JPS61136556A - Water-based coating composition - Google Patents

Abstract

PURPOSE:To provide a water-based coating compsn. with excellent storage stability and film properties, prepared by adding an aqueous dispersion of pigment to an emulsion obtained by dispersing a neutralized alkyd resin in water. CONSTITUTION:The water-based coating compsn. contains (A) 5-60wt% by solid emulsion obtained by dispersing a neutralized maleinized alkyd resin in water, (B) 0.001-6wt% by solid aqueous pigment dispersant selected from among polyoxyethylene nonionic surfactant, nonionic-anionic surfactant, carboxylate anionic surfactant and oligomeric or polymeric anionic surfactant, (C) 1-70wt% pigment, (D) 10-80wt% aqueous medium and (E) 0-7wt% amphipathic organic solvent. Combination of the emulsion (A) having excellent storage stability and the dispersant (B) suitable for the emulsion produces a water-based coating compsn. having improved storage stability and film properties.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a water-free paint with excellent storage stability and spreading performance, which is obtained by blending an aqueous pigment dispersant into an emulsion obtained by dispersing a neutralized maleated alkyd resin in water. Regarding the composition.

In recent years, water-soluble alkyd resins have been widely used as binder components for coatings for coatings and industrial applications due to their low cost and non-polluting properties.

Conventionally, methods for dispersing or dissolving alkyd resins, which are used as vehicle components in water-based paints, in water include forcing the alkyd resin to disperse in water using a surfactant; (1) polyethylene glycol-modified alkyd resin, (2) dimethylolpropion-modified alkyd resin, (3) t-alkyd resin after halfesterization with 7-taric anhydride and trimellitic anhydride, ( A generally known method is to dissolve tetramaleated alkyd fat or the like in a large amount of an amphipathic organic solvent, neutralize it if necessary, and then dissolve it in portions in water using the next solution.

The former method has the disadvantage that it is difficult to disperse the alkyd resin in water as fine particles, and a stable emulsion cannot be obtained. In the latter method, (1)
The aqueous solution of alkyd resin obtained using the resin in (2) has the drawback that the resin has many opportunities to come into contact with water, so it is easily hydrolyzed and becomes insoluble in water, resulting in poor storage stability. The aqueous dispersion of alkyd resin obtained using the resin of (3) has the disadvantage of poor storage stability because the resin is hydrolyzed by the antimeric effect.
However, the aqueous dispersion of alkyd resin obtained using the resin has the drawback that the amphiphilic organic solvent added to the resin swells the dispersed particles, accelerates hydrolysis, and impairs storage stability. However, when the water teaching solution is stored in a harsh atmosphere, the organic solvent redissolves the resin in the aqueous dispersion, resulting in a gel state.''!On the other hand, amphiphilic inorganic solvents In the case of self-emulsifying alkyd resins that do not use a self-emulsifying alkyd resin, it is impossible to disperse pigments into the resin, especially in the case of malicated alkyd resins. When the paste is dispersed in water and then added to the maleated alkyd resin emulsion, a characteristic of the dispersed emulsion, particularly the emulsion of the present invention, is that the emulsion coagulates due to mixing shock and forms lumps.

In light of the above-mentioned situation, there is a strong demand in this field for the development of water-based paints that have excellent storage stability and are non-polluting.

The inventors of the present invention have conducted extensive research to develop a water-based paint that eliminates these drawbacks.

First, regarding the problem of storage stability of emulsions, as mentioned above, it is possible to improve the emulsification type alkyd #I # fat emulsion by not containing or limiting the amount of amphipathic organic solvent contained in the emulsion. measured. As a result, the self-emulsifying alkyd resin emulsion that does not contain amphipathic organic solvents is limited and the emulsion of the self-emulsifying alkyd resin is safe for storage in harsh atmospheres, and It was found that water and neutralizing agent did not enter the inside of the emulsion particles, and hydrolysis was excellent, eliminating the above-mentioned drawbacks. In addition, in the above-mentioned self-emulsifying alkyd resin emulsions, especially those containing a maleated alkyd resin as a vehicle component, the resin has a structure in which a carboxyl group is directly attached to a lipophilic fatty acid; The particle surfaces of the resulting emulsion are covered with lipophilic parts, and are therefore superior to the above-mentioned drawbacks.

