WO2011013170A1 - Surfactant - Google Patents

Abstract

Provided is a surfactant which, even when applied to water-based coating fluids containing any binder resin, attains excellent forth control and satisfies coating film finish. The surfactant comprises, as an essential ingredient, at least one member selected from a group consisting of: a mixture (Y) comprising a polyoxyalkylene compound (Y1) of formula (1) and a polyoxyalkylene compound (Y2) of formula (2); a polymer obtained by the reaction of the mixture (Y) with a diisocyanate; a polymer obtained by the reaction of the mixture (Y) with a diglycidyl ether; and a polymer obtained by the reaction of the mixture (Y) with an epihalohydrin. {H(OA-)n}tQ                       (1) {H(OB-)m(OA-)n}tQ                (2) Q is a residue of a non-reducing di- or trisaccharide; OA is C2-3 oxyalkylene; OB is oxybutylene; the total number of moles of OA contained in Y1 is 15-100 per mole of Y1; the total number of moles of OA contained in Y2 is 15-50 per mole of Y2; and the total number of moles of OB is 2-6 per mole of Y2.

Description

Surfactant

The present invention relates to a surfactant. More specifically, the present invention relates to a surfactant suitable for an aqueous coating liquid (particularly cationic electrodeposition paint).

A surfactant comprising a polyoxyalkylene compound having a structure that can be produced by a chemical reaction between 1 mol part of a non-reducing di- or trisaccharide and 20 to 100 mol parts of an alkylene oxide having 2 to 4 carbon atoms is known. (Patent Document 1).

WO2004 / 101103 brochure

Aqueous coating liquid (especially cationic electrodeposition paint) has been detoxified by heavy metalization (lead-free) due to environmental problems, etc., and paint performance (high corrosion resistance, low temperature bakeability, VOC content, high throwing power) As a result of improvements in the binder resin, the foamability of the aqueous coating liquid has changed. For example, in the case of cationic electrodeposition paints, conventionally, rather than the electrodeposition paint itself, emphasis is placed on the foamability of the UF filtrate (the filtrate obtained by ultrafiltration of the electrodeposition paint with an ultrafilter, hereinafter abbreviated as UF filtrate). (JP-A-62-211400, Patent Document 1, etc.). However, the emphasis on foam control at the time of electrodeposition coating has come to be the most important. Along with this, the use of surfactants (more powerful antifoaming agents) for foam control has a major impact on the finish of coating films (remaining traces of water droplets, drying unevenness, repelling, leveling, etc.). It is exerting. In many cases, conventional surfactants cannot satisfy foam control and coating film finish (high appearance).
Accordingly, an object of the present invention is to provide a surfactant satisfying excellent foam control and coating film finishing performance regardless of the binder resin-containing aqueous coating liquid.

The surfactant of the present invention is characterized by a mixture of a polyoxyalkylene compound (Y1) represented by the general formula (1) and a polyoxyalkylene compound (Y2) represented by the general formula (2) (Y );
A multimer (PY1) obtained by reacting the mixture (Y) with a diisocyanate having 6 to 15 carbon atoms;
Multimer (PY2) obtained by reaction of mixture (Y) with diglycidyl ether having 10 to 100 carbon atoms; and Multimer (PY3) obtained by reaction of mixture (Y) and epihalohydrin The gist is that at least one kind is an essential component.

{H (OA−) _n } _t Q (1)

{H (OB−) _m (OA−) _n } _t Q (2)

Where Q is a reaction 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 3 carbon atoms, OB is an oxybutylene group, and H is hydrogen An atom, n is an integer of 1 to 35, m is 0 or an integer of 1 to 3, t is an integer of 2 to 4, and the oxy contained in the polyoxyalkylene compound (Y1) represented by the general formula (1) The total number of moles of the alkylene group (OA) is 15 to 100 moles per mole of the polyoxyalkylene compound (Y1), and the oxyalkylene group (Y2) represented by the general formula (2) ( The total number of moles of OA) is 15 to 50 moles per mole of polyoxyalkylene compound (Y2), and the total number of moles of oxybutylene group (OB) is 2 to 2 moles per mole of polyoxyalkylene compound (Y2). The mole, n, m, t may be the same or different.

The surfactant is produced by reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 100 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms. Step (1) for obtaining a polyoxyalkylene compound (Y1);
An adduct is obtained by reacting 1 mol part of a non-reducing disaccharide or trisaccharide (a1) with 15 to 50 mol part of an alkylene oxide (a2) having 2 to 3 carbon atoms, and then adding butylene oxide to the adduct. (A3) Step (2) for obtaining 2 to 6 mole parts to obtain polyoxyalkylene compound (Y2); and polyoxyalkylene compound (Y1) and polyoxyalkylene compound (Y2) are uniformly mixed to obtain a mixture Step (3) for obtaining (Y)
The point including

The aqueous coating liquid of the present invention contains the above surfactant.

The cationic electrodeposition paint of the present invention contains the above surfactant.

The surfactant of the present invention exhibits excellent surface activity {foam control property, water solubility (or water dispersibility), wettability (wetting improvement property and repellency suppression property)}. Therefore, the surfactant of the present invention satisfies the excellent foam controllability and the finish of the coating film, regardless of the aqueous coating liquid containing any binder resin.

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, raffinose, and meletitol are preferable from the viewpoint of surface activity and the like, more preferably trehalose and sucrose, and sucrose is particularly preferable from the viewpoint of supply ability and cost. These can be used alone or in combination.

Examples of the oxyalkylene group (OA) having 2 to 3 carbon atoms include oxyethylene and oxypropylene. Of these, oxypropylene and a mixture of oxypropylene and oxyethylene are preferred, and oxypropylene is more preferred from the viewpoint of surface activity (particularly the finish of the coating film).

When (OA-) n contains oxyethylene and oxypropylene, there is no particular limitation on the bonding order (block, random and combinations thereof) and the content ratio. However, it is preferable to include a block shape or a combination of a block shape and a random shape. When (OA-) n contains oxyethylene, the content ratio (% by weight) of oxyethylene is preferably 2 to 20, more preferably 2 to 15, based on the total weight of oxyethylene and oxypropylene. Particularly preferred is 5 to 15, and most preferred is 5 to 10.

In the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2), when (OA-) n contains oxyethylene and oxypropylene, the oxypropylene is located farthest from the reaction residue (Q). The oxyethylene is preferably located as close as possible to the reaction residue (Q), and more preferably, the oxyethylene is directly bonded to the reaction residue (Q).

In the polyoxyalkylene compound (Y2), it is necessary that the oxybutylene group (OB) is located farthest from the reaction residue (Q). However, a part of the oxybutylene group (OB) may be bonded to oxyethylene and / or oxypropylene at random.

N is an integer of 1 to 35, preferably an integer of 3 to 30, more preferably an integer of 5 to 25, and particularly preferably an integer of 7 to 20. Within this range, the surface activity (particularly the finish of the coating film) is further improved.

M is 0 or an integer of 1 to 3, preferably 0, 1 or 2, and more preferably 1 or 2. Within this range, the surface activity (particularly antifoaming property) is further improved. Of the t m, at least one m is an integer of 1 or more.

T is an integer of 2 to 4, preferably 3 or 4, and more preferably 3. Within this range, the surface activity is further improved. This t corresponds to the number of primary hydroxyl groups of the non-reducing di- or trisaccharide.

The total number of moles (moles) of the oxyalkylene group (OA) contained in the polyoxyalkylene compound (Y1) represented by the general formula (1) is 15 to 100 per mole of the polyoxyalkylene compound (Y1). It is preferably 15 to 80, more preferably 20 to 70, and particularly preferably 20 to 60. Within this range, the surface activity (particularly the finish of the coating film) is further improved.

