JP2013047199A - Surfactant, and coating composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surfactant having high surface-active power.SOLUTION: The surfactant is represented by formula (1) or (2) wherein D is a hydrogen atom or an organic group represented by formula 3; L and M are a residue obtained by removing hydrogen atoms from two hydroxyl groups of a glycol; U is a residue obtained by removing a hydrogen atom from a hydroxyl group of 2-hydroxypropylene group or the like; G is a residue obtained by removing a hydrogen atom from a hydroxyl group of a monool; p is 1 to 3; the proportion of hydrogen atoms in all D is 0 to 50 mol% in one molecule; and -X(-OA)-Q-{(AO-)H}(3), wherein X is 2-hydroxypropyl group or the like, Q is a residue obtained by removing hydrogen atoms from t primary hydroxyl groups of nonreducing disaccharides or trisaccharides, AO and OA are an oxyalkylene group, n is 2 to 40, t is 2 to 4, and the total number of AO and OA is 10 to 80 per organic group.

Description

  The present invention relates to a surfactant and a coating composition containing the same. More specifically, surfactants that are optimal for water-based paints (particularly preferably used as dispersants, anti-waxing agents, paint film contamination reducing agents, paint film surface conditioners, etc.) and paint compositions containing the same Related to things.

  In recent years, the demand for water-based paints has increased rapidly from the viewpoint of work safety and pollution-free. In addition, there is also a remarkable movement toward making water-based thermosetting paints in industrial coating lines, and in the near future, almost all base coats and intermediate paints for automobiles will become water-based. However, since the main component of the water-based paint is water, 1) problems such as toning and viscosity increase due to dispersibility of the pigment, and 2) the latent heat of evaporation of water used as the main solvent is large. As a result, the problem is that cracks are likely to occur due to foaming during heat curing. 3) When a surfactant is added to solve these problems, the paint is liable to foam. 4) There is a problem that it is necessary to add a foaming agent, etc. 4) There is a problem that the water resistance of the formed coating film decreases due to the addition of the surfactant, and the surfactant that can solve these problems Development was desired.

  As a pigment dispersant for water-based paint, polyacrylate (Patent Document 1) is known. Further, as an armpit inhibitor, an alkyl etherified product of benzoin having 1 to 4 carbon atoms (Patent Document 2) is known. Furthermore, a surfactant (Patent Document 3) that has high surface activity (pigment dispersibility, anti-flaking property during heat curing, leveling property, etc.) and can form a coating film with excellent water resistance is also known. ing.

JP-A-53-129200 Japanese Patent Publication No. 2-390 JP 2010-047715 A

The 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 pigment dispersion is used. Furthermore, when this dispersing agent is added, the coating tends to foam, and there is a problem that a surfactant (such as an antifoaming agent) is required to eliminate this.
Moreover, when the anti-wrinkle agent described in Patent Document 2 is used for a thermosetting water-based paint, the compatibility is insufficient, so that the smoothness and sharpness of the paint film are insufficient, and the finished appearance is impaired. There's a problem. In addition, there is a problem that a new surfactant needs to be added to improve compatibility.
With the surfactant described in Patent Document 3, if the water resistance of the coating film is improved, or the smoothness and sharpness are improved, further improvement of the level of addition, such as reduction of the required amount, is desired. .
That is, an object of the present invention is to provide a surfactant having a high surface activity, which is excellent in pigment dispersibility, anti-boilability during heat curing, coating surface adjustment (leveling properties, etc.), and the like. It is to provide a surfactant capable of forming a coating film excellent in water resistance.

The inventor of the present invention has reached the present invention as a result of intensive studies to solve the above problems.
That is, the feature of the surfactant of the present invention is that it contains the polyoxyalkylene compound (Y) represented by either the general formula (1) or (2).

However, D is a hydrogen atom or the organic group represented by General formula (3), L is the residue remove | excluding the hydrogen atom from two hydroxyl groups of C20-200 polyoxyalkylene glycol, M is C4. residue obtained by removing from the two hydrogen atoms of hydroxyl groups glycols ~ 44, U is 2-hydroxypropylene group _{{-CH 2 -CH (OH) -CH} 2 -} or hydroxymethyl ethylene group _{-CH 2 -CH A residue obtained by removing a hydrogen atom from a hydroxyl group of (CH ₂ OH) —}, G is a residue obtained by removing a hydrogen atom from a hydroxyl group of a monool having 3 to 18 carbon atoms, p represents an integer of 1 to 3, The proportion of hydrogen atoms in D of 0 to 0 mol% per molecule.

_{-X (-OA) n -Q - {} (AO-) n H} t-1 (3)

  X is a 2-hydroxypropylene group or hydroxymethylethylene group, Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, AO and OA are oxyoxygen having 2 to 4 carbon atoms An alkylene group, H is a hydrogen atom, n is an integer of 2 to 40, t is an integer of 2 to 4, the total number of AO and OA is 10 to 80 per organic group, and D, L, M , U, G, Q, (OA) n, (AO) n, n, p, t may be the same or different.

  The feature of the coating composition of the present invention is that it comprises a coating material and the above-mentioned surfactant, and the surfactant is contained in an amount of 0.1 to 5% by weight based on the weight of the coating material.

A feature of the production method of the present invention is a method for producing the above surfactant,
Step (1) for obtaining a compound (a12) from a chemical reaction (1) of 1 mol part of a non-reducing di- or trisaccharide (a1) and 10 to 80 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. And a method (1) comprising a step (4) of obtaining a polyoxyalkylene compound (Y1) from a chemical reaction (4) between 1 mol part of the compound (a45) and 2-8 mol parts of the glycidyl compound (a123). ;; or

Step (1) for obtaining a compound (a12) from a chemical reaction (1) of 1 mol part of a non-reducing di- or trisaccharide (a1) and 10 to 80 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. Step (3);
Step (5) of obtaining Compound (a456) from Chemical Reaction (5) of 1 mol part of Compound (a45) and 2 to 2.2 mol part of monoglycidyl ether (a6) having 6 to 21 carbon atoms; and Compound ( a456) A method (2) comprising a step (6) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (6) of 1 mol part and a glycidyl compound (a123) 2-8 mol part
The point consisting of

The surfactant of the present invention exhibits high surface activity with a smaller addition amount.
Even when the surfactant of the present invention is applied to a paint, it does not lower the water resistance of the formed coating film. Further, the surfactant of the present invention is excellent in dispersibility of the pigment, stably disperses the pigment in the paint, prevents its sedimentation, aggregation and the like over a long period of time, and improves the arrangement of the design pigment and the like. Greatly effective in improving toning. In addition, the surfactant of the present invention has a great effect of improving the wettability of the coating film, exhibiting antifogging properties, and washing away stains on the coating film surface due to rain. Furthermore, the surfactant of the present invention prevents defects such as cracks during heat curing in thermosetting paints, and is excellent in the effect of imparting leveling properties. Furthermore, the surfactant of the present invention hardly foams and also has a function as an antifoaming agent. Therefore, the surfactant of the present invention is extremely useful particularly for architectural water-based paints or aqueous heat-curing paints (electrodeposition paints, automobile base coat paints) and the like.

  Since the coating composition of this invention contains said surfactant, it does not reduce the water resistance of the coating film formed. Moreover, since it is excellent in the toning property of the coating film and the smoothness of the surface, the design is high. Therefore, the coating composition of the present invention is very useful for an architectural water-based coating composition coated on an outer wall or the like, an aqueous thermosetting coating composition (particularly an aqueous emulsion coating composition), and the like.

  The production method of the present invention is suitable for producing the above surfactant.

In the general formulas (1) and (2), a polyoxygen having 20 to 200 carbon atoms that can form a residue (L) obtained by removing a hydrogen atom from two hydroxyl groups of a polyoxyalkylene glycol having 20 to 200 carbon atoms. As oxyalkylene glycol, alkylene oxide addition of alkylene diol (2 to 6 carbon atoms; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol, hexamethylene glycol, etc.) body, cycloalkylene diols, alkylene oxide adducts and arylene diols (number 6 to 15 carbon atoms in the (carbon number 6-8 cyclohexyl glycol and di (hydroxymethyl) cyclohexane, etc.); hydroquinone, catechol and bisphenol a _{{HO-C 6 4} -C _{(CH 3)} alkylene oxide adducts of ₂ -C ₆ H 4 -OH} are included.

  Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. Among these, ethylene oxide, propylene oxide, and a mixture thereof are preferable from the viewpoint of hydrophilicity and water resistance, and a mixture of ethylene oxide and propylene oxide is further preferable from the viewpoint of wettability (resistance to dry unevenness).

  When propylene oxide and / or butylene oxide and ethylene oxide are included, the content ratio (mol%) of ethylene oxide is preferably 2 to 10, more preferably 2 to 8, based on the total number of moles of alkylene oxide. When a plurality of types of alkylene oxide are included, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and the content ratio of the alkylene oxide.

  These polyoxyalkylene glycols preferably have 20 to 200 carbon atoms, more preferably 50 to 150 carbon atoms.

  Among these polyoxyalkylene glycols, alkylene oxide adducts of alkylene diols and alkylene oxide adducts of arylene diols are preferred, more preferably alkylene oxide adducts of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol or hexamethylene glycol. Particularly preferred is an alkylene oxide adduct of propylene glycol or dipropylene glycol.

  Examples of polyoxyalkylene glycol that can form the residue (L) include propylene glycol 33.5 mol adduct of propylene glycol {Sanix Diol PP-2000, manufactured by Sanyo Chemical Industries Ltd.}, propylene glycol propylene oxide 12. 5 mol / ethylene oxide 2 mol adduct {Sannicks diol PL-910, manufactured by Sanyo Chemical Industries, Ltd.}, propylene glycol propylene oxide 50 mol adduct {Sannicks diol PP-3000, manufactured by Sanyo Chemical Industries, Ltd.} Etc. can be preferably exemplified.