However, the problem with the pigment dispersion method, on the other hand, can be solved by using an aqueous pigment fractionation agent that has excellent pigment dispersibility and dispersion stability, and has a stable effect when mixed with the maleated alkyd resin emulsion. I tried to improve it.

As described above, by using the above-mentioned alkyd emulsion having excellent storage stability and further combining it with a water-based pigment dispersion agent suitable for the emulsion/L/shock, a water-based paint composition without the above-mentioned drawbacks can be obtained. They discovered this and completed the present invention.

That is, the FIA of this invention includes (4) an emulsion formed by dispersing a maleated alkyd fN fat neutralized product in water with a solid content of 5 to 60% by weight, (2) a polyoxyethylene type nonionic surfactant,
0.001 to 6% by weight of at least one aqueous pigment fraction agent selected from nonionic-anionic surfactants, carposi salt type anionic surfactants, and oligomer or polymer type surfactants; (C) 1 to 70% by weight of aqueous medium, 10 to 80% by weight of an aqueous medium, and (Q) an amphiphilic organic solvent O to 711%.

The maleated alkyd beak fat used in component A of the present invention is mainly a resin obtained by reacting a (semi-)drying oil, a (semi-)drying oil fatty acid, a polybasic acid, a -basic acid, and a polyhydric alcohol. It can be obtained by further reacting with anhydrous leic acid.

The (semi-)drying oils and/or fatty acids used include, for example, linseed oil, safflower oil, soybean oil, sesame oil,
Poppy oil, Nino oil, hempseed oil, pudoku kernel oil, corn sorghum oil, tall oil, sunflower oil, cottonseed oil, walnut oil, rubber seed oil, tung oil, oyster oil, dehydrated and mustard oil, and other fatty acids, high diene fatty acids, etc. can be given. Among these, it is preferable to use maleated oak rasp, linseed oil, soybean oil and their fatty acids, and tall oil fatty acids, which have good water dispersibility.

The polybasic acid is a compound having 2 to 4 carboxyl groups in one molecule. Specifically, for example, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, succinic acid, maleic acid, adivicic acid, cepatic acid, azelaic acid, hymic acid, itaconic acid, methylcyclohexicitricarboxylic acid. , crotonic acid, pyromellitic acid, anhydrides thereof, and the like can be used. Among these, 7-Curic acid, inphthalic acid, and terephthalic acid are preferred.

Examples of monobasic acids include benzoic acid, para-butylbenzoic acid, methylbenzoic acid, non-drying oil fatty acids, etc. which do not contain sub-fatty acids and are generally used in the production of alkyd resins.

Among these, benzoic acid is preferred because it is low cost and has high coating film hardness.

The polyhydric alcohol is an alcohol having 2 to 6 hydroxyl groups in one molecule, and specifically, for example, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, cuccidiol, tecanediol, diethylene glycol, bentanediol, Examples include neopentifrechrycol, glycerin, trimethylo-l-reethane, trimethylolpropane, penquerythritol, sorbitol, l,4-cyclohexane dimetatool, tricyclodecane dimetatool, tris isocyanurate, and the like. The alkyd resin components mentioned above can be used alone or in combination of two or more.

The alkyd resin can be produced by subjecting each of the above nine fractions to a dehydration condensation reaction at about 150 to about 250°C for about 3 to about 10 hours in an inert gas atmosphere according to a synthesis method known per se. .

Next, the synthesis of the 1-maleic alkyd resin was performed by mixing the mixture of the maleic alkyd resin and maleic anhydride with a molecular weight of about 150 to about 230
C. for about 1 to about 5 hours. The acid value of the maleated alkyd resin thus obtained ranges from about 7 to about 70, preferably from 20 to 50. When the acid value of the resin falls within the above-mentioned range, the moisture content and the water resistance of the coating film are improved.