The total number of moles of the oxyalkylene group (OA) contained in the polyoxyalkylene compound (Y2) represented by the general formula (2) is 15 to 50 per mole of the polyoxyalkylene compound (Y2), preferably It is 15 to 45, more preferably 20 to 45, particularly preferably 20 to 40. Within this range, the surface activity (particularly the finish of the coating film) is further improved.

The total number of moles (mol) of the oxybutylene group (OB) is 2 to 6, preferably 2 to 5, more preferably 2 to 4, particularly preferably 3 to 1 mole per mole of the polyoxyalkylene compound (Y2). 4. Within this range, the surface activity (particularly antifoaming property) is further improved.

N, m and t may be the same or different. The n OA's may be the same or different, and the t (OA-) n may be the same or different. Further, t (OB−) m may be the same or different.

The content (% by weight) of the polyoxyalkylene compound (Y1) is preferably 40 to 90, more preferably 50 to 90, particularly preferably 55 to 85, and most preferably 60, based on the weight of the mixture (Y). ~ 80.
The content (% by weight) of the polyoxyalkylene compound (Y2) is preferably 10 to 60, more preferably 10 to 50, particularly preferably 15 to 45, most preferably 20 based on the weight of the mixture (Y). ~ 40.
Within these ranges, the surface activity (defoaming property and finish of the coating film) is further improved.

The polyoxyalkylene compound (Y1) comprises a step (1) of reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 100 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms, etc. Manufactured by.
This reaction causes distribution in the oxyalkylene group of the resulting polyoxyalkylene compound (Y1), but these mixtures may be used as they are.

The amount (mole parts) of the alkylene oxide (a2) is preferably from 15 to 100, more preferably from 15 to 80, particularly preferably from 20 to 70, based on 1 mole part of the non-reducing di- or trisaccharide (a1). And most preferably 20-60. Within this range, the surface activity 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 (1) can be used, and the preferred range is also the same.

As the alkylene oxide (a2), alkylene oxides having 2 to 3 carbon atoms can be used, and examples thereof include ethylene oxide, propylene oxide, and mixtures thereof. Among these, from the viewpoint of surface activity, propylene oxide and a mixture of propylene oxide and ethylene oxide are preferable, and propylene oxide is more preferable.

¡When multiple types of alkylene oxide are used, there is no limitation on the order of reaction (block, random, and combinations thereof) and the usage rate. However, it is preferable to include a block shape or a combination of a block shape and a random shape, and more preferable to react propylene oxide after reacting ethylene oxide.

When ethylene oxide is contained, the proportion (% by weight) of ethylene oxide is preferably 2 to 20, more preferably 2 to 15, particularly preferably 5 to 15, and most preferably 5 based on the total weight of ethylene oxide and propylene oxide. ~ 10.

The polyoxyalkylene compound (Y2) is obtained by reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 50 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms. Thereafter, this adduct is produced by reacting 2 to 6 parts by mole of butylene oxide (1,2-butylene oxide and / or 2,3-butylene oxide) (a3) (2).
This reaction causes distribution in the oxyalkylene group or oxybutylene group of the polyoxyalkylene compound (Y2), but these mixtures may be used as they are.

The amount (mole parts) of the alkylene oxide (a2) is preferably 15 to 50, more preferably 15 to 45, particularly preferably 20 to 45, based on 1 mole part of the non-reducing disaccharide or trisaccharide (a1). And most preferably 20-40. Within this range, the surface activity is further improved.

The amount (mole part) of butylene oxide (a3) is preferably 2 to 6, more preferably 2 to 5, particularly preferably 2 to 4 with respect to 1 mole part of the non-reducing disaccharide or trisaccharide (a1). And most preferably 3-4. Within this range, the surface activity tends to be even better.

The mixture (Y) is produced by the step (3) of uniformly mixing the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2). In this step (3), after producing the polyoxyalkylene compound (Y1), a part of the polyoxyalkylene compound (Y1) and the butylene oxide (a3) are reacted in the same reaction vessel. (Y2) may be produced and mixed uniformly. After producing the polyoxyalkylene compound (Y1), a part of the polyoxyalkylene compound (Y1) is set aside and then the remaining polyoxyalkylene compound (Y1) and butylene oxide (a3) may be reacted to produce a polyoxyalkylene compound (Y2), which may be set aside and mixed uniformly with the polyoxyalkylene compound (Y1). Moreover, the mixture (Y) obtained by uniformly mixing in this way and the polyoxyalkylene compound (Y2) manufactured with another container may be mixed uniformly.
On the other hand, after producing the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2) in separate containers, they may be uniformly mixed to obtain a mixture (Y).

Reaction of non-reducing di- or trisaccharide (a1) with alkylene oxide (a2) and reaction product of non-reducing di- or trisaccharide (a1) with alkylene oxide (a2) and butylene oxide (a3) (Hereinafter abbreviated as AOA reaction). } May be a known method {for example, Patent Document 1}, and may be performed in any form such as anionic polymerization, cationic polymerization, or coordinated 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 AOA reaction. 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, known alkylene oxide addition reaction catalysts described in {eg, Patent Document 1} can be used. Of these, alkali metal hydroxides and tertiary amines are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.

When a reaction catalyst is used, the amount used (% by weight) is 0.05 based on the total weight of the raw materials of the AOA reaction {eg, non-reducing di- or trisaccharide (a1) and alkylene oxide (a2)). To 2, more preferably 0.1 to 1, and particularly preferably 0.2 to 0.6.

When a reaction catalyst is used, it is preferable to remove the reaction catalyst from the reaction product, and a known method {eg, Patent Document 1} or the like can be applied as the method and the end point of the removal of the reaction catalyst.

A reaction solvent can be used for the AOA reaction. As the reaction solvent, a known solvent {for example, Patent Document 1} can be used. Of these, N-alkylamide and N-methylpyrrolidone are preferred, dimethylformamide (DMF), N, N-dimethylacetamide and N-methylpyrrolidone, particularly preferred DMF and N-methylpyrrolidone, most preferred DMF.

When a reaction solvent is used, the amount used (% by weight) is preferably 50 to 200, more preferably 60 to 180, particularly preferably 60 to 160, based on the weight of the raw material for the AOA reaction.

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 based on the weight of the polyoxyalkylene compound (Y1) and / or the polyoxyalkylene compound (Y2). Hereinafter, it is particularly preferably 0.01 or less. 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, a known method {for example, Patent Document 1} can be applied.

The multimer (PY1) is obtained by reacting the mixture (Y) with a diisocyanate having 6 to 15 carbon atoms.

The amount (mole) of the diisocyanate having 6 to 20 carbon atoms is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, particularly preferably 0.67, per mole of the mixture (Y). ~ 0.75.

As the diisocyanate, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate and the like can be used.

As the aliphatic diisocyanate, an alkylene diisocyanate having 6 to 8 carbon atoms is used, and examples thereof include 1,4-diisocyanatobutane and hexamethylene diisocyanate (HMDI).

As the aromatic diisocyanate, arylene diisocyanate having 8 to 15 carbon atoms is used, and paraphenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate ( XDI), 1,5-naphthalene diisocyanate and the like.

As the alicyclic diisocyanate, cycloalkylene diisocyanate having 12 to 15 carbon atoms is used, and isophorone diisocyanate (IPDI), hydrogenated MDI, trans 1,4-cyclohexane diisocyanate, hydrogenated TDI, hydrogenated 1,5-naphthalene. Diisocyanate etc. are mentioned.

Of these diisocyanates, aliphatic and alicyclic diisocyanates are preferable from the viewpoint of surface activity and the like, more preferably 1,4-diisocyanatobutane, HMDI, IPDI, and hydrogenated MDI, and from the viewpoint of coloring properties and the like. Particularly preferred are HMDI and IPDI.

The reaction between the mixture (Y) and the diisocyanate is an addition reaction. In the case of a reaction with a diisocyanate having a low reaction rate (such as an aliphatic diisocyanate or an alicyclic diisocyanate), for example, HMDI or IPDI, the reaction time can be shortened. For the purpose, a reaction catalyst can be used. As the reaction catalyst, dibutyltin dilaurate, stannous octoate, triethylenediamine and the like are common.