  Examples of the glycol having 4 to 44 carbon atoms that can form a residue (M) obtained by removing a hydrogen atom from two hydroxyl groups of a glycol having 4 to 44 carbon atoms include 1,4-butanediol, 1,2-butanediol, and C4-C6 alkylene diols such as hexamethylene glycol, and alkylene oxide adducts of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol or hexamethylene glycol ( C4-C44) etc. are mentioned.

  Of these glycols, 1,4-butanediol and hexamethylene glycol, and 1,4-butanediol, hexamethylene glycol or dipropylene glycol alkylene oxide adducts (4 to 44 carbon atoms) are preferred, and more preferred It is an alkylene oxide adduct (having 4 to 44 carbon atoms) of hexamethylene glycol and dipropylene glycol.

  Monools that can form a residue (G) obtained by removing a hydrogen atom from a hydroxyl group of a monool having 3 to 18 carbon atoms include aliphatic saturated alcohols {(iso) propyl alcohol, (iso) butyl alcohol, (iso) amyl Alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, etc. }, Aliphatic unsaturated alcohols {allyl alcohol, crotyl alcohol and octadecenyl alcohol, etc.}, alicyclic alcohols {cyclopentanol, cyclohexanol and adamant Alcohol, etc.}, aromatic alcohols {phenols include benzyl alcohol and cinnamyl alcohol or the like}, and monools such as by adding an alkylene oxide having 2 to 4 carbon atoms in these monool (18 carbons) are. Of these, butyl alcohol, 2-ethylhexyl alcohol, allyl alcohol and phenol are preferred.

  p represents the integer of 1-3, Preferably it is an integer of 1-2. Within this range, the surface activity (leveling properties, etc.) is further improved.

  D is a hydrogen atom or an organic group represented by the general formula (3). The proportion of hydrogen atoms in all D is from 0 to 50 mol%, preferably from 0 to 30 mol% per molecule.

  Non-reducing di- or trisaccharides that can constitute a residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of non-reducing di- or trisaccharides include sucrose, trehalose, Isotrehalose, isosaccharose, gentianose, raffinose, meretitol and planteose are included. Of these, sucrose, trehalose, gentianose, raffinose and planteose are preferable from the viewpoint of wettability and the like, more preferably sucrose and trehalose, and sucrose is particularly preferable from the viewpoint of supply ability and cost.

  Examples of the oxyalkylene group having 2 to 4 carbon atoms (OA, OA) include oxyethylene, oxypropylene, oxybutylene, and a mixture thereof. Of these, oxyethylene, oxypropylene, and a mixture thereof are preferable from the viewpoint of hydrophilicity and water resistance, and a mixture of oxyethylene and oxypropylene is more preferable from the viewpoint of wettability (resistance to dry unevenness).

  When oxypropylene and / or oxybutylene and oxyethylene are included, the content ratio (mol%) of oxyethylene is preferably 2 to 10, more preferably 2 to 8, based on the total number of moles of oxyalkylene groups. It is. In this case, it is preferable that oxypropylene and / or oxybutylene is located at the end away from the reaction residue (Q). That is, when (—OA) n and (OA—) n contain an oxyethylene group, the oxyethylene group is preferably directly bonded to the reaction residue (Q). Moreover, when (-OA) n and (OA-) n contain a plurality of types of oxyalkylene groups, there is no limitation on the bonding order (block shape, random shape, and combinations thereof) and the content ratio of the oxyalkylene groups.

  n is an integer of 2 to 40, preferably an integer of 5 to 38, more preferably an integer of 8 to 35, and particularly preferably an integer of 10 to 30. Within this range, the surface-active ability (dispersibility of pigment, leveling property during heat curing, etc.) is further improved.

  t is an integer of 2 to 4, preferably 3 or 4, and more preferably 3. Within this range, the water resistance (rust prevention) and wettability (drying unevenness) of the coating film are further improved. T corresponds to the number of primary hydroxyl groups of the di- or trisaccharide, and is, for example, 3 for sucrose, 2 for trehalose, and 4 for meretitose.

  The total number of AO and OA contained per organic group represented by the general formula (3) is 10 to 80, preferably 10 to 70, more preferably 20 to 70, and particularly preferably 20 to 60. It is. Within this range, the water resistance (rust prevention) and wettability (drying unevenness) of the coating film are further improved.

X represents a 2-hydroxypropylene group {—CH ₂ —CH (OH) —CH ₂ —} or a hydroxymethylethylene group {—CH ₂ —CH (CH ₂ OH) —}, and is obtained by a ring-opening addition reaction of a glycidyl group. Arise.

  The surfactant containing the polyoxyalkylene compound (Y) represented by the general formulas (1) and (2) is preferably produced by the following method.

That is, the process of obtaining a compound (a12) from the chemical reaction (1) of 1 mol part of non-reducing disaccharide or trisaccharide (a1) and 10 to 80 mol part of alkylene oxide (a2) having 2 to 4 carbon atoms ( 1);
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. And a method (1) comprising a step (4) of obtaining a polyoxyalkylene compound (Y1) from a chemical reaction (4) between 1 mol part of the compound (a45) and 2-8 mol parts of the glycidyl compound (a123). ;; or

Step (1) for obtaining a compound (a12) from a chemical reaction (1) of 1 mol part of a non-reducing di- or trisaccharide (a1) and 10 to 80 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. Step (3);
Step (5) of obtaining Compound (a456) from Chemical Reaction (5) of 1 mol part of Compound (a45) and 2 to 2.2 mol part of monoglycidyl ether (a6) having 6 to 21 carbon atoms; and Compound ( a456) A method (2) comprising a step (6) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (6) of 1 mol part and 2 to 8 mol parts of a glycidyl compound (a123).

  The polyoxyalkylene compound (Y) having a structure produced by these chemical reactions has a distribution in the number of oxyalkylene groups, n, p, etc. Strictly speaking, it becomes a mixture of a plurality of types of polyoxyalkylene compounds. In the mixture, polyoxyalkylene compounds represented by the general formulas (1) and (2) are included. Even in this case, the manufacturing method is not limited.

  When obtaining the glycidyl compound (a123), the glycidyl compound (a123) further reacts with the compound (a12), or a plurality of glycidyl compounds (a123) react with each other to have a plurality of compound (a12) units in one molecule. A glycidyl compound may be generated, and a polyoxyalkylene compound reacted with such a glycidyl compound is also included in the present invention.

  In the step (1), the amount (mole part) of the alkylene oxide (a2) used is preferably 10 to 80, more preferably 10 to 1 part by mole of the non-reducing di- or trisaccharide (a1). 70, particularly preferably 20 to 75, most preferably 20 to 60. Within this range, the surface active ability (dispersibility of pigment, leveling property during heat curing, etc.) and water resistance are further improved.

  In the step (2), the use amount (mol part) of the epihalohydrin (a3) is preferably 1 to 1.5 mol, more preferably 1.1 to 1.5 mol, relative to 1 mol part of the compound (a12). Particularly preferred is 1.2 to 1.5, and most preferred is 1.2 to 1.4. Within this range, desalting treatment and the like are facilitated in the purification step of the glycidyl compound (a123).

  In the step (3), the usage amount (mole part) of the polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms is as follows: 1 mol part of diglycidyl ether (a4) having 10 to 50 carbon atoms. It is preferably 33 to 2, more preferably 1.4 to 2, particularly preferably 1.5 to 2, and most preferably 1.5 to 1.9. Within this range, the surface activity (leveling properties during heat curing, etc.) and water resistance are further improved.

  In the step (4), the usage amount (mole part) of the glycidyl compound (a123) is preferably 2 to 8, more preferably 2 to 7, particularly preferably 3 to 1 mole part of the compound (a45). 7, most preferably 3-6. Within this range, the surface activity (dispersibility of pigment, etc.) is further improved.

  In the step (5), the usage amount (mole part) of the monoglycidyl ether having 6 to 21 carbon atoms (a6) is preferably 2 to 2.2, more preferably 1 mol part of the compound (a45). 2 to 2.1. Within this range, the surface activity (leveling properties during heat curing, etc.) and water resistance are further improved.

  In the step (6), the usage amount (mole part) of the glycidyl compound (a123) is preferably 2 to 8, more preferably 2 to 7, particularly preferably 3 to 1 mol part of the compound (a456). 7, most preferably 3-6. Within this range, the surface-active ability (dispersibility of pigment, leveling property during heat curing, etc.) is further improved.

  The non-reducing di- or trisaccharide (a1) is the same as the above di- or trisaccharide that can form the residue (Q), and the preferred range is also the same.

  As the alkylene oxide (a2), an alkylene oxide having 2 to 4 carbon atoms can be used, and examples thereof include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. Among these, PO is preferable, and PO and BO are mixed from the viewpoint of water resistance of the coating film, etc., but PO and / or BO and EO are mixed from the viewpoint of surface activity (dispersibility of pigment, etc.). But you can.

  Epihalohydrin (a3) includes epichlorohydrin and epibromohydrin.

  Examples of the diglycidyl ether (a4) having 10 to 50 carbon atoms include 1,4-butanediol diglycidyl ether, tetramethylene diglycidyl ether, 2,2-dimethylpropylene diglycidyl ether, hexamethylene diglycidyl ether, and polyoxyalkylene (Alkylene oxide adduct of alkylene diol (carbon number 4 to 44), alkylene having 2 to 4 carbon atoms) and diglycidyl ether. Of these, hexamethylene diglycidyl ether and polyoxyalkylene diglycidyl ether are preferable, and polyoxyalkylene diglycidyl ether is more preferable.