The oil strength of the maleated alkyd resin used in the present invention,
It ranges from about 15 to about 75, preferably from 25 to 65. When the oil length of the resin falls within the above range, stable maleated alkyd resin emulsion production can be obtained and the water resistance of the coating film can be improved.

The viscosity of the maleated alkyd resin used in the present invention is
Although not limited to, a 60% by weight diluted butyl cellosolve solution has a Gardner foam viscometer value in the range of 0 to Z5, preferably in the s-Za range. When the value of the Gardner foam viscometer falls within the above-mentioned range, the moisture content, stability of the emulsion, and water resistance of the coating film are improved.

The amphiphilic organic solvent (T) used in the present invention has the effect of helping the maleated alkyd resin to separate into water. It is an alcohol-based solvent with

Such solvents include, for example, the formula HO-CmH2m+1 (
In the formula, m is an integer from 2 to 6. ), for example, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n7′-thyl alcohol, isobutyl alcohol, Sec-7” thyl alcohol, tert-
7'thyl alcohol, isoamyl alcohol, 5eC-
Amyl alcohol, tert-amyl alcohol, etc.1 Formula H□-(CHHzn)q-0CDH2p+1 (In the formula, n and p represent an integer from 2 to 6, and q represents an integer of 1 or 2.) , such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and globylene glycol monomethyl ether.
Examples include 3-methoxy-3-methyl-getanol, ethylene glycol mobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and the like. In the above ceremony, Koshikake HO
It is a solvent with CmH2m + 1.

In the preparation of maleated alkyd resin emulsions,
If it's Seo no Ko'127 Resion! When the alcoholic solvent is removed under reduced pressure, it is preferable that the alcoholic solvent has a low boiling point.

Here, the term "low boiling point" means that the boiling point temperature range is approximately 0℃.
~about 150°C.

It varies depending on the blending amount of the solvent and the blending amount of the resin and pigment contained in the water-based paint containing the maleated alkyd resin emulsion as the binder component, but it is generally 0 to 7.
The weight percent range is preferably about 5% by weight or less, more preferably about 2% by weight or less. When the amount of the solvent is more than 7% by weight, the solubility in water is improved, but the storage stability is deteriorated, and furthermore, there is a disadvantage that it causes environmental pollution. The above solvents may be used alone or in combination of two or more.

The neutralizing agent used in the present invention is the following ammonia and organic amines that hydrate the maleated alkyd resin, for example, 4JFI 1st grade, 2nd grade''!9 is 4!1
Tertiary alkylamines, representative examples include methylamine, ethylamine, propylamine, methylamine, amylamine, dimethylamine, diethylamine, diethylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, morpholin; primary; Secondary to primary alkanolamines are tertiary alkanolamines, representative examples of which include monoethanolamine, jetanolamine, dimethylethanolamine, diethylethanolamine, and the like. Among these neutralizing agents, diethylamine, triethylamine, and dimethylethanolamine are preferred because they have good dispersibility and are highly volatile and do not easily remain in the coating film.

Further, the above neutralizing agents can be used alone or in combination of two or more. The amount of the neutralizing agent used is about 0.01 to about 2.0 equivalents, preferably 0.3 to 1.0 equivalents, based on the carboxyl group in the general KX resin.

Maleated alkyd resin emulsion used in the present invention (
2) is prepared by neutralizing the maleated alkyd resin with the neutralizing agent and, if necessary, containing the alcoholic organic solvent in an amount of 7% by weight or less of the aqueous coating composition. Gradually add water to the neutralized I# fat solution or! ! Next, a maleated alkyd resin emulsion prepared by adding the above-mentioned alcoholic organic solvent to the neutralized maleated alkyd resin in an amount exceeding 7% by weight of the aqueous coating composition was prepared under normal pressure. This is accomplished by removing the alcoholic organic solvent under reduced pressure to a concentration of 7% by weight or less, which is within the scope of the present invention.

Note that the temperature of the emulsion during water indoctrination and removal of the alcohol-based organic solvent is not particularly limited, but is approximately 20°C.
Preferably, the temperature is between 60°C and 60°C.