For the reaction between the mixture (Y) and the diisocyanate, a sealed container capable of heating, cooling and stirring can be used. The reaction temperature (° C.) is preferably 70 to 150, more preferably 90 to 130. The reaction atmosphere is preferably a dry inert gas atmosphere. In addition, the reaction end point can be confirmed by the following method or the like. That is, in the isocyanato group content measurement method using a dioxane solution of di-n-butylamine, the end point of the reaction is the time when the isocyanato group content becomes 0.01% by weight or less.

The multimer (PY2) is obtained by reacting the mixture (Y) with diglycidyl ether having 10 to 100 carbon atoms.

The amount (mole) of diglycidyl ether having 10 to 150 carbon atoms is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, particularly preferably 0, per mole of the mixture (Y). .67 to 0.75.

Examples of the diglycidyl ether having 10 to 100 carbon atoms include tetramethylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyoxypropylene glycol diglycidyl ether, and polyoxyalkylene adducts of various glycols. Among the diglycidyl ether compounds, diglycidyl ether having 10 to 100 carbon atoms can be mentioned. Of these, hexamethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether are preferred.

The reaction between the mixture (Y) and the diglycidyl ether is the same as the reaction between the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2), and the reaction apparatus, catalyst and removal thereof are the same.

The multimer (PY3) is obtained by reacting the mixture (Y) with epihalohydrin.

The amount (mol) of epihalohydrin used is preferably 0.5 to 0.8, more preferably 0.67 to 0.8, and particularly preferably 0.67 to 0.75, per mole of the mixture (Y). .

Epihalohydrins include epichlorohydrin and epibromohydrin.

For the reaction of the mixture (Y) and epihalohydrin, heating, cooling, stirring, and a vessel with a reflux tube can be used.
In this reaction, (1) the hydroxyl group of the polyoxyalkylene compound {(Y1) and / or (Y2)} and the epoxy group of epihalohydrin are subjected to an epoxy ring-opening reaction,
(2) Regenerate the epoxy ring by dehydrohalogenation reaction,
(3) A method of further reacting the regenerated epoxy group with a hydroxyl group of the polyoxyalkylene compound {(Y1) and / or (Y2)} (1); or
(4) First, by a dehydrohalogenation reaction (Williamson synthesis reaction: the reaction is driven by neutralizing hydrogen halide sequentially generated during the reaction with a basic substance), polyoxyalkylene compounds {(Y1) and / or Or the hydroxyl group of (Y2)} is glycidyl etherified (converted to a glycidyloxy group),
(5) Next, a method (2) in which the hydroxyl group of another polyoxyalkylene compound {(Y1) and / or (Y2)} and a glycidyloxy group are subjected to an epoxy ring-opening reaction may be mentioned.

The reaction temperature (° C.) of the epoxy ring-opening reaction in the above steps (1) and (5) is preferably 30 to 150, more preferably 40 to 100. The reaction atmosphere is preferably a dry inert gas atmosphere.

In the epoxy ring-opening reaction, a reaction catalyst can be used, which is the same as that used in the addition reaction of a non-reducing di- or trisaccharide (a1) and an alkylene oxide (a2), and is a known catalyst (special No. 2004-224945 and the like can be applied. The same applies to the removal of the catalyst.

The end point of the reaction 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. : 2001; corresponding international standard ISO3001: 1999; the disclosure content disclosed therein is incorporated into the present application by reference).

The epoxy ring regeneration reaction by the dehydrohalogenation reaction in the above steps (2) and (4) includes a basic substance that neutralizes the generated hydrogen halide, for example, an alkali metal or alkaline earth metal hydroxide ( Lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, etc.) are used as the catalyst. Of these, alkali metal hydroxides are preferred, and sodium hydroxide is more preferred.

The amount of the basic substance used is the base equivalent (eq.) Of the basic substance, based on the equivalent (eq.) Of the halogen of the halogenated hydrocarbon, based on the base equivalent of the basic substance / the halogen of the halogenated hydrocarbon. The equivalent ratio is preferably 1 to 1.4, more preferably 1.05 to 1.3, and most preferably 1.07 to 1.2.

In the case of an epoxy ring regeneration reaction, these reaction catalysts are preferably used as an aqueous solution of about 1 to 20% by weight, and the reaction temperature is preferably about 40 to 80 ° C.

In the case of the glycidyl etherification reaction in the above step (4), it is preferably carried out in an anhydrous state. The reaction temperature is preferably about 30 to 70 ° C.

After completion of all the reactions, it is preferable to remove the generated neutralized salt and the remaining basic substance. This removal method includes (1) a method in which the produced neutralized salt is first removed by filtration, and then a remaining basic substance is removed using an adsorbent and the like, and (2) an extraction / water washing method using an organic solvent. And (3) a salting-out method using salt or the like.

The removal method (1) can be removed in the same manner as the reaction catalyst used in the addition reaction of the alkylene oxide (a2). The extraction / washing method in (2) is to add water and an organic solvent (having extremely low solubility in water such as hexane, toluene, xylene, etc.) to the reaction product and mixing the reaction product with the organic solvent. In this method, a basic substance is extracted into an aqueous layer by separating it into layers, and this is separated. The organic solvent layer is further washed with deionized water or the like. A suitable volume ratio of reaction product: water: organic solvent is approximately 1: 1: 1. In the salting-out method (3), the reaction product is shaken by adding approximately the same volume of water and an appropriate amount (1 to 5% by weight of sodium chloride) to the reaction product and shaking. In this method, the basic substance is separated from the aqueous layer by precipitation from the aqueous layer.
When the removal method (2) or (3) is applied, it is preferable to finally remove the basic substance completely using an alkali adsorbent (synthetic aluminosilicate, etc .; for example, Kyword 700).

Examples of the polyoxyalkylene compound (Y1) include compounds shown in Table 1.
Q, t, and OA correspond to the general formula (1). Q1 represents a sucrose reaction residue, Q2 represents a trehalose reaction residue, and Q3 represents a meletitose reaction residue. P represents oxypropylene, and E represents oxyethylene. The subscript of P or E represents the number of moles per mole of the non-reducing di- or trisaccharide reaction residue (this sum corresponds to the total number of moles of oxyalkylene groups (OA)). Moreover, / in OA means a block shape, means that E is bound to a di- or trisaccharide, and · in OA means a random shape.

Of these, polyoxyalkylene compounds represented by No. 4, 5, 6, 8, 13, 17 or 18 are preferred, and polyoxyalkylene compounds represented by No. 5 or 17 are more preferred.

Examples of the polyoxyalkylene compound (Y2) include compounds shown in Table 2.
Q, t, OA, and OB correspond to the general formula (2). Q1 represents a sucrose reaction residue, Q2 represents a trehalose reaction residue, and Q3 represents a meletitose reaction residue. P represents oxypropylene, E represents oxyethylene, and B represents oxybutylene. The subscript P, E or B is the number of moles per mole of the non-reducing di- or trisaccharide reaction residue (the sum of the subscripts P and E is the total number of moles of oxyalkylene groups (OA)). The subscript of B represents the total number of oxybutylene groups (OB). Moreover, / in OA means a block shape, means that E is bound to a di- or trisaccharide, and · in OA means a random shape.

Of these, the polyoxyalkylene compounds represented by No22, 23, 24 or 29 are preferred, and the polyoxyalkylene compounds represented by No23 or 24 are more preferred.

Examples of the multimer (PY1) include compounds obtained by reacting the mixture (Y) shown in Table 3 with diisocyanate.
The mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and subscripts correspond to Tables 1 and 2, respectively. HMDI represents hexamethylene diisocyanate, IPDI represents isophorone diisocyanate, and XDI represents xylylene diisocyanate.