Examples of the polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms include alkylene diol (2 to 6 carbon atoms; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,2-butanediol. And alkylene oxide adducts of cycloalkylene diol (carbon number 6-8; cyclohexyl glycol and di (hydroxymethyl) cyclohexane etc.) and arylene diols (carbon number 6-15; hydroquinone) alkylene oxide adducts of catechol and bisphenol _{a {HO-C 6 H 4} -C (CH 3) 2 -C 6 H 4 -OH} are included.

These polyoxyalkylene glycols preferably have 20 to 200 carbon atoms, more preferably 50 to 150 carbon atoms.
Of these polyoxyalkylene glycols, alkylene oxide adducts of alkylene diols and alkylene oxide adducts of arylene diols are preferred, more preferred are alkylene oxide adducts of ethylene glycol, propylene glycol or hexamethylene glycol, and most preferred are propylene glycols. Is an alkylene oxide adduct.

  In the diglycidyl ether having 10 to 50 carbon atoms (a4) and the polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms, the alkylene oxide includes alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, Examples include butylene oxide and a mixture thereof. Among these, ethylene oxide, propylene oxide, and a mixture thereof are preferable from the viewpoint of hydrophilicity and water resistance, and a mixture of ethylene oxide and propylene oxide is further preferable from the viewpoint of wettability (resistance to dry unevenness).

  When propylene oxide and / or butylene oxide and ethylene oxide are included, the content ratio (mol%) of ethylene oxide is preferably 2 to 10, more preferably 2 to 8, based on the total number of moles of alkylene oxide. When a plurality of types of alkylene oxide are included, there is no limitation on the bonding order (block shape, random shape and combinations thereof) and the content ratio of the alkylene oxide.

  Examples of the monoglycidyl ether (a6) having 6 to 21 carbon atoms include alkenyl glycidyl ether {allyl glycidyl ether and the like}, alkyl glycidyl ether {butyl glycidyl ether, 2-ethylhexyl glycidyl ether and stearyl glycidyl ether and the like}, aryl glycidyl ether {phenyl Glycidyl ether and the like} and alkoxy (polyoxyalkylene) glycidyl ether {butoxy (polyoxyethylene) glycidyl ether and the like}. Of these, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether and phenyl glycidyl ether are preferred, and butyl glycidyl ether and 2-ethylhexyl glycidyl ether are more preferred.

  In the chemical reaction of the non-reducing disaccharide or trisaccharide (a1) and the alkylene oxide (a2), when multiple types of alkylene oxide are used, the order of reaction (block, random and combinations thereof) and the use ratio are as follows: Although there is no limitation, it is preferable to include a block shape or a combination of a block shape and a random shape. When EO is contained, the use ratio (mol%) of EO is preferably 1 to 10, more preferably 2 to 9, particularly preferably 3 to 8, most preferably based on the total number of moles of alkylene oxide. Is 4-7. When EO and PO or / and BO are included, it is preferable to react PO and / or BO after the reaction of EO to the di- or trisaccharide (a1).

  The chemical reaction {step (1)} of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2) may be performed 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 {step (1)} with 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, Triethylenediamine 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 {step (1)} of the non-reducing di- or trisaccharide (a1) and the alkylene oxide (a2). As the reaction solvent, those having no active hydrogen are preferred, and more preferably non-reducing disaccharides or trisaccharides (a1), alkylene oxides (a2) and products (a12) produced by these reactions are dissolved. Is 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 using a reaction solvent, the amount used (% by weight) is preferably 20 to 200 based on the weight of the compound (a12) produced by the reaction of the di- or trisaccharide (a1) and the alkylene oxide (a2). More preferably, it is 40-180, Most preferably, it is 60-150.

  When a reaction solvent is used, it is preferable to remove the reaction solvent after the reaction. The residual amount (% by weight) of the reaction solvent is preferably 0.1 or less, more preferably 0.05 or less, particularly preferably 0.01 or less, based on the weight of the compound (a12). 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 adsorption removal, a method of treating with an alkali adsorbent such as synthetic aluminosilicate can be applied. For example, when KYOWARD 700 is used, the addition amount (% by weight) of the alkali adsorbent is about 1 to 5 based on the weight of the compound (a12), the processing temperature is about 60 to 120 ° C., and the processing time is 0.00. About 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 {step (2)} between the compound (a12) and the epihalohydrin (a3), an ether bond is formed by dehydrohalogenation from the hydrogen atom of the hydroxyl group of the 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 compound (a12) and the epihalohydrin (a3), a vessel that can be heated, cooled, and stirred can be used. It is preferable to react in the presence of

  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 the base used is preferably such that the ratio {base equivalent of base (eq.) / Equivalent of halogen of epihalohydrin (a3) (eq.)} Is 0.7 to 1.1, more preferably 0.8. The amount is 8 to 1.0. If this ratio is used, the step of neutralizing the excess base can be omitted, and the excess epihalohydrin (a3) can be removed by a dehydration step under reduced pressure or the like.

  The amount of compound (a12) and epihalohydrin (a3) used is preferably such that the molar ratio of compound (a12) / epihalohydrin (a3) is 0.25 to 1, more preferably 0.33 to 1. is there. If it is this ratio, a desalting filtration process can be implemented simply.

  Prior to the start of chemical reaction (2) in step (2), the water content (wt%) can be adjusted to 2-5 based on the weight of compound (a12), epihalohydrin (a3) and base. More preferably, it is adjusted to 2.5 to 4.5, particularly preferably 3 to 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).

  In the step (2), water is by-produced with the neutralized salt. However, if the water content is within the above range at the start of the reaction, it may be exceeded in the middle of the reaction.

  40-90 are preferable and, as for reaction temperature (degreeC), More preferably, it is 50-80. 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.

  Confirmation of the end point of the chemical reaction (2) in the step (2) can be performed by the following method or the like. That is, when the pH of the reaction solution is measured and becomes 7 to 8, the reaction end point is reached. 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).

  Next, the glycidyl compound (a123) is isolated and purified through desalting (removal of neutralized salt), dehydration and the like by a conventional method (filtration).

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 30-100 are preferable, More preferably, it is 50-90.

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 100 ° C.

The water content (% by weight) after dehydration is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less, based on the weight of the glycidyl compound (a123).
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).

  When an excess base remains at the end of the chemical reaction (2) in the step (2), it is preferably removed. As the removal method, the removal method of “reaction catalyst that can be used for the addition reaction of alkylene oxide (a2)” described in the method for producing the basket (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 glycidyl compound (a123) corresponds to the glycidyl compound constituting the organic group represented by the general formula (3). As a glycidyl compound (a123), the glycidyl compound obtained through a process (1) and a process (2) using the compound shown in Table 1 can be illustrated preferably.

  Q1 represents sucrose, Q2 represents trehalose, Q3 represents meletitose, P represents propylene oxide, E represents ethylene oxide, B represents butylene oxide, and these subscripts are non-reducing di- or trisaccharides, respectively. The number of moles per mole, / represents a block shape, • represents a random shape, ECH represents epichlorohydrin, and the subscript represents the number of moles per mole of non-reducing di- or trisaccharide.

  Reaction of diglycidyl ether having 10 to 50 carbon atoms (a4) with polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms {step (3)}, reaction of glycidyl compound (a123) and compound (a45) { Step (4)}, reaction of compound (a45) with monoglycidyl ether having 6 to 21 carbon atoms (a6) {step (5)} and reaction of glycidyl compound (a123) with compound (a456) {step (6 )} May be the same reaction apparatus, catalyst and removal method as those used for the reaction of the non-reducing disaccharide or trisaccharide (a1) with the alkylene oxide (a2). As the end point of the reaction (quantification of epoxy group for confirming disappearance of epoxy group), hydrogen halide (HB) is generated from perchloric acid and quaternary ammonium salt (CTAB), and this is combined with epoxy group. A cetyltrimethylammonium bromide (CTAB) method (based on JIS K7236: 2001 (ISO3001: 1999)) can be applied.

  Of the polyoxyalkylene compounds (Y) represented by either general formula (1) or (2), the polyoxyalkylene compounds (Y1) represented by general formula (1) are shown in Table 2. Compounds obtained through steps (3) to (4) using raw materials {diglycidyl ether (a4), polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms and glycidyl compound (a123)} are preferred. It can be illustrated.

  M1 is polyoxypropylene (7 mol) glycol diglycidyl ether {Glicier PP-300P, manufactured by Sanyo Chemical Industries, epoxy equivalent 290g / eq, "Glicier" is a registered trademark of the company}, M2 is Polyoxypropylene (3 mol) glycol diglycidyl ether {Epiol P-200, manufactured by NOF Corporation, epoxy equivalent 155 g / eq, "Epiol" is a registered trademark of the same company}. L1 is propylene glycol / PO12.5 mol / EO2 mol adduct {Sanixdiol PL-910, manufactured by Sanyo Chemical Co., Ltd., "Sannicksdiol" is a registered trademark of the same company}, L2 is propylene Glycol / PO 33.5 mol adduct {Sannicksdiol PP-2000, manufactured by Sanyo Chemical Industries Ltd.} D1 to D8 are glycidyl compounds (a123) exemplified in Table 1. Each number in parentheses represents the number of moles used.

