JP2009001690A - Water-based paint composition - Google Patents

Abstract

An aqueous coating composition having excellent pigment storage stability and excellent rust prevention properties for buildings and steel structures is provided.
An aqueous coating composition containing a multi-chain polyhydrophilic group-type compound having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment is used. It is preferable that at least one of the multi-chain polyhydrophilic group type compounds has an amino acid residue in the molecule. At least one of the multi-chain polyhydrophilic group type compounds can be represented by the general formula Qn-X, where Q is a substituent having two or more acyl groups and hydrophilic groups in the molecule, and X is A spacer which is a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having a molecular weight of 1 million or less is shown.
[Selection figure] None

Description

  The present invention relates to a water-based coating composition containing a multi-chain polyhydrophilic group-type compound having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment. The present invention relates to a water-based coating composition excellent in rust prevention of steel products in the fields of architecture, ships, and automobiles.

In recent years, many of water-based paint compositions contain pigments and water-based synthetic resins, and these pigments are often used in a state of being dispersed in a medium such as water, but the pigment is dispersed in water. For this reason, surface active agents and dispersants are added and pigment surfaces are modified.
In addition to Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5, many other water-based coating compositions are known from the viewpoint of using a dispersant. Patent Documents 1 and 5 both relate to the dispersion stability of a fine cellulose aqueous coating composition, and are not described in detail regarding the stability of the pigment, and have a high specific gravity as in the present application. There is no disclosure about the dispersion stability of the pigment. Patent Document 2, Patent Document 3, and Patent Document 4 are intended for stabilization of latex fine particles of a cellulose composite, and are mainly used in the paper coating field. There is no description about the dispersion stability of the pigment.

JP 2001-247812 A JP-A-5-279576 JP-A-8-151504 JP-A-5-132644 JP-A-5-163445

  The present invention relates to a water-based coating composition containing a multi-chain polyhydrophilic group-type compound having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment. The present invention relates to an excellent aqueous coating composition.

As a result of intensive studies to solve the above problems, the present inventor contains a multi-chain polyhydrophilic group type compound having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment. By using the water-based paint composition, it has been found that it has excellent pigment storage stability and can be used in a wide range of fields such as architecture, ships and automobiles.
That is, the present invention is as follows.
1. An aqueous coating composition comprising one or more multi-chain polyhydrophilic group-type compounds each having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment.
2. At least one of the multi-chain polyhydrophilic group type compounds has an amino acid residue in the molecule. The aqueous coating composition as described.
3. At least one of the multi-chain polyhydrophilic group-type compounds is a compound represented by the following general formula (1): Or 2. The water-based paint composition described in 1.

（上記一般式（１）において、Ｘはｍ個の官能基、およびそれ以外の置換基を有していてもよい分子量１００万以下の直鎖または分枝鎖または環状鎖または芳香族炭化水素鎖であるスペーサーを示す。Ｘに結合しているｎ（ｍ≧ｎ）個のＱは、下記一般式（２）で表される置換基であり、それぞれ互いに同一でも異なっていてもよい。下記一般式（２）において、ＺはＸの有する官能基に由来する結合部であり、Ｒ^１ＣＯは炭素原子数２〜２０の飽和または不飽和の脂肪酸から誘導される長鎖アシル基を示し、Ｒ^２は水素であるか、またはヒドロキシル基またはカルボキシル基が置換していてもよい炭素原子数１〜３の低級アルキル基を示し、Ｙはカルボキシル基、スルホン酸基、硫酸エステル基、リン酸エステル基またはそれらの塩の内のいずれかを示す。ｊ、ｋはそれぞれ独立に０，１，２のいずれかであり、かつｊ、ｋは同時に０ではない。ｎは２〜２０の整数を示す。また、ｍはｍ≧ｎである整数を示す。）

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. The n (m ≧ n) Qs bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other. In Formula (2), Z is a bond derived from a functional group of X, R ¹ CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, R ² represents hydrogen, or a lower alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate group, or a phosphate group. Or of those salts J and k are each independently 0, 1, or 2 and j and k are not 0 simultaneously, n is an integer of 2 to 20, and m is m ≧ n Indicates an integer.)

  The water-based coating composition of the present invention contains one or more multi-chain, multi-hydrophilic group compounds each having two or more acyl groups and hydrophilic groups in the molecule, and has excellent pigment storage stability, rust prevention, It has excellent characteristics of anticorrosion and weather resistance.