Of these, multimers represented by No, 36, 37 or 38 are preferred, and multimers represented by No 36 or 37 are more preferred.

Examples of the multimer (PY2) include compounds obtained by reacting the mixture (Y) shown in Table 4 with diglycidyl ether.
The mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and each subscript correspond to Tables 1 and 2, respectively. G1 represents 1,6-hexamethylene glycol diglycidyl ether, G2 represents polyoxypropylene (7 mol) glycol diglycidyl ether, and G3 represents polyoxypropylene (20 mol) glycol diglycidyl ether.

Of these, multimers represented by No, 41, 42 or 43 are preferred, and multimers represented by No 41 or 42 are more preferred.

Examples of the multimer (PY3) include compounds obtained by reacting the mixture (Y) shown in Table 5 with epihalohydrin.
The mixture (Y) represents a compound shown in Table 1 or 2, and Q1, Q2, Q3, P, B and each subscript correspond to Tables 1 and 2, respectively. H1 represents epichlorohydrin and H2 represents epibromohydrin.

Of these, multimers represented by No, 46, 47 or 48 are preferred, and multimers represented by No 46 or 47 are more preferred.

In addition to the mixture (Y), multimer (PY1), multimer (PY2) and multimer (PY3) comprising the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2), the surfactant of the present invention includes If necessary, other surfactants and / or solvents can be contained.

As other surfactants, known nonionic, cationic, anionic or amphoteric surfactants can be used. Nonionic surfactants include alkylphenol alkylene oxide adducts, alcohol alkylene oxide adducts, polyhydric alcohol fatty acid esters, alkylamine alkylene oxide adducts, fatty acid amide alkylene oxide adducts, and acetylene glycol alkylene oxide additions. Body and polyoxyalkylene-modified silicone. Examples of the cationic surfactant include amine salts, quaternary ammonium salts, alkylene oxide addition type ammonium salts, and the like. Examples of anionic surfactants include fatty acid salts, α-olefin sulfonates, alkylbenzene sulfonic acids and salts thereof, alkyl sulfate esters, alkyl ether sulfate esters, N-acyl alkyl taurate salts, and alkyl sulfosuccinates. It is done. Examples of amphoteric surfactants include alanine, imidazolinium betaine, amide betaine, and betaine acetate.

Other commercially available surfactants include SN Wet 123 and 970 (San Nopco); Lionol TDL-30, 50 and 70 (Lion Corporation, “Lionol” is a registered trademark of the company) Ionette T-80C, S-80, DO-600, etc. (Sanyo Kasei Kogyo Co., Ltd., “Ionette” is a registered trademark of the company); Softanol 30, 30S, MES-5, etc. (Nippon Shokubai Co., Ltd.) "Sophanol" is a registered trademark of the company); and Surfinol 104, 440, and Emblem Gem AD01 (Air Products, "Surfinol" and "Embile Gem" are registered trademarks of the company) Can be mentioned.

When other surfactant is contained, the content (% by weight) is the total weight of the mixture (Y), multimer (PY1), multimer (PY2), multimer (PY3) and other surfactants. Is preferably 1 to 20, more preferably 5 to 15, and particularly preferably 5 to 10.

As the solvent, water, a water-soluble organic solvent, or the like can be used. Examples of water include ion exchange water, distilled water, tap water, and industrial water. Examples of the water-soluble organic solvent include alcohols having 1 to 3 carbon atoms (such as methanol, ethanol and isopropanol), ketones having 3 to 6 carbon atoms (such as acetone, methyl ethyl ketone and methyl isobutyl ketone), and ethers having 2 to 6 carbon atoms (dimethyl ether). And ethyl cellosolve and butyl cellosolve) and ether esters having 4 to 6 carbon atoms (such as butyl cellosolve acetate).

When the solvent is contained, the content (% by weight) is 1 to 30 based on the total weight of the mixture (Y), multimer (PY1), multimer (PY2), multimer (PY3) and solvent. More preferably, it is 5 to 25, and particularly preferably 5 to 20.

The surfactant of the present invention is suitable as a surfactant to be added to an aqueous coating liquid (cationic electrodeposition paint, aqueous architectural paint, aqueous automotive paint, paper coating paint, aqueous ink, etc.).
When the surfactant of the present invention is applied to an aqueous coating solution, the amount (% by weight) of the surfactant of the present invention is preferably 0.01 to 10, more preferably based on the weight of the aqueous coating solution. It is 0.05 to 5, particularly preferably 0.1 to 3.

Among aqueous coating liquids, it is particularly suitable for cationic electrodeposition coatings.
The cationic electrodeposition coating is generally composed of 1) a cationic resin emulsion, 2) a pigment paste, and 3) an aqueous medium. When used as a cationic electrodeposition coating, the surfactant of the present invention includes (1) a cationic resin emulsion, (2) a pigment paste, (3) an aqueous medium, (4) an electrodeposition coating prepared from these, and (5) You may add to any of UF filtrate.

When added to (1) a cationic resin emulsion, (2) a pigment paste or (3) an aqueous medium, the addition amount (% by weight) of the surfactant of the present invention is the amount of the cationic resin emulsion, pigment paste or aqueous medium. Based on the weight, it is preferably 0.01 to 5, more preferably 0.05 to 3, particularly preferably 0.1 to 2.

(4) When added to the electrodeposition paint, the addition amount (% by weight) of the surfactant of the present invention is preferably from 0.01 to 2, more preferably from 0.05 to 2, based on the weight of the electrodeposition paint. 1.5, particularly preferably 0.1 to 1.

(5) When added to the UF filtrate, the addition amount (% by weight) of the present invention is preferably 0.001 to 0.3, more preferably 0.002 to 0.2, based on the weight of the UF filtrate. Particularly preferred is 0.003 to 0.15.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. 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 {manufactured by Taiyo Co., Ltd. Chemical Co., Ltd., the same below} 1000 parts were charged, and then nitrogen gas was used until the gauge pressure was increased to 0.4 MPa and discharged to 0.02 MPa three times {hereinafter, This operation using nitrogen gas is abbreviated as nitrogen substitution. }. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 870 parts (15 parts by mole) of propylene oxide (PO) was dropped over 6 hours at this temperature, and stirring was continued for 1 hour at the same temperature. (PO) was reacted. Next, DMF was distilled off under reduced pressure (120 ° C., −0.05 to −0.098 MPa, the same applies hereinafter) to obtain a polyoxyalkylene compound {sucrose / (PO) 15 mol adduct} (Y101).

<Production Example 2>
In the same reaction vessel as in Production Example 1, 1212 parts (1 mole part) of sucrose / (PO) adduct (Y101) and potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., used in water The amount is expressed in terms of a pure content excluding the following, and the same applies to the following: 1.7 parts (0.03 mol part) and dehydrated at 120 ° C. under reduced pressure (-0.05 to -0.098 MPa, the same applies hereinafter) for 1 hour. did. Next, 290 parts (5 mol parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 4 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 2 hours. Next, after adding 20 parts of ion-exchanged water at 90 ° C., KYOWARD 700 (manufactured by Kyowa Chemical Industry Co., Ltd., “KYOWARD” is a registered trademark of the company. } 40 parts were added and stirred 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 then dehydrate at 120 ° C. for 1 hour under reduced pressure (hereinafter these treatments with Kyoword 700 etc. are abbreviated as Kyoword treatment). To obtain a polyoxyalkylene compound {sucrose / (PO) 20 mol adduct} (Y102).

<Production Example 3>
A reaction vessel similar to Production Example 1 was charged with 1212 parts (1 mole part) of sucrose / (PO) 15-mole adduct (Y101) and 2.8 parts (0.05 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 580 parts (10 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 5 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 2 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 25 mol adduct} (Y103).