  Of the polyoxyalkylene compounds (Y) represented by either general formula (1) or (2), the polyoxyalkylene compounds (Y2) represented by general formula (2) are shown in Table 3. Using the raw materials {diglycidyl ether (a4), polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms, monoglycidyl ether (a6) and glycidyl compound (a123)}, steps (3), (5) and ( Preferred examples include compounds obtained through 6).

  M1, M2, L1, and L2 are the same as in Table 2. G1 is butyl glycidyl ether {Epiol B, manufactured by NOF Corporation, epoxy equivalent 150 g / eq}, and G2 is 2-ethylhexyl glycidyl ether {Epiol. EH-N, manufactured by NOF Corporation, epoxy equivalent of 190 g / eq}. Each number in parentheses represents the number of moles used.

  Of these, Y12, Y14, Y16, Y18, Y22, Y24, Y26 and Y28 are preferred, Y22, Y24, Y26 and Y28 are more preferred, and Y26 and Y28 are particularly preferred.

The surfactant of the present invention contains known additives (viscosity adjusting agent, antifoaming agent, wetting agent and film forming adjusting agent, solvent, etc.) and the like as necessary in addition to the polyoxyalkylene compound (Y). Can be made.
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 ( San Nopco Co., Ltd.) and the like, as the film-formation regulator, texanol (manufactured by Eastman Chemical Co., etc.) . In addition, when it contains an additive, as these content, all are about 0.1 to 10 weight% based on the weight of a polyoxyalkylene compound (Y).

In the surfactant of the present invention, a plurality of non-reducing di- or trisaccharide residues are chemically bonded in one molecule, and the non-reducing di- or trisaccharide residues are subjected to a reaction. It has a secondary hydroxyl group having a large steric hindrance {of the non-reducing di- or trisaccharide hydroxyl group, the primary hydroxyl group reacts selectively and the secondary hydroxyl group is considered to remain unreacted. }. For this reason, the surfactant of the present invention imparts high hydrophilicity by a large number of hydroxyl groups and the like, and the steric hindrance of the secondary hydroxyl group is large, so that the water resistance is hardly lowered.
Therefore, the surfactant of the present invention can be used as a dispersant for hydrophilic pigments, etc., and also includes an emulsifier, a surface tension reducing agent (including a curtain flow coat property improving agent and a spraying proper agent), and an antifoaming agent (foam suppression). Agent, anti-foaming agent, foam stabilizer, etc.), anti-skinning agent (aqueous paint prevents the surface of paint from solidifying during storage in container), anti-icing agent, anti-condensation agent, anti-fogging agent In addition to contamination reducing agents and fingerprint adhesion preventing agents, it can be widely used as other paint additives, and can also be used as these raw materials.

Applications as emulsifiers and dispersants include paper coating paints, aqueous paints and pigment dispersants for various inks, and emulsifiers for various aqueous paint resins.
Examples of the antifoaming agent include an antifoaming agent for paper coating paint, an antifoaming agent for water-based paint, and an antifoaming agent for various inks.
As the surface tension reducing agent, there are applications as curtain flow coatability improvers such as paper coating paints and water-based paints, and spray-adjusting agents such as water-based paints and various inks.

  The amount (% by weight) of the surfactant of the present invention is appropriately determined according to the use, but it is 0.1 for non-aqueous (solvent, weak solvent, etc.) building paints, building material paints, baking paints, etc. -5 is preferable, More preferably, it is 0.02-4, Most preferably, it is 0.5-3. For example, when used for water-based paints (including building paints, building material paints, baking paints, paper coating paints, various inks, etc.), 0.1 to 5 is preferable based on the weight of water-based paints, etc. Preferably it is 0.5-4, Most preferably, it is 1-3.

  That is, the coating composition of the present invention comprises a coating material and the above-mentioned surfactant, and contains 0.1 to 5% by weight of this surfactant based on the weight of the coating material.

  The surfactant of the present invention can be applied to both aqueous paints and non-aqueous paints, and among these, it is suitable for aqueous paints, and particularly suitable for aqueous emulsion paints. Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints.

  When the surfactant of the present invention is added to the paint, the timing of adding the surfactant of the present invention to the paint is as follows: (1) When dispersing the pigment, (2) Resin component and various additives in the dispersed pigment And (3) immediately before coating, and any of them may be used, but when used as a pigment dispersant, it is preferably added at the time of pigment dispersion.

  The paint or the like to which the surfactant of the present invention is added can be applied to an object to be coated by an ordinary method, such as brush coating, roller coating, bell coating, air spray coating, airless coating, roll coater coating, and flow coater coating. The painting method etc. are 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 that can be stirred, heated, cooled, dripped, pressurized with nitrogen gas, etc. and depressurized with a vacuum pump, purified granulated sugar {manufactured by Taiyo Co., Ltd., the same applies hereinafter. } 342 parts (1 mole part) and DMF {Mitsubishi Gas Chemical Co., Ltd., the same applies hereinafter. } After throwing 1000 parts, the operation of pressurizing to 0.4 MPa with nitrogen gas and discharging until 0.02 MPa was repeated three times (hereinafter abbreviated as nitrogen substitution). Thereafter, the temperature was raised to 100 ° C. while stirring, and 1160 parts (20 mole parts) of PO (propylene oxide, the same shall apply hereinafter) was added dropwise at this temperature over 6 hours, followed by stirring at the same temperature for 3 hours. Then, the remaining PO was reacted. Next, DMF was removed under reduced pressure at 120 ° C. to obtain polyether (E1) (sucrose / PO 20 mol adduct).

  In a pressure resistant reaction vessel similar to Production Example 1, 1502 parts (1 mole part) of polyether (E1) (sucrose / PO 20 mole adduct), sodium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd., pure water 97% by weight, the same applies hereinafter. } 41.2 parts (1 mol part) and 50 parts of water were added, and 102 parts (1.1 mol parts) of epichlorohydrin were added dropwise over 4 hours while stirring at 50 ° C. 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)]. } Was confirmed. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.02% by weight), suction filtration with filter paper (filter paper No. 2: manufactured by ADVANTEC, reserved particle diameter: 5 μm, The same applies hereinafter) to obtain a glycidyl compound {uniformly transparent liquid} (D1) having an epoxy equivalent (g / eq.) 1620.

<Production Example 2>
Into a pressure resistant reactor similar to Production Example 1, 342 parts (1 mole part) of purified granulated sugar and 1000 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. with stirring, and at this temperature, 88 parts (2 mole parts) of EO (ethylene oxide, the same shall apply hereinafter) was added dropwise over 1 hour, and PO1624 parts (28 mole parts) were further added. The solution was added dropwise over 8 hours, and the stirring was continued at the same temperature for 3 hours to react the remaining PO. Next, DMF was removed under reduced pressure at 120 ° C. to obtain polyether (E2) (sucrose / EO2 mol / PO28 mol adduct).

  In a pressure resistant reaction vessel similar to Production Example 1, 2054 parts (1 mole part) of polyether (E2) (sucrose / EO2 mole / PO28 mole adduct), 41.2 parts (1 mole part) of sodium hydroxide and water 80 While stirring at 50 ° C., 111 parts (1.2 mole parts) of epichlorohydrin was added dropwise over 5 hours. Subsequently, stirring was continued at 60 ° C. for 5 hours, and it was confirmed that the pH of the reaction solution became 7-8. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.04% by weight), suction filtration using a filter paper was performed to obtain a glycidyl compound having an epoxy equivalent (g / eq.) Of 2160 { A uniformly transparent liquid} (D2) was obtained.

<Production Example 3>
In the same pressure resistant reactor as in Production Example 1, 2054 parts (1 mole part) of polyether (E2) (sucrose / EO2 mole / PO28 mole adduct) and potassium hydroxide {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd. The amount used was expressed as a pure equivalent amount excluding moisture. same as below. } 8 parts were added to perform nitrogen substitution, and dehydration was performed at 120 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, PO1508 parts (26 mol parts) were added dropwise over 6 hours at 100 ° C. with reduced pressure. Next, 288 parts (4 mole parts) of BO (butylene oxide) was added dropwise over 6 hours, and stirring was further continued at 120 ° C. for 4 hours.

  Next, after adding 60 parts of deionized water at 90 ° C., 90 parts of an alkali adsorbent (Kyoward 700, Kyowa Chemical Industry Co., Ltd.) was added and stirred at the same temperature for 1 hour. Next, at the same temperature, filter paper No. The Kyoward 700 is removed by filtration using 2 and dehydrated at 120 ° C. under reduced pressure of 1.3 to 2.7 kPa for 1 hour (hereinafter abbreviated as adsorption treatment. In addition, the amount of deionized water used) The amount of the alkali adsorbent used is 1.5 times the amount of deionized water.) To obtain polyether (E3) (sucrose / EO2 mol / PO54 mol / BO4 mol adduct). .

  In a pressure resistant reactor similar to Production Example 1, polyether (E3) (sucrose / EO2 mol / PO54 mol / BO4 mol adduct) 3850 parts (1 mol part), sodium hydroxide 45.4 parts (1.1 mol) Part) and 80 parts of water were added, and 139 parts (1.5 parts by mole) of epichlorohydrin was added dropwise over 6 hours while stirring at 50 ° C. Subsequently, stirring was continued at 60 ° C. for 5 hours, and it was confirmed that the pH of the reaction solution became 7-8. Subsequently, after dehydrating at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.03% by weight), suction filtration using a filter paper was performed, and a glycidyl compound having an epoxy equivalent (g / eq.) Of 3800 { A uniformly transparent liquid} (D3) was obtained.