Hereinafter, the present invention will be specifically described focusing on its preferred form.
The aqueous coating composition referred to in the present invention comprises an aqueous synthetic resin, a pigment, and one or more of a multi-chain polyhydrophilic group type compound having two or more long-chain hydrophobic groups and hydrophilic groups in the molecule. It is a composition.
In the water-based coating composition of the present invention, as the multi-chain polyhydrophilic group-type compound, each of the long-chain hydrophobic groups is independently a saturated or unsaturated linear, branched, or cyclic chain having 8 to 20 carbon atoms. It is sufficient if it has a hydrophobic group consisting of, and has this structure, and may be a compound known so far. As the hydrophilic group, each independently a carboxyl group, a sulfonic acid group, a sulfuric acid residue, a phosphoric acid residue or a salt thereof, an oxyalkylene group, a polyethylene glycol group, or the like, an amino group, a quaternary ammonium group, or pyridinium. Group, sulfonium group or a salt thereof.

For example, the long-chain hydrophobic group of the multi-chain poly-hydrophilic group type compound includes, for example, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl. , N-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, etc. and their branched isomers, and corresponding one, two or three non-residues Examples include unsaturated residues having a saturated portion.
Further, the long-chain hydrophobic group of the multi-chain polyhydrophilic group type compound is a long-chain acyl group derived from a saturated or unsaturated fatty acid having 8 to 20 carbon atoms, such as caprylic acid, pelargonic acid, capric acid. , Straight chain fatty acids such as undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachidic acid; 2-butyl-5-methylpentanoic acid, 2-isobutyl -5-methylpentanoic acid, dimethyloctanoic acid, dimethylnonanoic acid, 2-butyl-5-methylhexanoic acid, methylundecanoic acid, dimethyldecanoic acid, 2-ethyl-3-methylnonanoic acid, 2,2-dimethyl-
4-ethyloctanoic acid, methyldocosanoic acid, 2-propyl-3-methylnonanoic acid, methyltridecanoic acid, dimethyldodecanoic acid, 2-butyl-3-methylnonanoic acid, methyltetradecanoic acid, ethyltridecanoic acid, propyldodecanoic acid, butyl Undecanoic acid, pentyldecanoic acid, hexylnonanoic acid, 2- (3-methylbutyl) -3-methylnonanoic acid, 2- (2-methylbutyl) -3-methylnonanoic acid, butylethylnonanoic acid, methylpentadecanoic acid, ethyltetradecanoic acid, propyl Tridecanoic acid, butyldodecanoic acid, pentylundecanoic acid, hexyldecanoic acid, heptylnonanoic acid, dimethyltetradecanoic acid, butylpentylheptanoic acid, trimethyltridecanoic acid, methylhexadecanoic acid, ethylpentadecanoic acid, propyltetradecanoic acid, butyrate Tridecanoic acid, pentyldodecanoic acid, hexylundecanoic acid, heptyldecanoic acid, methylheptylnonanoic acid, dipentylheptanoic acid, methylheptadecanoic acid, ethylhexadecanoic acid, ethylhexadecanoic acid, propylpentadecanoic acid, butyltetradecanoic acid, pentyltridecanoic acid, Hexyl decanoic acid, heptyl undecanoic acid, octyl decanoic acid, dimethyl hexadecanoic acid, methyl octyl nonanoic acid, methyl octadecanoic acid, ethyl heptadecanoic acid, dimethyl heptadecanoic acid, methyl octyl decanoic acid, methyl nonadecanoic acid, methyl nonadecanoic acid, dimethyl octadecanoic acid, Branched fatty acids such as butyl heptyl nonanoic acid; octenoic acid, nonenoic acid, decenoic acid, caproleic acid, undecylenic acid, lindelic acid, succinic acid, lauroleic acid, Linear monoenoic acids such as lidodenic acid, tuzuic acid, myristoleic acid, pentadecenoic acid, hexedenoic acid, palmitoleic acid, heptadecenoic acid, octadecenoic acid, oleic acid, nonadecenoic acid, gondonoic acid; methylheptenoic acid, methylnonenoic acid, methylun Branched monoenoic acids such as decenoic acid, dimethyldecenoic acid, methyldodecenoic acid, methyltridecenoic acid, dimethyldodecenoic acid, dimethyltridecenoic acid, methyloctadecenoic acid, dimethylheptadecenoic acid, ethyloctadecenoic acid; linoleic acid, lino Di- or trienoic acids such as elaidic acid, eleostearic acid, linolenic acid, linolenic elaidic acid, pseudoeleostearic acid, parinaric acid, arachidonic acid;