<Production Example 4>
A reaction vessel similar to Production Example 1 was charged with 1502 parts (1 mol part) of sucrose / (PO) 20 mol adduct (Y102) and 2.8 parts (0.05 mol part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 580 parts (10 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 5 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 2 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 30 mol adduct} (Y104).

<Production Example 5>
A reaction vessel similar to Production Example 1 was charged with 1502 parts (1 mole part) of sucrose / (PO) 20-mole adduct (Y102) and 3.4 parts (0.06 mole part) potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 1160 parts (20 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 6 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 3 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 40 mol adduct} (Y105).

<Production Example 6>
Into the same reaction vessel as in Production Example 1, 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF were added, and then purged with nitrogen. Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, ethylene oxide (EO) 132 (3 mole parts) was added dropwise over 2 hours, and stirring was continued for 1 hour at the same temperature to remain (EO) ) Was reacted. Further, 580 parts (10 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 6 hours, and stirring was further continued at the same temperature for 1 hour to react the remaining (PO). Next, after distilling off DMF under reduced pressure, 3.4 parts (0.06 mol part) of potassium hydroxide was added and dehydrated at 120 ° C. under reduced pressure for 1 hour. Subsequently, 1740 parts (30 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 6 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 3 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (EO) 3 mol / (PO) 40 mol adduct} (Y106).

<Production Example 7>
Into the same reaction vessel as in Production Example 1, 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF were added, and then purged with nitrogen. Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, ethylene oxide (EO) 264 (6 mole parts) was added dropwise over 3 hours, and stirring was continued for 1 hour at the same temperature to remain (EO). ) Was reacted. Further, 580 parts (10 mole parts) of propylene oxide (PO) was added dropwise at the same temperature over 6 hours, and stirring was further continued at the same temperature for 1 hour to react the remaining (PO). Next, after distilling off DMF under reduced pressure, 4.0 parts (0.07 mol part) of potassium hydroxide was added and dehydrated at 120 ° C. under reduced pressure for 1 hour. Next, 1972 parts (34 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 7 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 3 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (EO) 6 mol / (PO) 44 mol adduct} (Y107).

<Production Example 8>
A reaction vessel similar to Production Example 1 was charged with 1502 parts (1 mol part) of sucrose / (PO) 20 mol adduct (Y102) and 10.1 parts (0.18 mol part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 3480 parts (60 mol parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 10 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 3 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 80 mol adduct} (Y108).

<Production Example 9>
Into a reaction vessel similar to Production Example 1, 342 parts (1 mole part) of trehalose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1000 parts of DMF were added, and then nitrogen substitution was performed. Then, after raising the temperature to 100 ° C. with stirring, 1160 parts (20 mole parts) of propylene oxide (PO) is added dropwise at this temperature over 10 hours, and stirring is continued for 2 hours at the same temperature. (PO) was reacted. Next, DMF was distilled off under reduced pressure to obtain a polyoxyalkylene compound {trehalose / (PO) 20 mol adduct} (Y109).

<Production Example 10>
In a reaction vessel similar to Production Example 1, 1502 parts (1 mole part) of trehalose / (PO) 20-mole adduct (Y108) and 3.4 parts (0.06 mole part) of potassium hydroxide were charged under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 580 parts (10 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 3 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 2 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {trehalose / (PO) 30 mol adduct} (Y110).

<Production Example 11>
Into the same reaction vessel as in Production Example 1, 342 parts (1 mol part) of trehalose and 1000 parts of DMF were added, and then nitrogen substitution was performed. Then, after heating up to 100 degreeC, stirring, the mixture of ethylene oxide (EO) 220 parts (5 mol parts) and propylene oxide (PO) 290 parts (5 mol parts) was dripped over 6 hours at this temperature. Further, stirring was continued at the same temperature for 2 hours to react the remaining (EO, PO). Subsequently, after distilling off DMF under reduced pressure, 9.0 parts (0.16 mol part) of potassium hydroxide was added and dehydrated at 120 ° C. under reduced pressure for 1 hour. Next, 2900 parts (50 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 8 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 2 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {trehalose / (EO) 5 mol · (PO) 5 mol / (PO) 50 mol adduct)} (Y111).

<Production Example 12>
Into the same reaction vessel as in Production Example 1, 504 parts (1 mole part) of Meretitos {special reagent grade, manufactured by Tokyo Chemical Industry Co., Ltd.} and 1000 parts of DMF were added, followed by nitrogen substitution. Then, after raising the temperature to 100 ° C. with stirring, 1740 parts (30 mole parts) of propylene oxide (PO) is added dropwise at this temperature over 15 hours, and stirring is continued for 3 hours at the same temperature. (PO) was reacted. Next, DMF was distilled off under reduced pressure to obtain a polyoxyalkylene compound {meletitol / (PO) 30 mol adduct} (Y112).

<Production Example 13>
A reaction vessel similar to Production Example 1 was charged with 1212 parts (1 mole part) of sucrose / (PO) 15-mole adduct (Y101) and 1.1 parts (0.02 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 444 parts (6 mol parts) of 1,2-butylene oxide (hereinafter abbreviated as butylene oxide) (BO) (120 mol parts) was added dropwise at 120 ° C. over the course of 3 hours, and the mixture was further stirred at the same temperature for 1 hour. Subsequently, the remaining (BO) was reacted. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 15 mol / (BO) 6 mol adduct)} (Y201).

<Production Example 14>
In a reaction vessel similar to Production Example 1, 1502 parts (1 mol part) of sucrose / (PO) 20 mol adduct (Y102) and 1.7 parts (0.03 mol part) of potassium hydroxide were charged under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 370 parts (5 parts by mole) of butylene oxide (BO) was added dropwise over 3 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 20 mol / (BO) 5 mol adduct)} (Y202).

<Production Example 15>
A reaction vessel similar to Production Example 1 was charged with 1792 parts (1 mole part) of sucrose / (PO) 25 mole adduct (Y103) and 1.7 parts (0.03 mole part) potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 296 parts (4 mole parts) of butylene oxide (BO) was added dropwise at 120 ° C. over 3 hours with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 25 mol / (BO) 4 mol adduct)} (Y203).

<Production Example 16>
A reaction vessel similar to Production Example 1 was charged with 2082 parts (1 mol part) of sucrose / (PO) 30 mol adduct (Y104) and 2.2 parts (0.04 mol part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 222 parts (3 parts by mole) of butylene oxide (BO) was added dropwise over 2 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 30 mol / (BO) 3 mol adduct)} (Y204).

<Production Example 17>
A reaction vessel similar to Production Example 1 was charged with 2662 parts (1 mole part) of sucrose / (PO) 40-mol adduct (Y105) and 2.8 parts (0.05 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Then, 148 parts (2 mole parts) of butylene oxide (BO) was added dropwise at 120 ° C. over 2 hours with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 40 mol / (BO) 2 mol adduct)} (Y205).

<Production Example 18>
In the same reaction vessel as in Production Example 1, sucrose / (EO) 3 mol / (PO) 40 mol adduct (Y106) 2794 parts (1 mol part) and potassium hydroxide 2.8 parts (0.05 mol part) Was dehydrated at 120 ° C. under reduced pressure for 1 hour. Next, 222 parts (3 parts by mole) of butylene oxide (BO) was added dropwise over 2 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (EO) 3 mol / (PO) 40 mol / (BO) 3 mol adduct)} (Y206).

<Production Example 19>
In the same reaction vessel as in Production Example 1, 3248 parts (1 mol part) of sucrose / (EO) 6 mol / (PO) 44 mol adduct (Y107) and 3.4 parts (0.06 mol part) of potassium hydroxide Was dehydrated at 120 ° C. under reduced pressure for 1 hour. Next, 296 parts (4 mole parts) of butylene oxide (BO) was added dropwise at 120 ° C. over 3 hours with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (EO) 6 mol / (PO) 44 mol / (BO) 4 mol adduct)} (Y207).