<Production Example 4>
Into a pressure-resistant reaction vessel similar to Production Example 1, 2170 parts (1 mole part) of polyether (E2) (sucrose / EO2 mole / PO28 mole adduct) and 10 parts of potassium hydroxide were added, and nitrogen substitution was carried out. Dehydration was performed at 120 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, 2100 parts (50 mol parts) of PO was added dropwise over 7 hours at 100 ° C. with reduced pressure, and stirring was further continued for 4 hours at 120 ° C. Next, adsorption treatment (60 parts) was carried out to obtain polyether (E4) (sucrose / EO2 mol / PO78 mol adduct).

  In a pressure-resistant reaction vessel similar to Production Example 1, 5070 parts (1 mole part) of polyether (E4) (sucrose / EO2 mole / PO78 mole adduct), 41.2 parts (1 mole part) of sodium hydroxide and water 200 Then, 130 parts (1.4 parts by mole) of epichlorohydrin was added dropwise over 6 hours while stirring at 50 ° C. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7-8. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.03% by weight), suction filtration using a filter paper was performed, and a glycidyl compound having an epoxy equivalent (g / eq.) Of 5180 { A uniformly transparent liquid} (D4) was obtained.

<Production Example 5>
Into a pressure-resistant reaction vessel similar to Production Example 1, 342 parts (1 mole part) of trehalose {special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.} and 2000 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 580 parts (10 mole parts) of PO was dropped at this temperature over 4 hours, and stirring was continued for 3 hours at the same temperature to react with the remaining PO. It was. Next, DMF was removed under reduced pressure at 120 ° C. to obtain a polyether (E5) (trehalose / PO10 molar adduct).

  In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mol part) of polyether (E5) (trehalose / PO 10 mol adduct), 45.4 parts (1.1 mol parts) of sodium hydroxide and 35 parts of water And 92.5 parts (1 mole part) of epichlorohydrin was added dropwise over 6 hours while stirring at 50 ° C. Next, after stirring at 60 ° C. for 8 hours, 12 parts of lactic acid {50% by weight aqueous solution, “Musashino Lactic Acid 50”, manufactured by Musashino Chemical Laboratory Co., Ltd.} was added and stirred. It was confirmed to be ˜8. Subsequently, after dehydrating at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.04% by weight), suction filtration using filter paper is performed, and a glycidyl compound having an epoxy equivalent (g / eq.) Of 1020 { A uniformly transparent liquid} (D5) was obtained.

<Production Example 6>
In a pressure-resistant reaction vessel similar to Production Example 1, 922 parts (1 mole part) of polyether (E5) (trehalose / PO 10 mole adduct) and 8 parts of potassium hydroxide were added, and nitrogen substitution was performed. And dehydrated under reduced pressure of 0.6 to 1.3 kPa. Next, at 100 ° C. with reduced pressure, a mixture of 406 parts (7 mol parts) of PO and 132 parts (3 mol parts) of EO was added dropwise over 2 hours, then 1740 parts (30 mol parts) of PO were added dropwise over 7 hours, Further, stirring was continued at 120 ° C. for 4 hours. Next, adsorption treatment (40 parts) was carried out to obtain polyether (E6) (trehalose / PO10 mol / EO3 mol · PO7 mol / PO30 mol adduct).

  Polyether (E6) (trehalose / PO10 mol / EO3 mol · PO7 mol / PO30 mol adduct) 3200 parts (1 mol part), sodium hydroxide 41.2 parts (1 Mol part) and 120 parts of water were added, and 120 parts (1.3 parts by mole) of epichlorohydrin were added dropwise over 6 hours while stirring at 50 ° C. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7-8. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.04% by weight), suction filtration using a filter paper was performed to obtain a glycidyl compound having an epoxy equivalent (g / eq.) Of 3300 { A uniformly transparent liquid} (D6) was obtained.

<Production Example 7>
Into a pressure-resistant reaction vessel similar to Production Example 1, 504 parts (1 mole part) of Metetose {special reagent grade, manufactured by Wako Pure Chemical Industries, Ltd.} and 1500 parts of DMF were added, and then nitrogen substitution was performed. Thereafter, the temperature was raised to 100 ° C. while stirring, and then 2320 parts (40 mole parts) of PO was added dropwise at this temperature over 10 hours, and stirring was continued for 3 hours at the same temperature to react with the remaining PO. It was. Next, DMF was removed under reduced pressure at 120 ° C. to obtain a polyether (E7) (meletitol / PO 40 mol adduct).

  A pressure-resistant reaction vessel similar to Production Example 1 was charged with 2824 parts (1 mole part) of polyether (E7) (meletitol / PO 40 mole adduct), 41.2 parts (1 mole part) of sodium hydroxide and 100 parts of water. While stirring at 50 ° C., 111 parts (1.2 mole parts) of epichlorohydrin was added dropwise over 6 hours. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7-8. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.04% by weight), suction filtration using filter paper is performed, and a glycidyl compound having an epoxy equivalent (g / eq.) Of 3030 { A uniformly transparent liquid} (D7) was obtained.

<Production Example 8>
In a pressure-resistant reaction vessel similar to Production Example 1, 2824 parts (1 mole part) of polyether (E7) (meletose / PO 40 mole adduct) and 12 parts of potassium hydroxide were added, and nitrogen substitution was performed. And dehydrated under reduced pressure of 0.6 to 1.3 kPa. Next, at 100 ° C. under reduced pressure, 220 parts (5 mol parts) of EO was added dropwise over 3 hours, 1450 parts (25 mol parts) of PO was further added dropwise over 7 hours, and stirring was further continued at 120 ° C. for 4 hours. It was. Next, adsorption treatment (60 parts) was carried out to obtain a polyether (E8) (meletose / PO 40 mol / EO 5 mol / PO 25 mol adduct).

  Polyether (E8) (Meletitose / PO 40 mol / EO 5 mol / PO 25 mol adduct) 4494 parts (1 mol part), sodium hydroxide 41.2 parts (1 mol part) in a pressure-resistant reaction vessel similar to Production Example 1 Then, 230 parts of water was charged, and 130 parts (1.4 parts by mole) of epichlorohydrin was added dropwise over 6 hours while stirring at 50 ° C. Subsequently, stirring was continued at 60 ° C. for 6 hours, and it was confirmed that the pH of the reaction solution became 7-8. Next, after dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa (water content: 0.04% by weight), suction filtration with filter paper was performed to obtain a glycidyl compound having an epoxy equivalent (g / eq.) 4620 of { A uniformly transparent liquid} (D8) was obtained.

<Production Example 9>
In a pressure resistant reaction vessel similar to Production Example 1, polyoxypropylene (7 mol) glycol diglycidyl ether {Gliciere PP-300P, Sanyo Chemical Industries, Ltd.} 580 parts (1 mol part), propylene glycol / PO33.5 Mole adduct {Sannicks diol PP-2000, Sanyo Chemical Industries, Ltd.} 4000 parts (2 mole parts) and 10 parts of potassium hydroxide were added to perform nitrogen substitution, and further 0.6 to It dehydrated under a reduced pressure of 1.3 kPa. Subsequently, stirring was continued for 10 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group, thereby obtaining a compound (Be1).

<Production Example 10>
In a pressure resistant reaction vessel similar to Production Example 1, polyoxypropylene (7 mol) glycol diglycidyl ether {Gliciere PP-300P, Sanyo Chemical Industries, Ltd.} 1160 parts (2 mol parts), propylene glycol / PO12.5 Mole / EO2 mole adduct {Sanixdiol PL-910, manufactured by Sanyo Chemical Industries, Ltd.} 2700 parts (3 mole parts) and 9 parts of potassium hydroxide were added to perform nitrogen substitution. It dehydrated under reduced pressure of 6 to 1.3 kPa. Subsequently, stirring was continued for 8 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed to obtain a compound (Be2).

<Production Example 11>
In the same pressure resistant reaction vessel as in Production Example 1, polyoxypropylene (7 mol) glycol diglycidyl ether {Gliciere PP-300P, Sanyo Chemical Industries, Ltd.} 1740 parts (3 mol parts), propylene glycol / PO12.5 Mole / EO 2 mol adduct {Sanixdiol PL-910, manufactured by Sanyo Chemical Industries, Ltd.} 3600 parts (4 mole parts) and 12 parts of potassium hydroxide were added to perform nitrogen substitution. It dehydrated under reduced pressure of 6 to 1.3 kPa. Subsequently, stirring was continued for 8 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group, thereby obtaining a compound (Be3).

<Production Example 12>
In a pressure resistant reaction vessel similar to Production Example 1, polyoxypropylene (7 mol) glycol diglycidyl ether {Gliciere PP-300P, Sanyo Chemical Industries, Ltd.} 1160 parts (2 mol parts), propylene glycol / PO33.5 Mole adduct {Sanixdiol PP-2000, manufactured by Sanyo Chemical Industries, Ltd.} 6000 parts (3 mole parts) and 15 parts of potassium hydroxide were added to perform nitrogen substitution, and further at 80 ° C, 0.6 to It dehydrated under a reduced pressure of 1.3 kPa. Subsequently, stirring was continued for 10 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group, and thus a compound (Be4) was obtained.

<Production Example 13>
In a pressure resistant reactor similar to Production Example 1, polyoxypropylene (3 mol) glycol diglycidyl ether {Epiol PP-200, manufactured by NOF Corporation} 310 parts (1 mol part), propylene glycol / PO 33.5 mol Addition {Sanix Diol PP-2000, Sanyo Chemical Industries, Ltd.} 4000 parts (2 mole parts) and 10 parts of potassium hydroxide were added to perform nitrogen substitution, and further 0.6-1 at 80 ° C. It dehydrated under reduced pressure of 3 kPa. Subsequently, stirring was continued for 10 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group, thereby obtaining a compound (Be5).