Acetylene acids such as octinoic acid, nonionic acid, decinic acid, undecinic acid, dodecinic acid, tridecinic acid, tetradecic acid, pentadecinic acid, heptadecinic acid, octadecinic acid, nonadesinic acid, dimethyloctadesinic acid; methyleneoctadecenoic acid, methyleneoctadecane Derived from cyclic acids such as acid, aleprolic acid, alepresinic acid, alleprilic acid, allepuric acid, hydnocarpic acid, sorghumulinic acid, gorulinic acid, α-cyclopentylic acid, α-cyclohexylic acid, α-cyclopentylethylic acid Acyl group and the like.
Moreover, the acyl group derived from the fatty acid obtained from natural fats and oils may be sufficient, and what is necessary is just the acyl group derived from the mixed fatty acid containing 80% or more of said saturated or unsaturated fatty acid having 8-20 carbon atoms. For example, acyl groups derived from coconut oil fatty acid, palm oil fatty acid, linseed oil fatty acid, sunflower oil fatty acid, soybean oil fatty acid, sesame oil fatty acid, castor oil fatty acid, olive oil fatty acid, camellia oil fatty acid, rapeseed oil fatty acid, palm kernel oil fatty acid, etc. Etc.

  In the water-based ink composition of the present invention, as an example of a multi-chain polyhydrophilic group type compound, a compound having at least one hydrophobic group and a hydrophilic group in the molecule is structurally linked with a suitable spacer. The structure may be any structure as long as it has this structure, and may be a compound that has been known so far. The spacer is preferably a linear, branched, cyclic, or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have a substituent. More preferably, a spacer which is a straight chain, branched chain, cyclic chain or aromatic hydrocarbon chain having 1 to 40 carbon atoms is preferred.

In the aqueous coating composition of the present invention, it is preferable that the hydrophilic group of the multi-chain polyhydrophilic group-type compound is independently a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group or a salt thereof. Here, examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like, specifically, alkali metals such as sodium, potassium, lithium, calcium, 1 selected arbitrarily from alkaline earth metals such as magnesium, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, basic amino acids such as arginine and lysine A salt with a seed or two or more. Among these, sodium salts, potassium salts, organic amine salts, and basic amino acid salts are particularly preferable.

In the aqueous coating composition of the present invention, it is preferable from the viewpoint of biodegradability and safety that at least one of the multi-chain polyhydrophilic group type compounds is a compound having an amino acid residue in the molecule. Furthermore, it is more preferable that at least one of the multi-chain polyhydrophilic group type compounds is a compound represented by the above general formula (1).
In the general formula (1), the long-chain acyl group represented by R ¹ CO may be independent, that is, each may be different or the same, and as described above, a saturated or unsaturated fatty acid having 8 to 20 carbon atoms. Any material can be used as long as it is derived from the straight chain, branched or cyclic. Further, R ¹ CO in the molecule are the same is preferably be viewed such as the reaction conditions.

In the general formula (1), R ² is hydrogen, or the number of carbon atoms that may be substituted by a hydroxyl group or a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. 1 to 3 lower alkyl groups, for example, methyl group, ethyl group, propyl group, isopropyl group, hydroxymethyl group, hydroxyethyl group, hydroxy (iso) propyl group, dihydroxy (iso) propyl group, carboxymethyl group, A carboxyethyl group, a carboxypropyl group, a sulfoethyl group, etc. are mentioned.
In the general formula (1), n substituents attached to X (the general formula (2)) may be independent, that is, may be different or the same. Moreover, the said General formula (2) shows what the so-called acidic amino acid was N-acylated, and it does not ask | require whether they are optical isomers, for example, D-form, L-form, and a racemate.

  The acidic amino acid is a monoaminodicarboxylic acid having 2 and 1 carboxyl groups and 1 amino group, respectively, in the molecule, and the amino group may be an N-methyl group or an N-ethyl group. It does not matter whether it is an optical isomer, for example, a D-form, an L-form, or a racemate. Examples of acidic amino acids include glutamic acid, aspartic acid, lanthionine, β-methyllanthionine, cystathionine, diencholic acid, ferrinin, aminomalonic acid, β-oxyaspartic acid, α-amino-α-methylsuccinic acid, β-oxyglutamic acid. , Γ-oxyglutamic acid, γ-methylglutamic acid, γ-methyleneglutamic acid, γ-methyl-γ-oxyglutamic acid, α-aminoadipic acid, α-amino-γ-oxyadipic acid, α-aminopimelic acid, α-amino- Examples thereof include γ-oxypimelic acid, β-aminopimelic acid, α-aminosuberic acid, α-aminosebacic acid, pantothenic acid and the like.