<Production Example 20>
In the same reaction vessel as in Production Example 1, 1502 parts (1 mol part) of trehalose / (PO) 20 mol adduct (Y108) and 1.7 parts (0.03 mol part) of potassium hydroxide were charged under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 296 parts (4 mole parts) of butylene oxide (BO) was added dropwise at 120 ° C. over 3 hours with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {trehalose / (PO) 20 mol / (BO) 4 mol adduct)} (Y208).

<Production Example 21>
A reaction vessel similar to Production Example 1 was charged with trehalose / (PO) 30 mol adduct (Y109) 2082 parts (1 mol part) and 2.8 parts (0.05 mol parts) potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Subsequently, 222 parts (3 parts by mole) of butylene oxide (BO) was added dropwise over 3 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {trehalose / (PO) 30 mol / (BO) 3 mol adduct)} (Y209).

<Production Example 22>
A reaction vessel similar to Production Example 1 was charged with 2244 parts (1 mole part) of meletitose / (PO) 30 mole adduct (Y110) and 2.8 parts (0.05 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 296 parts (4 mole parts) of butylene oxide (BO) was added dropwise over 4 hours at 120 ° C. with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Next, Kyoward treatment was carried out to obtain a polyoxyalkylene compound {meletitol / (PO) 30 mol / (BO) 4 mol adduct)} (Y210).

<Example 1>
The surfactant (S101) of the present invention was obtained by uniformly mixing 60 parts of the polyoxyalkylene compound (Y101) obtained in Production Example 1 and 40 parts of the polyoxyalkylene compound (Y205) obtained in Production Example 17. .

<Example 2>
70 parts of the polyoxyalkylene compound (Y102) obtained in Production Example 2 and 30 parts of the polyoxyalkylene compound (Y210) obtained in Production Example 22 were uniformly mixed to obtain the surfactant (S102) of the present invention. .

<Example 3>
The surfactant (S103) of the present invention was obtained by uniformly mixing 90 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 10 parts of the polyoxyalkylene compound (Y201) obtained in Production Example 13. .

<Example 4>
The surfactant (S104) of the present invention was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 50 parts of the polyoxyalkylene compound (Y204) obtained in Production Example 16. .

<Example 5>
The surfactant (S105) of the present invention was obtained by uniformly mixing 55 parts of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 45 parts of the polyoxyalkylene compound (Y207) obtained in Production Example 19. .

<Example 6>
80 parts of the polyoxyalkylene compound (Y106) obtained in Production Example 6 and 20 parts of the polyoxyalkylene compound (Y202) obtained in Production Example 14 were uniformly mixed to obtain the surfactant (S106) of the present invention. .

<Example 7>
85 parts of the polyoxyalkylene compound (Y107) obtained in Production Example 7 and 15 parts of the polyoxyalkylene compound (Y208) obtained in Production Example 20 were uniformly mixed to obtain the surfactant (S107) of the present invention. .

<Example 8>
The surfactant (S108) of the present invention was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y108) obtained in Production Example 8 and 50 parts of the polyoxyalkylene compound (Y209) obtained in Production Example 21. .

<Example 9>
The surfactant (S109) of the present invention was obtained by uniformly mixing 10 parts of the polyoxyalkylene compound (Y109) obtained in Production Example 9 and 90 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 15. .

<Example 10>
30 parts of the polyoxyalkylene compound (Y110) obtained in Production Example 10 and 70 parts of the polyoxyalkylene compound (Y206) obtained in Production Example 18 were uniformly mixed to obtain the surfactant (S110) of the present invention. .

<Example 11>
30 parts of the polyoxyalkylene compound (Y111) obtained in Production Example 11, 30 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 40 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 15 were uniformly mixed. To obtain a surfactant (S111) of the present invention.

<Example 12>
Uniformly 65 parts of the polyoxyalkylene compound (Y112) obtained in Production Example 12, 15 parts of the polyoxyalkylene compound (Y204) obtained in Production Example 16 and 20 parts of the polyoxyalkylene compound (Y208) obtained in Production Example 20 To obtain a surfactant (S112) of the present invention.

<Example 13>
A reaction vessel similar to Production Example 1 was charged with 2244 parts (1 mole part) of meretito / (PO) 30 mole adduct (Y110) and 3.4 parts (0.06 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 290 parts (5 mole parts) of propylene oxide (PO) was added dropwise at 105 ° C. over 5 hours with the same reduced pressure, and the remaining (PO) was allowed to react by continuing stirring at the same temperature for 1 hour. / (PO) 35 mol adduct was obtained. Subsequently, 1269 parts of an amount corresponding to ½ of the reaction product was extracted from the reaction vessel, and then dehydrated at 120 ° C. for 1 hour under reduced pressure. Next, 111 parts (1.5 mole parts) of butylene oxide (BO) was added dropwise at 120 ° C. over 3 hours with the same reduced pressure, and the remaining (BO) was reacted by continuing stirring at the same temperature for 1 hour. Metetose / (PO) 35 mol / (BO) 3 mol adduct was obtained. Thereafter, 1269 parts of the previously extracted meletitose / (PO) 35 mol adduct is returned to the reaction vessel and mixed uniformly, and then subjected to Kyoward treatment to give a polyoxyalkylene compound {meretitol / (PO) 35 mol adduct 48. The surfactant (S113) of the present invention comprising, by weight, 52% by weight of an adduct of melityose / (PO) 35 mol / (BO) 3 mol was obtained.

<Example 14>
In a reaction vessel capable of stirring, heating, cooling, substituting with nitrogen, and depressurizing with a vacuum pump, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and obtained in Production Example 16 A mixture (Y104Y204) 2553 parts (1 mol part) uniformly mixed with 1152 parts (0.5 mol part) of a polyoxyalkylene compound (Y204) was charged and dehydrated at 120 ° C. for 2 hours under reduced pressure. Next, hexamethylene diisocyanate (HMDI) {made by Mitsui Takeda Chemical Co., Ltd., Takenate 700, "Takenate" is a registered trademark of the company at 50 ° C. } Nitrogen substitution was repeated 3 times while charging 101 parts (0.6 mol parts) and stirring. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 6 hours at the same temperature. After confirming disappearance of the isocyanate group, a multimer (PY101) was obtained. And this multimer (PY101) was made into the surfactant (S114) of this invention as it is.

<Example 15>
In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. (3 mol parts) was uniformly mixed with 2706 parts (1.0 mol parts) (Y105Y205) and dehydrated at 120 ° C. for 2 hours under reduced pressure. Next, isophorone diisocyanate (IPDI) {manufactured by Sumika Bayer Urethane Co., Ltd., Death Module I, "Death Module" is a registered trademark of Bayer Aktiengesellschaft. } 149 parts (0.67 mole part) was charged and the nitrogen substitution was repeated three times while stirring. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 6 hours at the same temperature. After confirming disappearance of the isocyanate group, a multimer (PY102) was obtained. And this multimer (PY102) was made into the surfactant (S115) of this invention as it is.

<Example 16>
In a reaction vessel similar to that in Example 14, 1481 parts (0.53 mol) of the polyoxyalkylene compound (Y106) obtained in Production Example 6 and 981 parts of polyoxyalkylene compound (Y203) obtained in Production Example 15 (0 (47 mol parts) was uniformly mixed with 2462 parts (1.0 mol parts) (Y106Y203) and dehydrated at 120 ° C. for 2 hours under reduced pressure. Subsequently, 167 parts (0.75 mol part) of isophorone diisocyanate (IPDI) was charged at 60 ° C., and nitrogen substitution was repeated three times while stirring. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 6 hours at the same temperature. After confirming the disappearance of the isocyanate group, a multimer (PY103) was obtained. And this multimer (PY103) was made into the surface active agent (S116) of this invention as it is.