<Production Example 14>
In a pressure-resistant reaction vessel similar to Production Example 1, polyoxypropylene (3 mol) glycol diglycidyl ether {Epiol PP-200, manufactured by NOF Corporation} 620 parts (2 mol parts), propylene glycol / PO 33.5 mol Addition {Sanix Diol PP-2000, Sanyo Chemical Industries, Ltd.} 6000 parts (3 mole parts) and 14 parts of potassium hydroxide were added to carry out nitrogen substitution, and further 0.6-1 at 80 ° C. It dehydrated under reduced pressure of 3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed to obtain a compound (Be6).

<Production Example 15>
In a pressure-resistant reaction vessel similar to Production Example 1, polyoxypropylene (3 mol) glycol diglycidyl ether {Epiol PP-200, manufactured by NOF Corporation} 930 parts (3 mol parts), propylene glycol / PO 12.5 mol / EO 2 mol adduct {Sanix Diol PL-910, Sanyo Chemical Industries, Ltd.} 3600 parts (4 mol parts) and 15 parts of potassium hydroxide were added to perform nitrogen substitution. It dehydrated under reduced pressure of 6-1.3 kPa. Subsequently, stirring was continued for 8 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed to obtain a compound (Be7).

<Production Example 16>
In a pressure-resistant reaction vessel similar to Production Example 1, polyoxypropylene (3 mol) glycol diglycidyl ether {Epiol PP-200, manufactured by NOF Corporation} 620 parts (2 mol parts), propylene glycol / PO 12.5 mol / EO 2 mol adduct {Sanix Diol PL-910, Sanyo Chemical Industries, Ltd.} 2700 parts (3 mol parts) and 10 parts of potassium hydroxide were added to carry out nitrogen substitution. It dehydrated under reduced pressure of 6-1.3 kPa. Subsequently, stirring was continued for 7 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed to obtain a compound (Be8).

<Example 1>
In a pressure resistant reactor similar to Production Example 1, 4580 parts (1 mole part) of the compound (Be1) obtained in Production Example 9 and 10360 parts (2 mole parts) of the glycidyl compound (D4) obtained in Production Example 4 were added. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (150 parts) was performed to obtain the surfactant (S1) of the present invention.

<Example 2>
In a pressure resistant reactor similar to Production Example 1, 3860 parts (1 mol) of the compound (Be2) obtained in Production Example 10 and 8640 parts (4 mol) of the glycidyl compound (D2) obtained in Production Example 2 were added. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (120 parts) was performed to obtain the surfactant (S2) of the present invention.

<Example 3>
In a pressure resistant reactor similar to Production Example 1, 5340 parts (1 mole part) of the compound (Be3) obtained in Production Example 11 and 8160 parts (8 mole parts) of the glycidyl compound (D5) obtained in Production Example 5 were added. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (120 parts) was performed to obtain a surfactant (S3) of the present invention.

<Example 4>
In a pressure resistant reactor similar to Production Example 1, 7160 parts (1 mole part) of the compound (Be4) obtained in Production Example 12 and 9240 parts (2 mole parts) of the glycidyl compound (D8) obtained in Production Example 8 were used. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 13 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (180 parts) was performed to obtain a surfactant (S4) of the present invention.

<Example 5>
In a pressure resistant reactor similar to Production Example 1, 4310 parts (1 mole part) of the compound (Be5) obtained in Production Example 13 and 11400 parts (3 mole parts) of the glycidyl compound (D3) obtained in Production Example 3 were used. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (200 parts) was performed to obtain a surfactant (S5) of the present invention.

<Example 6>
In a pressure-resistant reaction vessel similar to Production Example 1, 6620 parts (1 mol) of the compound (Be6) obtained in Production Example 14 and 13200 parts (4 mol) of the glycidyl compound (D6) obtained in Production Example 6 were used. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 14 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group. Next, adsorption treatment (180 parts) was performed to obtain a surfactant (S6) of the present invention.

<Example 7>
In a pressure resistant reactor similar to Production Example 1, 4530 parts (1 mol) of the compound (Be7) obtained in Production Example 15 and 9720 parts (6 mol) of the glycidyl compound (D1) obtained in Production Example 1 were added. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 12 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (140 parts) was performed to obtain a surfactant (S7) of the present invention.

<Example 8>
In a pressure-resistant reaction vessel similar to Production Example 1, 3320 parts (1 mole part) of the compound (Be8) obtained in Production Example 16 and 15150 parts (5 mole parts) of the glycidyl compound (D7) obtained in Production Example 7 were used. Then, nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 14 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group. Next, adsorption treatment (180 parts) was performed to obtain a surfactant (S8) of the present invention.

<Example 9>
In a pressure-resistant reaction vessel similar to Production Example 1, 4580 parts (1 mol part) of the compound (Be1) obtained in Production Example 9 and 300 parts (2 mol parts) of butyl glycidyl ether {Epiol B, manufactured by NOF Corporation) And nitrogen substitution was performed, and dehydration was performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 10 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed.

  Next, 10360 parts (2 mole parts) of the glycidyl compound (D4) obtained in Production Example 4 was charged, nitrogen substitution was performed, and dehydration was further performed at 80 ° C. under a reduced pressure of 0.6 to 1.3 kPa. Stirring was continued for 13 hours at 120 ° C., and disappearance of the epoxy group was confirmed. Next, adsorption treatment (140 parts) was performed to obtain a surfactant (S9) of the present invention.

<Example 10>
In a pressure-resistant reaction vessel similar to Production Example 1, 3860 parts (1 mol) of the compound (Be2) obtained in Production Example 10 and 399 parts of 2-ethylhexyl glycidyl ether {Epiol EH-N, manufactured by NOF Corporation} (2.1 mol parts) was charged and nitrogen substitution was carried out, followed by dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 10 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, 8640 parts (4 mole parts) of the glycidyl compound (D2) obtained in Production Example 2 was charged and nitrogen substitution was performed. Further, dehydration was performed at 80 ° C. under a reduced pressure of 0.6 to 1.3 kPa, and the reduced pressure was reduced. Stirring was continued for 13 hours at 120 ° C., and disappearance of the epoxy group was confirmed. Next, adsorption treatment (100 parts) was performed to obtain the surfactant (S10) of the present invention.

<Example 11>
In a pressure-resistant reaction vessel similar to Production Example 1, 4310 parts (1 mol) of the compound (Be5) obtained in Production Example 13 and 315 parts of butyl glycidyl ether {Epiol B, manufactured by NOF Corporation} (2.1 Mole part) was charged and nitrogen substitution was carried out, followed by dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 8 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Subsequently, 11400 parts (3 mol parts) of the glycidyl compound (D3) obtained in Production Example 3 was charged, nitrogen substitution was performed, and dehydration was further performed at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 13 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, adsorption treatment (140 parts) was performed to obtain a surfactant (S11) of the present invention.

<Example 12>
In a pressure-resistant reaction vessel similar to Production Example 1, 6620 parts (1 mole part) of the compound (Be6) obtained in Production Example 14 and 2-ethylhexyl glycidyl ether {Epiol EH-N, manufactured by NOF Corporation} 380 parts (2 mol parts) was charged and nitrogen substitution was carried out, followed by dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 8 hours at 120 ° C. under reduced pressure, and disappearance of the epoxy group was confirmed. Next, 13200 parts (4 mol parts) of the glycidyl compound (D6) obtained in Production Example 6 was charged, followed by nitrogen substitution, and dehydration at 80 ° C. under reduced pressure of 0.6 to 1.3 kPa. Subsequently, stirring was continued for 14 hours at 120 ° C. under reduced pressure to confirm the disappearance of the epoxy group. Next, adsorption treatment (160 parts) was performed to obtain a surfactant (S12) of the present invention.

<Comparative Example 1>
SN Dispersant 5044 {manufactured by Sannopco, polycarboxylic acid sodium salt type (polymer concentration: 43%)} was used as a comparative surfactant (H1).

<Comparative example 2>
SN Dispersant 5047 (manufactured by San Nopco, polycarboxylic acid ammonium salt type (polymer concentration 33% product)) was used as a comparative surfactant (H2).

<Comparative Example 3>
Benzoin n-propyl ether {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} was used as a comparative surfactant (H3).

<Comparative example 4>
Benzoin iso-butyl ether {reagent special grade, manufactured by Wako Pure Chemical Industries, Ltd.} was used as a comparative surfactant (H4).

<Comparative Example 5>
In a pressure resistant reactor similar to Production Example 1, 2054 parts (1 mole part) of the polyether (E2) (sucrose / EO2 mole / PO28 mole adduct) obtained in Production Example 2 was charged at 0.6 at 120 ° C. It dehydrated under a reduced pressure of ˜1.3 kPa. Next, at 70 ° C., 148.7 parts (0.67 mol parts) of isophorone diisocyanate was charged, and nitrogen substitution was repeated three times. Thereafter, the temperature was raised to 110 ° C. over 1 hour while stirring, and stirring was continued for 4 hours at the same temperature. After confirming the disappearance of the isocyanate group, a polyoxyalkylene compound (YH1) was obtained. The polyoxyalkylene compound (YH1) was used as a comparative surfactant (H5) as it was.

Using the surfactants obtained in Examples and Comparative Examples, A normally dry water-based paint was prepared, and gloss, toning property, antifoaming property and water resistance were evaluated, and the results are shown in Table 5. Similarly, 2. A thermosetting water-based paint was prepared, and the film thickness limit value, smoothness and sharpness were evaluated. The results are shown in Table 7. Furthermore, 3. The paint for exterior building walls was prepared, the pollution reduction property was evaluated, and the results are shown in Table 9.
In addition, about the surfactant of the comparative example 1 or 2, it was converted and used so that the polymer weight might become predetermined amount in consideration of polymer concentration.