The solids content of the maleated alkyd resin emulsion used in the present invention is, but is not limited to, about 10 to about 65% by weight.
, preferably from 25 to 60% by weight. The particles are manufactured so that the average particle diameter as measured by a turbidity method is about 0.5 μm or less, preferably 0.2 μm or less.

If the average particle size is larger than 0.5 scale, the sedimentation stability of the maleated alkyd resin emulsion is poor, the grain particles are not stable, the hydrolysis resistance is poor, and the water resistance and corrosion resistance of the coating film is poor. Sex also gets worse. Here, in the turbidity method, a water-diluted solution of clear emulsion is measured with a spectrophotometer, and the absorbance ratio is calculated using the following formula.
Industrial, Chemical, Release
rchVoL, 42 p145-152 (1964)
) Determine the average particle diameter using the dangerous amount curve described in K.

The aqueous pigment dispersant (B) used in the present invention is (
1) Polyoxyethylene type nonionic surfactant, (seal)
Surfactants such as nonionic-anionic surfactants, (■) carboxylate-type anionic surfactants, and QV) oligomeric or polymeric surfactants can be used, and these will be explained below.

(1) A polyoxyethylene type nonionic surfactant is used to separate the hydrophilic and lipophilic parts in the aqueous solution state.
! The parent tree has a hydroxyl group and an ester bond group. Examples include polyoxyethylene adducts of higher alcohols, polyoxyethylene adducts of alkylphenols, condensates of higher fatty acids and polyethylene glycol, and ethylene oxide adducts of fatty acid esters of polyhydric alcohols.

Incidentally, the term "high class" here means an alkyl group of C6 or higher.

(1) A nonionic-ionic surfactant is one in which a sulfonic acid ester group or a phosphate Nisder group, which dissolves into an ether group and an anion, is introduced into the parent moiety in the state of an aqueous solution. For example, the formula RO(CnH2nOq(X)
M+ (wherein R is a C6-24 alkyl group or JdC
6,300 represents an alkylphenol group, X represents a sulfonic acid ester group, M represents an organic cation, and n represents an integer from 2 to 3. , q represents an integer from 1 to 4o).

(1) Carvone-type anionic surfactant (c) In an aqueous solution, a carboxyl group that dissociates into an anion is introduced into the parent moiety. Examples include salts of saturated or unsaturated fatty acids of 06 or more, such as sodium lafinate, sodium stearate, and sodium oleate, and benzoates unsubstituted or substituted with alkyl groups of 01 to 24.

(Iv) Oligomeric or polymeric surfactants are water-soluble unsaturated monomers (a) and/or nitrogen-containing unsaturated monomers (υ is an essential component, and long-chain unsaturated monomers are optionally added). Monomer (c) and α other than the above (a) to (c),
Average molecular weight 500 to 100.000 obtained by copolymerizing β-ethylenically unsaturated monomers (d) in appropriate combinations
belongs to. Next, these monomers will be explained.

Water-soluble unsaturated monomer (a) J-1'', carboxyl group, is a water-soluble monomer having a sulfonic acid (salt) group, and representative examples thereof are as follows.

(υ Carboxyl group-containing unsaturated monomers: such as (meth)acrylic acid, 2-carboxyethyl (meth)acrylic acid, maleic anhydride, crotonic acid, fumaric acid, etc. (2) Sulfonic acid (salt) unsaturated monomer mer: e.g. (meth)acrylic acid ethyl sulfosyl sodium trichum, (meth)acrylate
Sodium propyl sulfonate acrylate, sodium styrene sulfonate, 2-acryleamide-2-methyl-propanesulfonic erminol JS-2 (manufactured by Sanyo Chemical Industries, Ltd., trade name, 2 CH
2-COORCH2=CHCHzOOC-CH-SO3
Represented by Na, R ke C12H25, then C 13 H
27), sodium allylsulfosinate, etc.

These water-soluble unsaturated monomers may be used alone or in combination of two or more.