<Example 17>
In a reaction vessel similar to that in Example 14, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 1152 parts (0 of polyoxyalkylene compound (Y204) obtained in Production Example 16) 0.5 mol part) (Y104Y204) 2553 parts (1.0 mol part), potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. displayed. same as below. } 6.0 parts and 1,6-hexamethylene glycol diglycidyl ether {Epogosei HD, "Epogosei HD" manufactured by Yokkaichi Synthesis Co., Ltd. is a registered trademark of the same company. } 138 parts (0.6 mol parts) were charged and dehydrated at 70 ° C. under reduced pressure for 2 hours. Next, the reaction was carried out at 110 ° C. for 4 hours and at 130 ° C. for 8 hours with reduced pressure to confirm the disappearance of the epoxy group. Next, Kyoward treatment and dehydration were performed to obtain a multimer (PY201). And this multimer (PY201) was made into the surfactant (S117) of this invention as it is.

<Example 18>
In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. Mixture (Y105Y205) 2706 parts (1.0 mol part), potassium hydroxide 6.0 parts and polyoxypropylene (7 mol) glycol diglycidyl ether {Sanyo Chemical Industries, Ltd. Glicier PP-300P, epoxy equivalent: 300, “Gricier” is a registered trademark of the same company. } After 402 parts (0.67 mole part) was added, dehydration was performed at 80 ° C. under reduced pressure. Next, the reaction was carried out at 110 ° C. for 4 hours and at 130 ° C. for 8 hours with reduced pressure to confirm the disappearance of the epoxy group. Next, Kyoward treatment and dehydration were performed to obtain a multimer (PY202). And this multimer (PY202) was made into the surfactant (S118) of this invention as it is.

<Example 19>
In a reaction vessel similar to that in Example 14, 1725 parts (0.83 mol) of the polyoxyalkylene compound (Y110) obtained in Production Example 10 and 434 parts of the polyoxyalkylene compound (Y210) obtained in Production Example 22 (0 (17 mol parts) and 2159 parts (1.0 mol parts), potassium hydroxide 6.0 parts and polyoxypropylene (7 mol) glycol diglycidyl ether (Glicier PP-300P) After adding 300 parts (0.5 mol part), it was dehydrated at 80 ° C. under reduced pressure. Next, the reaction was carried out at 110 ° C. for 4 hours and at 130 ° C. for 8 hours with reduced pressure to confirm the disappearance of the epoxy group. Next, Kyoward treatment and dehydration were performed to obtain a multimer (PY203). And this multimer (PY203) was made into the surfactant (S119) of this invention as it is.

<Example 20>
In a reaction vessel similar to that in Example 14, 1041 parts (0.5 mol parts) of the polyoxyalkylene compound (Y104) obtained in Production Example 4 and 1152 parts (0 of polyoxyalkylene compound (Y204) obtained in Production Example 16) 0.55 parts) uniformly mixed (Y104Y204) 2553 parts (1.0 mole parts), sodium hydroxide {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd. displayed. same as below. } After 30.0 parts (0.75 mole part) was added, dehydration was performed at 110 ° C. under reduced pressure. Subsequently, 55.6 parts (0.6 mol parts) of epichlorohydrin {manufactured by Kashima Chemical Co., Ltd., the same shall apply hereinafter) were added dropwise over 4 hours at 40 ° C with reduced pressure, and further stirred at 40 ° C for 4 hours. Thereafter, the temperature was raised to 100 ° C., and stirring was continued for 4 hours and then at 130 ° C. for 3 hours, and disappearance of the epoxy group was confirmed. Next, Kyoward treatment and dehydration gave a multimer (PY301). And this multimer (PY301) was made into the surfactant (S120) of this invention as it is.

<Example 21>
In a reaction vessel similar to that in Example 14, 1863 parts (0.7 mol parts) of the polyoxyalkylene compound (Y105) obtained in Production Example 5 and 843 parts (0) of the polyoxyalkylene compound (Y205) obtained in Production Example 17 were used. .3 mol parts) and 2706 parts (1.0 mol parts) of a mixture (Y105Y205) and 34.0 parts (0.85 mol parts) of sodium hydroxide were added at 110 ° C. under reduced pressure. Dehydrated. Next, 62.0 parts (0.67 mol part) of epichlorohydrin was added dropwise over 5 hours at 40 ° C. with reduced pressure, and the mixture was further stirred at 40 ° C. for 5 hours. Thereafter, the temperature was raised to 100 ° C. and stirring was continued for 5 hours and then at 130 ° C. for 3 hours, and the disappearance of the epoxy group was confirmed. Next, Kyoward treatment and dehydration gave a multimer (PY302). And this multimer (PY302) was made into the surfactant (S121) of this invention as it is.

<Example 22>
In a reaction vessel similar to that in Example 14, 910 parts (0.41 mol) of the polyoxyalkylene compound (Y112) obtained in Production Example 12 and 1369 parts (0) of the polyoxyalkylene compound (Y209) obtained in Production Example 21 were used. 259 parts (1.0 mole part) and 34.0 parts (0.85 mole part) of sodium hydroxide, and then at 110 ° C. under reduced pressure. Dehydrated. Next, 74.0 parts (0.8 mole part) of epichlorohydrin was added dropwise over 5 hours at 40 ° C. under reduced pressure, and the mixture was further stirred at 40 ° C. for 5 hours. Thereafter, the temperature was raised to 100 ° C. and stirring was continued for 5 hours and then at 130 ° C. for 3 hours, and the disappearance of the epoxy group was confirmed. Next, Kyoward treatment and dehydration gave a multimer (PY303). And this multimer (PY303) was made into the surfactant (S122) of this invention as it is.

<Comparative Example 1>
The polyoxyalkylene compound (Y103) obtained in Production Example 3 was used as a comparative surfactant (C1).

<Comparative Example 2>
The polyoxyalkylene compound (Y106) obtained in Production Example 6 was used as a comparative surfactant (C2).

<Comparative Example 3>
Surfactant (C3) for comparison was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y103) obtained in Production Example 3 and 50 parts of the polyoxyalkylene compound (Y110) obtained in Production Example 10. .

<Comparative Example 4>
The polyoxyalkylene compound (Y204) obtained in Production Example 14 was used as a comparative surfactant (C4).

<Comparative Example 5>
A comparative surfactant (C5) was obtained by uniformly mixing 50 parts of the polyoxyalkylene compound (Y203) obtained in Production Example 13 and 50 parts of the polyoxyalkylene compound (Y208) obtained in Production Example 18. .

<Comparative Example 6>
A reaction vessel similar to Production Example 1 is charged with 2662 parts (1 mole part) of sucrose / (PO) 40-mole adduct (Y105) and 4.5 parts (0.08 mole part) of potassium hydroxide under reduced pressure. Dehydrated at 1 ° C. for 1 hour. Next, 2900 parts (50 mole parts) of propylene oxide (PO) was added dropwise at 110 ° C. over 10 hours with the same reduced pressure, and the remaining (PO) was reacted by continuing stirring at the same temperature for 4 hours. Next, Kyoward treatment was performed to obtain a polyoxyalkylene compound {sucrose / (PO) 90 mol adduct} (C6).

Using the surfactants (S101) to (S122) of the present invention and the surfactants (C1) to (C6) for comparison, a cationic electrodeposition paint is prepared, and water solubility, foam controllability and finish are improved. The results are shown in Table 6.

<Preparation of cationic electrodeposition paint>
(1) Preparation of Emulsion Epicoat 1004 {trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 950, “Epicoat” is a registered trademark of Resolution Research Netherland Bethloten Fuennaut Shap. } 200 parts, Epicoat 828EL {trade name, manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent: 190}, 200 parts, methyl isobutyl ketone (MIBK) 200 parts, N-methylethanolamine 60 parts, diethylenetriamine MIBK diketiminate 75 A base emulsion was obtained by adding 90 parts of MIBK solution containing 1% by weight.

