co., Ltd. contact angle meter CAA.

[Hydrophilicity, contact angle with water (after immersion)]
The test piece was immersed in deionized water for 14 days in a temperature control room. Next, after drying in a temperature-controlled room for 3 days, a test piece having a size of 1 × 5 cm was cut out, and the contact angle with water was measured in the same manner as described above, and the contact angle after immersion was measured. It was.

[Color unevenness]
The coating composition is diluted with ion-exchanged water to 85 KU (25 ° C.) and then sprayed on a stainless steel plate degreased with acetone {Wider W-88 Cup Gun (Iwata Paint Co., Ltd.) )} (Wet film thickness: about 0.2 mm), and immediately after that, half of the surface is brushed (made by Otsuka Brush Manufacturing Co., Ltd., using # 70 for water-based paint) and is normally dried (temperature: 25). After drying for 7 days at 70 ° C. and humidity of 40% RH), using SPECTRO COLOR METERMODEL PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. The color difference (ΔE value) was measured, and the absolute value was defined as the toning property (color unevenness). The smaller this value, the better the toning property.

[Floating spot]
The spray coating portion on which the above [color unevenness] evaluation was performed was visually determined according to the following criteria.
Judgment ○: floating mottle cannot be seen Δ: some floating mottle can be seen ×: many floating mottle can be seen

[water resistant]
[Gloss] The coating piece prepared in the evaluation was immersed in ion-exchanged water in a temperature-controlled room for 3 days, then pulled up from the water and blistered (blister) mark (diameter 0.2 mm) within a 10 cm × 10 cm area in the center part. The above was visually judged according to the following criteria to make it water resistant.
Judgment ○: 0 to 4 △: 5 to 15 ×: 16 or more

  From Tables 8-10, when using the surfactants of the present invention (Y11-14, YG11-14, Y21-24, YG21-24), when using comparative surfactants (H1-H3), and the interface Compared to the case where no activator is used, the toning property and the like are greatly improved, and the hydrophilicity and water resistance are also excellent.

  The surfactant of the present invention can be applied to improve the toning properties of various pigments and can impart hydrophilicity to the coating film. Moreover, although it can apply to an aqueous coating agent, a non-aqueous coating agent, etc., it is suitable for an aqueous coating agent among these, and is suitable for an aqueous emulsion paint. Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints. The toning property improving agent of the present invention is extremely useful for an aqueous ordinary dry paint and an aqueous thermosetting coating agent.

Claims (8)

It contains a polyoxyalkylene compound (YG) obtained by reacting 1 mol of a polyoxyalkylene compound (Y) represented by the general formula (1) with 1 to 5 mol of an alkyl glycidyl ether having 6 to 21 carbon atoms. A surfactant characterized by comprising

However, S is the general formula (2) a group represented by, U is 2-hydroxypropylene group _{{-CH 2 -CH (OH) -CH} 2 -} or hydroxymethyl ethylene group _{-CH 2 -CH (CH ₂ OH)-}, m represents 3 or 4, and S and U may be the same or different.

{H (OA) _n −} _t−2 Q {− (OA) _n −} ₂ (2)

Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, OA is an oxyalkylene group having 2 to 4 carbon atoms, H is a hydrogen atom, and t is an integer of 2 to 4 , N represents an integer of 5-30, the total number of OA is an integer of 20-60, and Q, OA, t, n 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. A pigment composition comprising the pigment and the surfactant described in claim 1 or 2 and comprising 10 to 100% by weight of the surfactant based on the weight of the pigment. A coating composition comprising the coating agent and the pigment composition according to claim 3 , wherein the pigment composition is contained in an amount of 1 to 20% by weight based on the weight of the coating agent. A coating comprising the coating agent and the surfactant according to claim 1 or 2 and comprising 0.5 to 5% by weight of the surfactant based on the weight of the coating agent Composition. The coating composition according to claim 4 or 5 , wherein the coating agent is an aqueous coating agent. A method for producing a surfactant comprising a polyoxyalkylene compound,
Step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of the non-reducing di- or trisaccharide (a1) and 20 to 60 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. ;
A step (2) of obtaining a monoglycidyl ether compound (MG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 1.2 to 2 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (4) of obtaining a dimer (DM) by reacting 1 mol part of the polyoxyalkylene compound (a12) with 0.95 to 1.15 mol part of a monoglycidyl ether compound (MG); and dimer (DM) 1 A method (1) comprising a step (5) of reacting a mole part with 0.95 to 1.15 mole part of a diglycidyl ether compound (DG) to obtain a polyoxyalkylene compound (Y1); or

Step (1) of obtaining a polyoxyalkylene compound (a12) by chemically reacting 1 mol part of the non-reducing di- or trisaccharide (a1) and 20 to 60 mol parts of the alkylene oxide (a2) having 2 to 4 carbon atoms. ;
A step (3) of obtaining a diglycidyl ether compound (DG) by chemically reacting 1 mol part of the polyoxyalkylene compound (a12) and 2.5 to 4 mol parts of the epihalohydrin (a3) in the presence of a base;
A step (6) of obtaining a trimer (TM) by reacting 2 mol parts of the polyoxyalkylene compound (a12) with 1 to 1.2 mol parts of the diglycidyl ether compound (DG);
A method (2) comprising a step (7) of reacting 1 mol part of trimer (TM) with 0.95 to 1.2 mol part of diglycidyl ether compound (DG) to obtain a polyoxyalkylene compound (Y2)
A method for producing a surfactant, comprising: A polyoxyalkylene compound (YG) represented by the general formula (1) is reacted with 1 to 5 moles of an alkyl glycidyl ether having 6 to 21 carbon atoms to obtain a polyoxyalkylene compound (YG). A method for producing a surfactant containing a polyoxyalkylene compound (YG).

  However, S is group represented by General formula (2), U is 2-hydroxypropylene group {-CH. ₂ -CH (OH) -CH ₂ -} Or hydroxymethylethylene group {-CH ₂ -CH (CH ₂ OH)-}, m represents 3 or 4, and S and U may be the same or different.

{H (OA) _n −} _t-2 Q {-(OA) _n −} ₂             (2)

  Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, OA is an oxyalkylene group having 2 to 4 carbon atoms, H is a hydrogen atom, and t is an integer of 2 to 4 , N represents an integer of 5-30, the total number of OA is an integer of 20-60, and Q, OA, t, n may be the same or different.