Nitrogen-containing unsaturated monomers (bJ include monomers containing one or more basic nitrogen atoms and one ethylenically unsaturated bond in one molecule. A typical example is as follows.

(1) Aminoalkyl (meth)acrylates diN
．． N-dimethylaminoethyl (meth)acrylate, N
．． N-diethylaminoethyl (meth)acrylate, N
-j-butylaminoethyl (meth)acrylate, N.
N-dimethylaminopropyl (meth)acrylate), N
, N-dimethylaminobutyl (meth)acrylate, N
-Propylami/ethyl (meth)acrylate, N-butylami/ethyl (meth)acrylate, etc.

(2) (Meth)acrylamides: (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-gutyl (meth)acrylamide, N. N-dimethyl (meth)
Acrylamide, N,N-diethyl (meth)acrylamide, N. N-dipropyl (meth)acrylamide, N
-Methylol (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N,N-dimethylaminopropylacrylamide cap.

(3) Vinylpyrrolidones: For example, 1-vinyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone, and the like.

(4) Vinylpyridines: For example, 2-vinylpyridine, 4-vinylpyridine, 5
-Methyl-2-vinylpyridine>, 5-ethyl-2-vinylpyridine group (5) Vinylimidazoles: For example, 1-vinylcarbazole, 1-vinyl-2-
Methylimidazole etc.

(6) Vinyl carbazoles: Examples tl'1m, N-vinylcarbazole, etc.

(7) Vinylquinolines: For example, 2-vinylquinoline and the like.

(8) Vinylpiperidines 6 Examples include 3-vinylpiperidine, N-methyl-3-vinylpiperidine, etc.

(9) Mollephorins: For example, N-(meth)acryloylmorpholins (10)
pyrrolidine>: For example, N(meth)acryloylpyrrolidine (11) Others: For example, the above-mentioned aminoalkyl (meth)acrylate (1), the above-mentioned (2) (meth)acrylamide, sodium monochloroacetate, etc. reaction product with monohalogenated fatty acids. ``!9 The aminoalkyl (meth)acrylates are B (meth)acrylamides and 1.3
- Reaction products with sultones such as propionate sulfate, etc.

These nitrogen-containing monomers may be used alone or in combination of two or more.

Long chain unsaturated monomer (O is a radically polymerizable 2 monomer in one molecule)
It is an oil-based long-chain unsaturated monomer with one type bond and a molecular weight of about 150 to 1,000. Examples of such monomers include (1) hexyl (meth)acrylate, (meth)
C of (meth)acrylic acid such as octyl acrylate, acrylic (meth)acrylate, and stearyl (meth)acrylate
7 to 24 alkyl esters; (monocarboxylic acids such as non-drying oil fatty acids, semi-drying oil fatty acids, non-drying oil fatty acids, synthetic saturated fatty acids, etc., and 2- and droxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate Hydroxyalkyl (meth)acrylates represented by 9 are glycidyl (meth)acrylate, epoxy group-containing (meth)acrylates represented by zinclopenteny!Remeth I rare acrylate monoepoxide, etc., and aziridinylmethyl (meth)acrylates. Acrylate, aziridine group-containing (meth)acrylates represented by aziridinylethyl (meth)acrylate, etc., reaction products with epoxy group-containing allyl ethers represented by glycidyl allyl ether; (3) 1 hydroxyl group and 1 in the molecule
(4) Reaction product with oxyacid acrylate having a carboxyl group or epoxy group-containing (meth)acrylate, 1t aziridinyl group-containing (meth)acrylate, or epoxy group-containing allyl ether, etc.; (4) n-offal alcohol; Oleyl alcohol, phthyl cellosol, butyl calhitol, pesidyl alcohol, C2-z
+f) Compounds with one hydroxyl group in the molecule, such as adducts of % aliphatic monocarboxylic acid and 1,2-epoxy compounds, or compounds with one primary hydroxyl group and one secondary hydroxyl group in the molecule. Adducts of compounds having a tertiary hydroxyl group and incyanate ethyl (meth)acrylate, 2,2-didorotyl-m-improbenylpecidyl isocyanate, the above-mentioned hydroxyalkyl (meth)acrylate and diisocyanate, etc. Reaction products with incyanate group-containing acrylic monomers or incyanate group-containing styrene monomers represented by, or C-18 represented by (iso)butyl isocyanate tracryl isocyanate, phenyl isocyanate, etc. A reaction product of a saturated alkyl monoisocyanate compound or an aromatic monoisocyanate compound with the above-mentioned hydroxyalkyl (meth)acrylate, or a C6-24 compound represented by diptylamine, N-methyl-stearylamine, stearylamine, etc. A reaction product of a higher amine compound and the above-mentioned incyanate group-containing acrylic monomer or incyanate group-containing styrene monomer, etc. and (51C8-24 vinyl ether, (6) typified by Veo/ValO C6-24
(vinyl ester monomers).