1. Evaluation with a normal dry water-based paint <Preparation of pigment dispersion> Conforms to JISK5600-2-5: 1999 (1) Preparation of pigment dispersion Excel auto homogenizer equipped with impeller blades (Model ED, manufactured by Nippon Seiki Co., Ltd.) , The same shall apply hereinafter), and in the usage amount shown in Table 4 (upper column, pigment dispersion), a mixture of ion exchange water, ethylene glycol, surfactant for evaluation, SN wet, SN deformer and nopcoside (“Taipeke” is a registered trademark of Ishihara Sangyo Co., Ltd.) was added with stirring, and the pigment was dispersed until uniform to obtain a pigment dispersion.

  In addition, it was confirmed by the crush gauge method (based on JIS K5600-2-5: 1999) that the pigment dispersion had no particles of 5 microns or more. The pigment dispersion was defoamed with a defoamer {Model AR-250, manufactured by Awatori Nertaro Co., Ltd.] for 3 minutes, and then the viscosity was measured with a Brookfield viscometer (25 ° C, 60 rpm). The results are shown in Table 5 (unit: mPa · s).

<Preparation of paint and test paint pieces> JISK 5600-2-5: In accordance with 1999 (2) Preparation of evaluation paint The obtained pigment dispersion was used in the amounts shown in Table 4 (lower column, red down). , Primal, texanol, SN deformer, SN thickener and unilant were added, and a red down process was performed with an Excel auto homogenizer equipped with impeller type blades to obtain a paint for evaluation.
In addition, it was confirmed that the coating material for evaluation was free of particles of 5 microns or more by the crush gauge method.

* 1 Wetting agent manufactured by San Nopco Co., Ltd. * 2 Antifoaming agent manufactured by San Nopco Co., Ltd. * 3 Preservative manufactured by Kumiai Chemical Co., Ltd., “Biotac” is a registered trademark of the company.
* 4 Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. and “Taipeke” are registered trademarks of the same company.
* 5 Acrylic-styrene resin “Primal” manufactured by Nippon Acrylic Co., Ltd. is a registered trademark of ROHM End Hearthcompany.
* 6 Eastman Chemical's membrane modifier, “Texanol” is a registered trademark of Yoshimura Oil Chemical Co., Ltd.
* 7 Thickener manufactured by San Nopco * 8 Color pigment (black) and "unirant" manufactured by Yokohama Chemical Co., Ltd. are registered trademarks of the company.

<Preparation of test paint pieces>
Using the coating material for evaluation, the coating was performed under the following coating conditions and tested for gloss, toning, defoaming and water resistance.

[Coating conditions]
Coating method: Spray painting with spray gun {Wider W-88 cup gun (Iwata Painting Co., Ltd.)} and brush painting with brush (Otsuka Brush Manufacturing Co., Ltd., # 70 for water-based paint) Drying method: Normal drying (temperature) : 25 ° C, humidity: 40% RH)

[Glossy]
Polyester film (length: 150 mm, width: 150 mm, thickness: 0.10 mm, Toray Mirror L-100T60, Toray Industries, Inc., manufactured by diluting an evaluation paint (water-based paint) to 85 KU (25 ° C.) and degreased with acetone ) With a spray gun (wet film thickness: approx. 0.2 mm), air-dried, dried for 7 days, and gloss meter (Nippon Denshoku Industries Co., Ltd., VGS-300A) at an incident angle of 60 °. Gloss (gross) was measured at six locations, the average value was calculated, and this was defined as gloss.

[Toning]
The paint for evaluation (water-based paint) is diluted to 85 KU (25 ° C) with ion-exchanged water and spray coated on a stainless steel plate (length: 200 mm, width: 120 mm, thickness: 1.2 mm) degreased with acetone. (Wet film thickness: approx. 0.2mm) Immediately after that, paint half of it, dry it for 7 days in normal drying, and then use SPECTRO COLOR METERMODEL PF-10 made by Nippon Denshoku Industries Co., Ltd. The color difference (ΔE value) between the spray-coated part and the brush-coated part was measured, and the difference between the two was calculated by the following formula to obtain the toning property. The smaller this value, the better the toning property. | ΔE | means the absolute value of ΔE.
(Toning) = | △ E (Spray) − △ E (Bake) |

[Defoaming]
A stainless steel plate degreased with acetone immediately after the evaluation paint (water-based paint) was diluted to 85 KU (25 ° C) with ion-exchanged water, stirred for 2 minutes at 500 rpm with an Excel auto homogenizer equipped with impeller blades (Vertical: 200 mm, Horizontal: 120 mm, Thickness: 1.2 mm) Brushed (wet film thickness: about 0.2 mm), dried at 25 ° C. for 1 day, and then a bubble mark within a 10 cm × 10 cm area in the center portion (A diameter of 1.0 mm or more) was counted to make it defoaming.

[water resistant]
Polyester film (Toler mirror L-100T60, length: 150 mm, width: 150 mm, thickness: 0.10 mm) obtained by diluting an evaluation paint (water-based paint) to 85 KU (25 ° C.) with ion-exchanged water and degreased with acetone ) With a spray gun (wet film thickness: about 0.2 mm), dried for 7 days under normal drying, and then immersed in ion-exchanged water (20 ° C.) for 14 days. Subsequently, it was pulled up from water and counted for blister (water bulge) traces (diameter of 1.0 mm or more) in a 10 cm × 10 cm area in the center portion to make it water resistant.

  Note that the surfactants of Comparative Examples 3 and 4 are generally used as anti-cracking agents, and even though the above evaluation was made, it was expected to be significantly inferior to other surfactants. (Noted as “-” in the table above).

  From Table 5, the surfactants of the present invention (Examples 1 to 12) have a low pigment dispersion, high glossiness, and high toning properties due to improved pigment dispersibility compared to comparative surfactants. It was confirmed that the antifoaming property and water resistance were good.

2. Evaluation by thermosetting water-based paint <Preparation of paint and test piece> According to JISK5600-2-5: 1999 (1) Preparation of thermosetting water-based paint Impeller using raw materials and amounts used shown in Table 6 A thermosetting water-based paint was obtained with an Excel auto homogenizer equipped with a mold blade. In addition, it was confirmed by the crush gauge method that this coating material has no particles of 5 microns or more.

* 1 Water-soluble acrylic resin “Boncoat” manufactured by Dainippon Ink and Chemicals, Inc. is a registered trademark of the company.
* 2 Water-soluble melamine resin, “Cymel”, manufactured by Mitsui Cyanamid Co., Ltd. is a registered trademark of Cytec Technology Corporation.
* 3 Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. and “Taipeke” are registered trademarks of the same company.
* 4 “Nopco”, a defoaming agent manufactured by San Nopco Co., Ltd., is a registered trademark of Cognis, Deutschland, Geselsyaft, Mito, Besyulenktel, Haftung und, Company, Comandate Geselsyaft.
* 5 Thickener manufactured by San Nopco Co., Ltd.

(2) Preparation of test piece for test The obtained thermosetting water-based paint was subjected to Ford Cup No. 1 with ion-exchanged water. 4 (conforming to JIS K-5600-2-2) is diluted to 20 seconds (25 ° C.), coated under the following coating conditions, and measured for the critical film thickness, smoothness and sharpness. Went.

[Coating conditions]
Object to be coated: Tin plate degreased with acetone (length: 120 mm, width: 80 mm, thickness: 0.06 mm)
Coating method: Using spray gun {Wider W-88 cup gun (Iwata Painting Co., Ltd.)}, film thickness gradient coating baking condition: set in booth for 10 minutes after coating, then baked at 160 ° C for 20 minutes

[Waki limit film thickness value]
If a coating film having a difference in film thickness is formed by applying an inclined coating under the above [Coating conditions], and then baking and drying is performed, it becomes easier to generate a crack in a thicker part than in a thinner part. The film thickness of the portion where the coating film abnormality starts to occur (the limit film thickness value) was measured with an electromagnetic fine film thickness meter {Owell Co., Ltd., SEM-100 type} (unit: μm). The higher the evaluation value, the higher the ability to prevent armpits.

[Smoothness]
Using the test piece for which the armor limit film thickness value was evaluated, the smoothness of the surface of the coating film thinner than the armor limit film thickness value was evaluated with the naked eye. The evaluation was made smooth by counting the number of repellencies and craters (each having a diameter of 1.0 mm or more) on the surface of the coating film with a width of 20 mm and a length of 100 mm in a portion thinner than the critical film thickness value.

[Vividness]
Using a test piece that has been evaluated for the thickness of the armpit limit film, measure the gloss (gross) at an incident angle of 20 ° in the area thinner than the armature limit thickness with the gloss meter (described above), and calculate the average value. This was calculated and defined as clearness. The higher this value, the better the clarity.

  Note that the surfactants of Comparative Examples 1 and 2 are generally used as dispersants, and even though the above evaluation was performed, it was expected to be significantly inferior to other surfactants. No (denoted with “-” in the table above).

  From Table 7, it was recognized that the surfactants of the present invention (Examples 1 to 12) are superior in anti-skid properties as compared with the surfactant for comparison.