The n substituents (the above general formula (2)) attached to X are preferable because the acidic amino acid is an L-acidic amino acid molecule because it is excellent in biodegradability. Among these, it is preferable that the substituents are the same.
In the above general formula (1), n Z attached to X are m functional groups (hydroxyl group, amino group, thiol group) substituted with X (m ≧ n and an integer of 2 to 20). It is the bond part (-O-, -NR < ³ >-, -S-) which originates, and may be independent, that is, may be the same or different.
Here, R ³ is hydrogen, or an alkyl group, alkenyl group, aryl group or alkylaryl group having 1 to 10 carbon atoms.

In the general formula (1), X is a linear, branched or cyclic chain having a molecular weight of 1 million or less and having m functional groups consisting of one or more selected from a hydroxyl group, an amino group and a thiol group. Or a spacer which is an aromatic hydrocarbon chain, and X is the hydroxyl group,
You may have substituents other than an amino group and a thiol group.
In the general formula (1), X is preferably a residue of an m-valent compound having a molecular weight of 1 million or less and having m functional groups of one kind or two or more kinds selected from a hydroxyl group, an amino group and a thiol group. And a compound residue that may have a substituent other than a hydroxyl group, an amino group, and a thiol group. Here, the m-valent compound means that a bond derived from m functional groups can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

  Examples of such m-valent compounds include amino acids such as serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline; aminoethanol, aminopropanol , Aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid, aminophenol, amino Compounds having amino and hydroxyl groups in the molecule such as phenethyl alcohol and glucosamine; mercaptoethanol, mercaptofe Lumpur, mercapto propanediol, compounds having a thiol group and a hydroxyl group in the molecule such as Gurukochiosu; aminothiophenol, compounds having a thiol group and an amino group in the molecule such as aminotriazole thiol; and the like. Further, proteins, peptides, etc., or those obtained by hydrolyzing them may be used.

  X preferably has 1 to 40 carbon atoms among the residues of such compounds, and more preferably X has 1 to 20 carbon atoms. Particularly preferred are those having 1 to 10 carbon atoms. Furthermore, X is a substituent other than a hydroxyl group, amino group, or thiol group in the molecule, and at least one or more independent carboxyl groups, sulfonic acid groups, sulfate ester groups, phosphate ester groups, or salts thereof, etc. When it contains, the multi-chain polyhydrophilic group type compound represented by the general formula (1) is preferable in that it has excellent solubility in weak acidity. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

In the general formula (1), X is preferably an m-valent (m ≧ n) polyhydroxyl compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a hydroxyl group. Here, the m-valent polyhydroxyl compound means that m ester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
Examples of such m-valent polyhydroxyl compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , Pentanediol, 1,6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl -1,5-pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydro Shi tartaric, mevalonate, 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine, and the like, and divalent hydroxyl compounds such as isomers thereof;

Glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl- Trivalent poly, such as 2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine, trihydroxystearic acid Hydroxyl compounds; pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, , 3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, 1,3,4,5-hexanetetrol, diglycerin, sorbitan, and other tetravalent polyhydroxyl compounds; adonitol, arabitol , Pentavalent polyhydroxyl compounds such as xylitol, triglycerin; hexavalent polyhydroxyl compounds such as dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, allose; or their dehydration condensates, polyglycerin, etc. It is done.

Sugars such as tetroses such as erythrose, sreose, erythrulose;
Pentose such as ribose, arabinose, xylose, lyxose, xylulose, ribulose; monosaccharides such as hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose, tagatose; maltose, iso Examples thereof include oligosaccharides such as maltose, cellobiose, gentiobiose, melibiose, lactose, turanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, stachyose.
In addition, other saccharides such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether, glycoside, etc. It may be a group, and may be a polysaccharide such as starch, glycogen, cellulose, chitin, chitosan or the like, or a hydrolyzed product thereof.

X preferably has 1 to 40 carbon atoms among the residues of such compounds, more preferably X has 1 to 20 carbon atoms. Particularly preferred are those having 1 to 10 carbon atoms.
Furthermore, when X contains at least one or more independent carboxyl group, sulfonic acid group, sulfuric acid ester group, phosphoric acid ester group or a salt thereof as a substituent, it is represented by the general formula (1). The multi-chain polyhydrophilic group type compound is preferable in that it has a weak acid solubility. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.
In the general formula (2), X is preferably an m-valent polyamino compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than an amino group. Here, the m-valent polyamino compound means that m acid amide bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.