As these monocarposi acid compounds, semi-drying oil fatty acids and drying oil fatty acids are preferably used.

The molecular weight of these long chain unsaturated monomers is approximately 170~
The range is 500.

These unsaturated monomers or unsaturated compounds may be used alone or in combination of two or more.

The α,β-ethylenically unsaturated monomers ((t) other than (2) to (O) above can be selected from a wide range depending on the desired performance of the dispersant. Such unsaturated monomers Representative examples are as follows.

(1) Esters of (meth)acrylic acid: For example, C1-Is alkyl esters of (meth)acrylic acid, 02-8 alkenyl esters of (meth)acrylic acid, (meth)
C2-8 hydroxyalkyl ester of acrylic acid, (
C3-18 alkenyloxyalkyl ester of meth)acrylic acid, general formula cHz-CHCOOC1Hz10R
' (wherein n is 2 to 6 and R' is a C1 to C6 alkyl group), an alkoxyalkyl acrylate ester with the general formula CH2-CHCOO+CmH2mO+
R' (where m is 2-3, R" is a hydrogen atom, 01-
c6 alkyl group), etc.

<2 Vinyl aromatic compounds: e.g. styrene, σ-
Methylstyrene, vinyltoluene, P-10 Rustyreshi, etc.

(3) Olefin compounds; for example, ethylene, propylene, diisobutene, butylene, olefin, isoprene, chloroprene, etc.

(4) Vinyl ethers: for example, methyl vinyl ether, ethyl vinyl ether, phthyl vinyl ether, etc.

(5) Vinyl esters: for example, vinyl propionate, vinyl pivalate, vinyl acetate, etc.

(6) Other monomers: For example, (meth)acrylonitrile.

These α,β-ethylenically unsaturated monomers may be used alone or in combination of two or more.

The method for producing the oligomer or polymer type surfactant includes the above component (a), component (C), and component (C).
Obtained by copolymerizing components d) with each other. The copolymerization can be produced by a method known per se.

The dispersing agent obtained by copolymerizing the above component (c) has a comb-shaped structure and clearly consists of a hydrophilic part and a lipophilic part. This shows excellent properties that do not impair the stability of alkyd resin emulsions.

The above-mentioned blending ratio in copolymerization can be changed depending on the desired performance of the dispersant, but it is appropriate to blend them in the following ratios.

Water-soluble unsaturated monomer (a): 0 to 70% by weight, or 3 to 50% by weight from the viewpoint of pigment dispersion. (υ: 0 to 70% by weight, preferably pigment dispersion) 5 to 60% by weight from the viewpoint of water-soluble unsaturated monomer (a) and/or nitrogen-containing unsaturated monomer (Tsuru: 5% by weight or more, preferably 10% by weight from the viewpoint of hydrophilicity) , long chain unsaturated monomer (c): 0 to 70% by weight, preferably 5 to 60% by weight considering the balance between hydrophilicity and hydrophobicity of the dispersant, α, l-ethylenically unsaturated monomer (d ): 0 to 90% by weight, the average molecular weight of the oligomer or polymer type dispersant of the present invention is 500 to ioo, ooo, preferably 1.000 to
30,000, more preferably 2,000 to IO,
The range is 000.