After 1100 parts of isophorone diisocyanate, 600 parts of MIBK, 1.5 parts of dibutyltin dilaurate and 250 parts of trimethylolpropane were reacted at 40 to 70 ° C., 450 parts of methyl ethyl ketoxime was added at the same temperature, and 50 parts of n-butanol was further added. In addition, a completely blocked polyisocyanate resin solution was obtained.

After mixing 1230 parts of base emulsion, 570 parts of fully blocked polyisocyanate resin solution and 100 parts of ethylene glycol monobutyl ether, neutralize by adding 550 parts of 6% aqueous acetic acid, and then add 2400 parts of deionized water to make it uniform It was. Thereafter, low-boiling substances were distilled off under reduced pressure to obtain an emulsion having a concentration of 35%.

(2) Preparation of pigment paste 20 parts of base emulsion, titanium dioxide {Ishihara Sangyo Co., Ltd., trade name: Taipei R-930, "Taipeke" is a registered trademark of the company}, 30 parts kaolin {Tsuchiya Kaolin Co., Ltd. ) Product, trade name: Ultra white 90} 15 parts, aluminum phosphomolybdate {special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.} 3.5 parts, carbon black {special grade of reagent manufactured by Wako Pure Chemical Industries, Ltd.} 1 part, Sannonic SS-70 {Sanyo Kasei Kogyo Co., Ltd., nonionic surfactant, "Sannonic" is a registered trademark of the same company} 0.5 part and deionized water 30 parts Excel auto homogenizer equipped with impeller blades ( Dispersed to a maximum particle size of 10 μm or less (measured according to JIS K5600-2-5: 1999) with Nippon Seiki Co., Ltd. (Model ED) (30 0 rpm × 30 min) to obtain a pigment paste.

(3) Preparation of electrodeposition coating material for evaluation After 400 parts of the emulsion obtained above and 1.5 parts of the evaluation sample (surfactant) were stirred uniformly at 25 ° C. for 2 hours using a magnetic stirrer, 500 parts of deionized water was added and uniformly mixed at 25 ° C., and 100 parts of the pigment paste obtained above was added thereto and further uniformly mixed at 25 ° C. to obtain an electrodeposition paint for evaluation. A blank paint was obtained in the same manner as described above except that 1.5 parts of the evaluation sample was changed to 1.5 parts of water.

<Foam control>
In an atmosphere of 30 ° C. and 60% relative humidity, 100 ml of the electrodeposition paint for evaluation adjusted to 30 ° C. was added to a flow cup {JIS K5600-2-2: 1999, No. 4} and dropped into a 500 mL glass graduated cylinder (inner diameter: 50.0 mm, cylindrical length: 340 mm) placed under 1.0 m, and almost all of the electrodeposition paint for evaluation dropped into the graduated cylinder. Immediately after the start, when observing from the opening of the graduated cylinder, the time until a part of the foam layer in the graduated cylinder was cut and the coating liquid level in the lower layer started to be seen was defined as the defoaming time (minutes). The blank paint was similarly evaluated.

<Water solubility (water dispersibility)>
About the evaluation electrodeposition coating material and blank coating material which were obtained above, after leaving still at 30 degreeC for 24 hours, it evaluated on the following reference | standard.

0: No oil film or oil droplets are observed on the surface of the electrodeposition paint 1: A slight oil film is observed on the surface of the electrodeposition paint 2: Oil droplets are observed on the surface of the electrodeposition paint

<Finish finish>
A test panel in which the evaluation electrodeposition paint or blank paint obtained above was treated with zinc phosphate {trade name: zinc phosphate-treated steel sheet, manufactured by Nippon Test Panel Co., Ltd., dimensions, 150 mm × 70 mm × 0.8 mm} at 150 V Electrodeposition coating was carried out for 3 minutes, then pulled up from the coating bath, showered with tap water and washed with water. After naturally drying for 5 minutes in an atmosphere of 25 ° C. and 40% relative humidity, after baking for 20 minutes in an electric hot air drier adjusted to 160 ° C., it is cooled to about 25 ° C. and finished according to the following criteria. Was visually evaluated.

(1) Finishability-1
0: No occurrence of water droplets on the surface of the coating film 1-2: Very little water droplets on the coating surface (about 1 to 2 places) 3-4: Water droplets on the coating surface Slight occurrence (about 3 to 4 places) 5 <: Many water drop marks are seen on the coating film surface (more than 5 places)

(2) Finishability-2
0: No occurrence of residual bubble marks on the surface of the coating film 1-2: Very little generation of residual bubble marks (about 1 to 2 places) on the surface of the coating film 3-4: Remaining on the surface of the coating film Slight generation of bubble marks (about 3 to 4 places) 5 <: Many generations of residual bubble marks (5 or more places) are observed on the coating film surface

The surfactants of the present invention (Examples 1 to 22) were extremely excellent in foam controllability and finish. On the other hand, with the surfactants of the blank and Comparative Examples 1, 2, and 3, the foam controllability was poor. In addition, the surfactants of Comparative Examples 4, 5, and 6 were inferior in water solubility (water dispersibility) in addition to many water droplet traces.

Claims (7)

A mixture (Y) comprising the polyoxyalkylene compound (Y1) represented by the general formula (1) and the polyoxyalkylene compound (Y2) represented by the general formula (2);
A multimer (PY1) obtained by reacting the mixture (Y) with a diisocyanate having 6 to 15 carbon atoms;
Multimer (PY2) obtained by reaction of mixture (Y) with diglycidyl ether having 10 to 100 carbon atoms; and Multimer (PY3) obtained by reaction of mixture (Y) and epihalohydrin A surfactant comprising at least one kind as an essential component.

{H (OA−) _n } _t Q (1)

{H (OB−) _m (OA−) _n } _t Q (2)

Where Q is a reaction 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 3 carbon atoms, OB is an oxybutylene group, and H is hydrogen An atom, n is an integer of 1 to 35, m is 0 or an integer of 1 to 3, t is an integer of 2 to 4, and the oxy contained in the polyoxyalkylene compound (Y1) represented by the general formula (1) The total number of moles of the alkylene group (OA) is 15 to 100 moles per mole of the polyoxyalkylene compound (Y1), and the oxyalkylene group (Y2) represented by the general formula (2) ( The total number of moles of OA) is 15 to 50 moles per mole of polyoxyalkylene compound (Y2), and the total number of moles of oxybutylene group (OB) is 2 to 2 moles per mole of polyoxyalkylene compound (Y2). The mole, n, m, t 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 content of (Y1) is 40 to 90% by weight and the content of (Y2) is 10 to 60% by weight based on the weight of the polyoxyalkylene compound (Y1) and the polyoxyalkylene compound (Y2). The surfactant according to 1 or 2. Step (1) for obtaining a polyoxyalkylene compound (Y1) by reacting 1 mol part of a non-reducing di- or trisaccharide (a1) with 15 to 100 mol parts of an alkylene oxide (a2) having 2 to 3 carbon atoms ;
An adduct is obtained by reacting 1 mol part of a non-reducing disaccharide or trisaccharide (a1) with 15 to 50 mol part of an alkylene oxide (a2) having 2 to 3 carbon atoms, and then adding butylene oxide to the adduct. (A3) Step (2) for obtaining 2 to 6 mole parts to obtain polyoxyalkylene compound (Y2); and polyoxyalkylene compound (Y1) and polyoxyalkylene compound (Y2) are uniformly mixed to obtain a mixture Step (3) for obtaining (Y)
A method for producing a surfactant, comprising: As an essential component at least one selected from the group consisting of multimers (PY1), multimers (PY2) and multimers (PY3),
5. The amount of the diisocyanate having 6 to 15 carbon atoms, the diglycidyl ether having 10 to 100 carbon atoms or the epihalohydrin used is 0.5 to 0.8 mol per mol of the mixture (Y). The surfactant described. An aqueous coating liquid comprising the surfactant according to any one of claims 1 to 5. A cationic electrodeposition paint comprising the surfactant according to any one of claims 1 to 5.