Examples of such m-valent polyamino compounds include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, Aliphatic diamines such as diaminodecane, diaminododecane, diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and their isomers; diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl -Octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6-triaminohexane, 1,6,11-triaminoundecane, di (aminoethyl) amine, and isomers thereof of Aliphatic triamines; Alicyclic polyamines such as diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, triaminocyclohexane; diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, Aromatic polyamines such as diaminobenzenesulfonic acid, diaminobenzoic acid, and their respective isomers; diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, di (aminomethyl) naphthalene,
And araliphatic polyamines such as their respective isomers; polyamines substituted with hydroxyl groups such as diaminohydroxypropane and their respective isomers, and the like.

X preferably has 1 to 40 carbon atoms among the residues of such compounds, and more preferably X has 1 to 20 carbon atoms. Particularly preferred are those having 1 to 10 carbon atoms.
Furthermore, when X contains at least one or more independent carboxyl group, sulfonic acid group, sulfuric ester group, phosphoric ester group or a salt thereof as a substituent, it is represented by the above general formula (1). The compound is preferable in that it is weakly acidic and excellent in solubility. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

In the general formula (1), X is preferably an m-valent polythiol compound residue having a molecular weight of 1,000,000 or less, which may have a substituent other than a thiol group. Here, the m-valent polythiol compound means that m thioester bonds can be formed. It does not matter whether they are optical isomers such as D-form, L-form, and racemate.
Examples of such m-valent polythiol compounds include dithiol compounds such as dithioethylene glycol, dithioerythritol, and dithiothreitol. X preferably has 1 to 40 carbon atoms among the residues of such compounds, more preferably X has 1 to 20 carbon atoms. Particularly preferred are those having 1 to 10 carbon atoms.
Further, when X contains 1 to 10 independent carboxyl groups, sulfonic acid groups, sulfuric acid ester groups, phosphoric acid ester groups or salts thereof as a substituent, it is represented by the above general formula (1). A polychain polyhydrophilic group-type compound is preferable in that it has excellent solubility in weak acidity. X is preferably a naturally occurring type from the viewpoint of excellent biodegradability.

In the general formula (2), a carboxyl group represented by Y, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, and a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, etc. that can be contained in X Can form salts with various basic substances.
Examples of such salts include alkali metal salts, alkaline earth metal salts, ammonium salts, organic amine salts, basic amino acid salts, and the like. Specifically, alkali metals such as sodium, potassium and lithium, calcium and magnesium 1 type arbitrarily selected from alkaline earth metals such as aluminum, metals such as aluminum and zinc, organic amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine, and basic amino acids such as arginine and lysine Or it is a salt with 2 or more types. Among these, sodium salt, potassium salt, organic amine salt, and basic amino acid salt are preferable.
As a method for producing such a multi-chain polyhydrophilic group compound represented by the general formula (1), an N-long chain acyl acidic amino acid anhydride represented by the following general formula (3) and a hydroxyl group in the molecule, It can be obtained by reacting a compound having one or two or more m functional groups selected from an amino group and a thiol group in water and / or a mixed solvent of water and an organic solvent.

Alternatively, the multi-chain polyhydrophilic group compound represented by the general formula (1) is an N-long chain acyl acidic amino acid anhydride represented by the general formula (3) and a polyhydroxyl compound, a polyamino compound, or a polythiol compound, or A compound having any two or three of hydroxyl group, amino group, and thiol group in the molecule at a temperature higher than any melting point, or tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform, acetone It can obtain by mixing at -5-200 degreeC using inert solvents, such as.

  Alternatively, the multi-chain polyhydrophilic group type compound represented by the general formula (1) is an N-long chain acyl acidic amino acid mono-lower ester (eg, methyl ester, ethyl ester) and a polyhydroxyl compound, a polyamino compound, or a polythiol compound, Alternatively, a compound having any two or three of hydroxyl group, amino group, and thiol group in the molecule is dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and- It can be obtained by carrying out a heating reaction at 5 ° C. to 250 ° C. and then removing the reaction solvent. Alternatively, the polychain polyhydrophilic group type compound used in the present invention can be obtained by heating and melting without solvent, adding a catalyst such as sodium hydroxide, and causing a transesterification reaction at room temperature to 250 ° C.