3. Evaluation by water-based paint for building exterior walls The relationship between contamination resistance and the contact angle of the paint film with water is well known. The smaller the contact angle, the more water droplets from the rain carry away dirt on the surface. Is said to be good. In addition, it has been reported that a paint film that maintains a water contact angle of 50 degrees or less even after the accelerated durability test is unlikely to generate dirt [Nobuhiro Kenmochi: Surface properties and contamination of exterior wall paints, paint engineering, 28, [4] 147 (1993)] [Toshikazu Nakaya: Technological development of antifouling paint for buildings, JETI, 42, [5] 8 (1994)]. Therefore, the contamination resistance and its sustainability index were evaluated based on the contact angle with water, and an outdoor exposure test was conducted, and the stain on the coating film was evaluated by measuring the whiteness.

<Adjustment of paint and test paint pieces> Conforms to JISK 5600-2-5: 1999 (1) Standard paint Excel auto homogenizer with impeller blades in the grinding process and let-down process with the raw material composition shown in Table 8 ( Nippon Seiki Co., Ltd. model ED) was used as the paint. The obtained paint was confirmed to be free of particles of 5 microns or more by the crush gauge method (conforming to JISK5600-2-5: 1999), and this aqueous emulsion paint was used as a standard paint.

1: Dispersant manufactured by San Nopco Co., Ltd. 2: Thickener manufactured by San Nopco Co., Ltd. 3: Defoamer manufactured by San Nopco Co., Ltd. 4: Titanium dioxide manufactured by Ishihara Sangyo Co., Ltd. 5: BASF Japan Co., Ltd. Acrylic emulsion 6 manufactured by: San Nopco Co., Ltd. Preservative 7: Film forming regulator 8 manufactured by Eastman Chemical Co. 8: Thickener manufactured by San Nopco Co., Ltd.

(2) Paint for evaluation 1.5 parts of the surfactant obtained in Examples or Comparative Examples was added to 98.5 parts of the standard paint, and an Excel auto homogenizer (impeller type blade) was used, and room temperature (20-30 ° C). ) At 2000 rpm for 3 minutes to prepare an evaluation paint.
A blank paint was prepared in the same manner as described above except that 1.5 parts of the surfactant was changed to 1.5 parts of deionized water.

(3) Test piece Polyester film degreased with acetone {trade name: Lumirror 75-S10, manufactured by Panac Co., Ltd., with a thickness of 0.1 mm cut to 10 × 8 cm and used. }, The coating thickness when wet was set to 300 μm, and after applying the evaluation paint or the blank paint, the control room (hereinafter abbreviated as the temperature control room) adjusted to 25 ° C. and 60% relative humidity for 7 days. It dried and it was set as the test coating piece.

<Performance evaluation>
1. Contact angle with water Take a 1 × 5 cm test piece from the test piece, drop 0.005 ± 0.001 mL of deionized water onto the surface of the coating, and contact the water drop after 1 minute. Was used as the initial contact angle. The contact angle was measured in a temperature control room using a contact angle meter CAA manufactured by Kyowa Chemical.

2. Contact angle after immersion treatment (sustainability promotion test)
A test piece having a size of 1 × 5 cm was taken from the test piece and immersed in deionized water at 25 ° C. for 14 days. Next, after drying in a temperature-controlled room (25 ° C., 60% relative humidity) for 2 days, the contact angle with water was measured in the same manner as described above, and this was defined as the contact angle after the immersion treatment.

3. After taking a test piece having a size of 5 × 5 cm from a paint piece for water resistance test and immersing it in deionized water at 25 ° C. for 14 days, it is lifted from the water, and the number of blisters generated on the surface of the coating film and The size and the like were determined according to the following criteria, and this was evaluated as water resistance.

A: No blister.
○: There are some blisters having a diameter of about 0.1 mm.
Δ: Some blisters with a diameter of 0.5 mm or more.
X: There are many blisters with a diameter of 0.5 mm or more.

4). Difference in whiteness (-△ L value, outdoor dripping test)
Test plate (prepared by spray-coating each evaluation paint with a wet film thickness of 1.5 mm on a 10 x 30 cm stainless steel plate and drying it) 18 m above ground in Tokai City, Aichi Prefecture (6 floor building rooftop) ) Outdoor raindrop test stand (made of stainless steel, 80 cm long, 110 cm wide, with a 5 mm deep rain collecting groove at a 5 mm interval (with a 30-degree inclination relative to the horizontal plane)) And with the painted surface facing true north, rainwater from the rain collecting groove on the roof flows along the painted surface, and is about 11 months from the beginning of August 2010 to the end of July 2011. Tested for a while. Then, after rubbing off dust, dirt, etc. adhering to the surface of the test coating piece with a wet cotton cloth, the whiteness (L2) was measured. Next, a value obtained by subtracting the whiteness (L1) of the test coating piece before exposure from the whiteness (L2) was calculated, and this value was defined as the difference in whiteness (absolute value: -ΔL). It shows that pollution resistance is so favorable that-(DELTA) L is small. As a whiteness measurement tester, SPECTRO COLOR METERMODEL PF-10 manufactured by Nippon Denshoku Industries Co., Ltd. was used.

  The surfactants of Comparative Examples 1 to 4 are generally used as dispersants or anti-waxing agents, and even when evaluated as described above, it was expected to be significantly inferior to other surfactants. , Not evaluated (indicated by "-" in the table above).

  From Table 9, it was recognized that the surfactants of the present invention (Examples 1 to 12) were superior in contamination reduction and water resistance compared to the surfactants for comparison.

  The surfactant of the present invention can be applied as various paints and ink additives. In particular, the present invention can be applied to water-based paints and non-water-based paints. Examples of the aqueous emulsion paint include acrylic, vinyl acetate, styrene, halogenated olefin, urethane, acryl-silicon, and fluorine paints. The surfactant of the present invention is extremely useful for water-based ordinary dry paints and water-based thermosetting paints.

Claims (10)

A surfactant comprising the polyoxyalkylene compound (Y) represented by either the general formula (1) or (2).

However, D is a hydrogen atom or the organic group represented by General formula (3), L is the residue remove | excluding the hydrogen atom from two hydroxyl groups of C20-200 polyoxyalkylene glycol, M is C4. residue obtained by removing from the two hydrogen atoms of hydroxyl groups glycols ~ 44, U is 2-hydroxypropylene group _{{-CH 2 -CH (OH) -CH} 2 -} or hydroxymethyl ethylene group _{-CH 2 -CH A residue obtained by removing a hydrogen atom from a hydroxyl group of (CH ₂ OH) —}, G is a residue obtained by removing a hydrogen atom from a hydroxyl group of a monool having 3 to 18 carbon atoms, p represents an integer of 1 to 3, The proportion of hydrogen atoms in D of 0 to 0 mol% per molecule.

_{-X (-OA) n -Q - {} (AO-) n H} t-1 (3)

X is a 2-hydroxypropylene group or hydroxymethylethylene group, Q is a residue obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide, AO and OA are oxyoxygen having 2 to 4 carbon atoms An alkylene group, H is a hydrogen atom, n is an integer of 2 to 40, t is an integer of 2 to 4, the total number of AO and OA is 10 to 80 per organic group, and D, L, M , U, G, Q, (OA) n, (AO) n, n, p, t may be the same or different. The surfactant according to claim 1, wherein the residue (Q) obtained by removing a hydrogen atom from t primary hydroxyl groups of a non-reducing di- or trisaccharide is a sucrose residue. A coating composition comprising the paint and the surfactant according to claim 1, wherein the surfactant is contained in an amount of 0.1 to 5% by weight based on the weight of the paint. The coating composition according to claim 3, wherein the paint is an architectural water-based paint or an aqueous heat-curing paint. The surfactant according to claim 1 or 2, wherein the surfactant is used as a surfactant for paints. The surfactant according to claim 1 or 2, wherein the surfactant is used as an anti-waxing agent for water-based paints. The surfactant according to claim 1 or 2, wherein the surfactant is used as a dispersant for water-based paints. The surfactant according to claim 1 or 2, wherein the surfactant is used as a paint film contamination reducing agent for water-based paints. A method for producing the surfactant according to claim 1, comprising:
Step (1) for obtaining a compound (a12) from a chemical reaction (1) of 1 mol part of a non-reducing di- or trisaccharide (a1) and 10 to 80 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. And a method (1) comprising a step (4) of obtaining a polyoxyalkylene compound (Y1) from a chemical reaction (4) between 1 mol part of the compound (a45) and 2-8 mol parts of the glycidyl compound (a123). ;; or

Step (1) for obtaining a compound (a12) from a chemical reaction (1) of 1 mol part of a non-reducing di- or trisaccharide (a1) and 10 to 80 mol parts of an alkylene oxide (a2) having 2 to 4 carbon atoms ;
Step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3);
A compound (a45) is obtained from a chemical reaction (3) of 1 mol part of a diglycidyl ether (a4) having 10 to 50 carbon atoms and 1.33 to 2 mol parts of a polyoxyalkylene glycol (a5) having 20 to 200 carbon atoms. Step (3);
Step (5) of obtaining Compound (a456) from Chemical Reaction (5) of 1 mol part of Compound (a45) and 2 to 2.2 mol part of monoglycidyl ether (a6) having 6 to 21 carbon atoms; and Compound ( a456) A method (2) comprising a step (6) of obtaining a polyoxyalkylene compound (Y2) from a chemical reaction (6) of 1 mol part and a glycidyl compound (a123) 2-8 mol part
The manufacturing method characterized by comprising. In the step (2) of obtaining a glycidyl compound (a123) from a chemical reaction (2) between 1 mol part of the compound (a12) and 1 to 1.5 mol parts of epihalohydrin (a3),
Performing chemical reaction (2) in the presence of a base;
The production method according to claim 9, wherein the reaction is started by adjusting the content of water to 2 to 5% by weight based on the weight of the compound (a12), epihalohydrin (a3) and base.