The blending amount of the multi-chain polyhydrophilic group type compound in the aqueous coating composition of the present invention is not particularly limited, but is preferably 0.1% by weight or more, more preferably 0.5% by weight based on the solid content of the composition. % Or more, more preferably 1% by weight or more. If the amount of the multi-chain polyhydrophilic group-type compound is large as long as there is no other problem, the stability is improved, but if it exceeds 10% by weight, there are problems such as a decrease in water resistance of the aqueous coating composition depending on the use. May occur.
The following aqueous synthetic resins can be used for the aqueous coating composition of the present invention. For example, aqueous acrylic resin, aqueous reaction curable acrylic resin, aqueous acrylic urethane paint, aqueous urethane resin, aqueous acrylic urethane resin, aqueous vinyl chloride resin, aqueous vinyl acetate resin, aqueous epoxy resin, aqueous alkyd resin Commonly used materials such as aqueous polyamide resins and aqueous cellulose resins can be used.

  Examples of the monomer of the aqueous synthetic resin include aliphatic conjugated dienes such as butadiene, isoprene, 2-chloro-1,3-butadiene, aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, methyl methacrylate, Methacrylic acid alkyl esters such as ethyl methacrylate and butyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid alkyl esters such as 2-ethylhexyl acrylate, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and acetic acid Examples include vinyl, vinyl chloride, vinylidene chloride, urethane, and ethylene.

  Further, as other copolymerizable monomers, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycyl methacrylate, N-methylol acrylamide, N-butoxymethyl acrylamide, acrylamide, sodium styrene sulfonate, if necessary And ethylenically unsaturated carboxylic acids such as itaconic acid, fumaric acid, acrylic acid, methacrylic acid and crotonic acid. Examples of polymer emulsions of these monomers include styrene-butadiene copolymer latex, polystyrene polymer latex, polybutadiene polymer latex, acrylonitrile-butadiene copolymer latex, polyurethane polymer latex, polymethyl Methacrylate polymer latex, methyl methacrylate-butadiene copolymer latex, polyacrylate polymer latex, vinyl chloride polymer latex, vinyl acetate polymer emulsion, vinyl acetate-ethylene copolymer emulsion, polyethylene emulsion, etc. Is mentioned. The blending amount of these aqueous synthetic resins in the aqueous coating composition is preferably 20 to 70% by weight, more preferably 35 to 60% by weight, based on the solid content of the composition. If the water-based synthetic resin is less than 20% by weight, the physical properties of the water-based paint deteriorate, and if it exceeds 70% by weight, the content of the pigment component in the water-based paint composition becomes relatively small, and the hiding power. , Coloring power, rust prevention power, etc. are reduced.

  The aqueous paint composition of the present invention contains a pigment, specifically, anticorrosive paint such as zinc chromate, zinc paste, zinc phosphate, titanium oxide, lead white, basic lead sulfate, basic silicic acid. White pigments such as lead, zinc white, zinc sulfide, antimony trioxide, calcium composites, body pigments such as calcium carbonate, barium sulfate, alumina white, silica, diatomaceous earth, kaolin, talc, organic bentonite, white carbon, carbon black , Yellow lead, molybdenum red, bengara, yellow iron oxide, iron black, ocher, senna, amber, green earth, mars violet, cadmium yellow, cadmium red, cadmium red, cadmium red, ultramarine, bitumen, etc. Can be used. In addition, wetting agents, pigment dispersants, emulsifiers, thickeners, anti-settling agents, anti-skinning agents, anti-sagging agents, leveling agents, leveling agents, anti-blocking agents, antioxidants, UV rays Absorber, radical scavenger, curing accelerator, surfactant, light resistance improver, preservability improver, filler, defoamer, plasticizer, desiccant, preservative, fragrance, pearl agent, lame agent, drug Etc. can be included. The blending amount of these pigments in the aqueous coating composition is preferably 20 to 70% by weight, more preferably 35 to 60% by weight, based on the solid content of the composition. If the pigment is less than 20% by weight, it will exhibit optical properties such as pigment color tone and coloring power, or chemical properties such as dispersibility, fluid physical properties, weather resistance, and heat resistance as an aqueous paint. If it exceeds 70% by weight, it becomes difficult to stabilize the pigment.

The aqueous coating composition of the present invention can further contain an organic solvent. Examples thereof include solvents composed of one or a combination of two or more selected from hydrocarbons, alcohols, polyhydric alcohols, derivatives of polyhydric alcohols, ketones, esters, and carbonates.
Examples of hydrocarbons include xylene, toluene, hexane, cyclohexane, mineral spirit, turpentine oil, sorben naphtha, and the like. Alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n-decanol, n-undecanol, or these Isomers, cyclopentanol, cyclohexanol and the like. Alcohols having 1 to 6 alkyl carbon atoms are preferred.

  Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexane Examples include diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like. Polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Examples include ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and cellosolve acetate.

Examples of ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone, and cyclohexanone.
Esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate, butyrate, dibutyl phthalate, dioctyl phthalate, and cyclic such as ε-caprolactone and ε-caprolactam. Examples include esters.
Examples of ethers include diethyl ether, isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.

Examples of carbonates include dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethylene carbonate.
The coating method of the water-based coating composition of the present invention can be applied on a substrate by brush, bar coater, roll coater, spray or the like. As a base material, the base material according to the use of the synthetic resin paint to be used is used. For example, metal, wood, resin, glass, cement, asphalt, soil and the like can be mentioned.
As described above, according to the present invention, distributed, useful for construction, building materials, structures, ships, new cars, automobile repairs, electricity, metals, plastics, machinery, railways, aircraft, woodworking, home use, road surface display, leather applications, etc. It becomes possible to provide an aqueous coating composition having good stability, fluidity and moderate viscosity. In particular, it is preferably used as a paint for construction, a base coat paint for automobile intermediate coating or top coating, a paint for ship steel plates, and a paint for cans.

EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not restrict | limit the scope of the present invention. In addition, the manufacture example of the polychain polyhydrophilic group type compound in an Example is explained in full detail below.
(Production Example 1 of a multi-chain polyhydrophilic group type compound)
9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. While this solution was adjusted to a pH range of 10 to 11 with a 25% aqueous sodium hydroxide solution and the reaction temperature was maintained at 5 ° C., 31.1 g of N-lauroyl-L-glutamic anhydride (0. 1 mol) was added over 2 hours to carry out the reaction. After stirring for another 30 minutes, tertiary butanol was added to a concentration of 20% by weight in the liquid, 75% sulfuric acid was added dropwise to bring the liquid pH value to 2, and the liquid temperature to 65 ° C. It was adjusted. After completion of the dropwise addition, stirring was stopped, and the mixture was allowed to stand at 65 ° C. for 20 minutes. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the same water washing operation on the obtained organic layer, the solvent was removed from the obtained organic layer, and neutralized with sodium hydroxide to an aqueous solution having a solid content of 30% by weight and a pH of 7 (25 ° C.). After drying, a composition containing a polychain polyhydrophilic group compound represented by the following general formula (4) was obtained.

(Production Example 2 of Multi-Chain Polyhydrophilic Group Type Compound)
In Production Example 1, N-lauroyl-L-glutamic anhydride (0.1 mol) was changed to N-cocoyl-L-glutamic anhydride (0.1 mol), and the solid content was adjusted to 30% by weight and pH 7 (25 ° C.). Except for the above, the same conditions as in Production Example 1 were carried out to obtain a composition containing a multi-chain polyhydrophilic group type compound.

<Storage stability>
50 g of the prototype sample was weighed into a glass sample bottle, and this sample was left in a thermostatic chamber at 25 ° C. for 7 days to evaluate the water separation rate (%). The water separation rate indicates the ratio of the distance (mm) from the upper liquid surface to the bottom surface of the suspension layer with respect to the distance (mm) from the upper liquid surface to the bottom surface of the entire sample.
○: Water separation rate of less than 5% △: Water separation rate of 5% or more and less than 10% ×: 10% or more

<Rust prevention>
A salt spray test was conducted for 1000 hours in accordance with JISZ2371 on a steel sheet that had been subjected to phosphozinc treatment and cross-cut in a bathtub in which the aqueous rust preventive coating composition was stirred, and the degree of rust generation was confirmed.
○: Good. Δ: Slightly good X: Inferior.

<Anti-corrosion>
Each of the test coated plates was prepared by coating the prototype paint and applying the polished steel plate with a film applicator having a gap of 100 μm and drying in an atmosphere of 20 ° C. and 65% RH for 10 days. The test coated plate was cross-cut with a cutter on the coated surface and left in the salt spray test of JIS-Z-2371 (or JIS-K5600) for 192 hours (1000 hr), and the state of rust formation was observed.
○: No rusting △: Partial rusting ×: Fully rusting

<Weather resistance test>
According to JIS K5600, weather resistance was implemented for 1000 hours. After the test, the following evaluation test was performed.
A) Pencil hardness test In accordance with JIS K5600, a pencil was pressed against the surface of the coating to investigate the hardness of the coating.
○: No change in hardness compared to before the test.
(Triangle | delta): The change of 1 rank is recognized by hardness compared with the test before.
X: A change of 2 ranks or more in hardness is recognized as compared with before the test.
* 1 rank means that the hardness changes from H to 2H, for example.
B) Adhesive strength test According to ASTM D-3359, the adhesive strength when a cross-cut was put on the coating film and the adhesive tape was brought into close contact and peeled immediately was investigated.
○: No peeling is observed. Δ: Partial peeling is observed. X: Peeling is recognized over the entire surface.

[Example 1] Preparation of aqueous coating composition This aqueous coating composition had the following composition, and these mixtures were stirred with a commercially available sand grinder mill to prepare a coating composition.
55 parts by weight of aqueous acrylic resin liquid (solid content 45% by weight)
Zinc phosphate (rust preventive pigment) 8 parts by weight Carbon black (colored pigment) 2 parts by weight Barium sulfate (extreme pigment) 20 parts by weight Product of Production Example 1 0.5 part by weight Water 14.5 parts by weight The aqueous rust preventive After preparing the coating composition, an evaluation test was carried out according to the above method. The evaluation results are shown in Table 1.

[Example 2] Preparation of aqueous coating composition The aqueous coating composition had the following composition, and these mixtures were stirred with a commercially available sand grinder mill to prepare a coating composition.
55 parts by weight of aqueous acrylic resin liquid (solid content 45% by weight)
Zinc phosphate (rust preventive pigment) 8 parts by weight Carbon black (color pigment) 2 parts by weight Barium sulfate (extreme pigment) 20 parts by weight Product of Production Example 2 1 part by weight Water 14 parts by weight After the preparation, an evaluation test was performed according to the above method. The evaluation results are shown in Table 1.

[Comparative Example 1] Preparation of aqueous coating composition The aqueous coating composition had the following composition, and these mixtures were stirred with a commercially available sand grinder mill to prepare a coating composition.
55 parts by weight of aqueous acrylic resin liquid (solid content 45% by weight)
Zinc phosphate (rust preventive pigment) 8 parts by weight Carbon black (color pigment) 2 parts by weight Barium sulfate (extreme pigment) 20 parts by weight 12.5% cellulose aqueous dispersion 2.4 parts by weight Water 12.6 parts by weight After preparing the rust preventive coating composition, an evaluation test was performed according to the above method. The evaluation results are shown in Table 1.

[Comparative Example 2] This aqueous coating composition had the following composition, and the mixture was stirred with a commercially available sand grinder mill to prepare a coating composition.
55 parts by weight of aqueous acrylic resin liquid (solid content 45% by weight)
Zinc phosphate (rust preventive pigment) 8 parts by weight Carbon black (colored pigment) 2 parts by weight Barium sulfate (extreme pigment) 20 parts by weight 2% sodium carboxymethylcellulose dispersion
15 parts by weight After preparing the water-based anticorrosive coating composition, an evaluation test was carried out according to the above method. The evaluation results are shown in Table 1.

  The composition of the present invention can be suitably used in the field of water-based paints excellent in rust prevention of steel products in the fields of architecture, ships and automobiles.

Claims (3)

  An aqueous coating composition comprising one or more multi-chain polyhydrophilic group-type compounds each having two or more acyl groups and hydrophilic groups in the molecule, an aqueous synthetic resin, and a pigment.   The water-based coating composition according to claim 1, wherein at least one of the multi-chain polyhydrophilic group type compound has an amino acid residue in the molecule. The aqueous coating composition according to claim 1 or 2, wherein at least one of the multi-chain polyhydrophilic group type compound is a compound represented by the following general formula (1).

(In the above general formula (1), X is a linear, branched, cyclic or aromatic hydrocarbon chain having a molecular weight of 1,000,000 or less, which may have m functional groups and other substituents. The n (m ≧ n) Qs bonded to X are substituents represented by the following general formula (2), which may be the same as or different from each other. In Formula (2), Z is a bond derived from a functional group of X, R ¹ CO represents a long-chain acyl group derived from a saturated or unsaturated fatty acid having 2 to 20 carbon atoms, R ² represents hydrogen, or a lower alkyl group having 1 to 3 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and Y represents a carboxyl group, a sulfonic acid group, a sulfate group, or a phosphate group. Or of those salts J and k are each independently 0, 1, or 2 and j and k are not 0 simultaneously, n is an integer of 2 to 20, and m is m ≧ n Indicates an integer.)