Furthermore, although the pigment dispersant of the present invention is an aqueous separating liquid using water as a medium, the alcohol-based organic solvent can be used if necessary.

The pigment (c) used in the present invention can be any commonly used inorganic or organic pigment. Examples of inorganic pigments include (1) oxides (zinc white, titanium dioxide, red iron oxide); , chromium oxide, cobalt blue, iron black, etc.);
(Dihydroxide type (alumina white, yellow iron oxide, etc.)
: (3) Sulfide, selenide type (zinc 'EIt) vermilion, cadmium yellow, cadmium red, etc.): (4) 7
(C) Sulfate series (precipitated baricum sulfate, etc.); (η carbonate series (sedimentated carbonate) (8) Silicates (hydrated silicates,
(9) Phosphate-based (manganese violet, etc.); (10) Carbon-based (carbon black, etc.)
(11) Metal powder-based pigments (aluminum powder, bronze powder, zinc powder #l) are listed, and organic pigments include (υnitroso pigment-based (naphthol green B, etc.)
(Knitro pigment type (Naphthol Yellow S, etc.): (3)
Azo pigments (Lysol Red, Lake Red C, Fast Yellow, Naphthol Red, Red, etc.): (4) Dyeing Lake Pigments (Alkali Blue Lake, "-Ta E N L")
/ -e, etc.): (5) 7-lycyanine l1lr series (7-lycyanine blue, 7-asto sky blue, etc.): (6)
Combined polycyclic pigment systems (perylene red, quinacridoshi red, dioxazine violet, isoindolinone yellow, etc.) are included.

It is appropriate that the aqueous coating composition of the present invention be blended in the following proportions.

The maleated alkyd resin emulsion (4) is 85 to 60% by weight in terms of solid content, preferably 10 to 50% by weight in terms of coating performance and coating appearance, and pigment (o: used in the coating material of the present invention). The application i9 is the required coating film properties fP.
! , VC6: 1 to 70% by weight, preferably 3 to 6% by weight, preferably 3 to 6% by weight, determined by the above meaning, Pigment dispersant: 0.001 to 6% by weight, determined by the type and amount of pigment used , 0901 from the viewpoint of storage stability, coating film performance, coating cost, etc.
-3% by weight Water [Weight: 10-807% by weight, preferably 20-70% by weight from the viewpoint of paint storage stability, painting workability, etc.

The aqueous coating composition obtained by blending as described above contains substantially no organic solvent, and is therefore suitable for use as a pollution-free coating.

The paint of the present invention is prepared by blending the pigment dispersant and the pigment within the scope of the present invention, and further using a ball mill, roll mill, homomixer, sand grinder, shaker, attritor, etc., which are commonly used in the paint industry. An aqueous pigment dispersion is prepared using a dispersing device. Further, it can be obtained by mixing the aqueous pigment dispersion with the maleated alkyd resin emulsion which does not substantially contain an organic solvent.

The aqueous coating composition of the present invention may optionally contain a dryer, an antifoaming agent, a thickener, a preservative, an aqueous resin other than the above, etc., but a wetting agent that helps reduce the pigment fraction is This is not preferred because it impairs water resistance.

In addition, the aqueous pigment dispersant used in the present invention makes it possible to stably mix and disperse pigments in maleated alkyd resin emulsions that do not contain amphiphilic organic solvents or emulsifiers, and the coatings obtained therefrom. G is excellent in coating film appearance and water resistance.

Although the effects of the present invention are not based on facts, the maleated alkyd resin emulsion of the present invention has a structure in which a carboxyl group is directly attached to a lipophilic fatty acid as described above, and an organic solvent is carefully added. Therefore, the particle surface of the resulting emulsion has a clear interface with the aqueous phase, which prevents intrusion by water or a neutralizing agent, and has excellent hydrolysis resistance. However, unlike other emulsions that are protected by hydrophilic groups other than anions, this structure is sensitive to shock, and these emulsions are treated with sulfate ester salts or sulfate-low salts used in emulsion paints as general pigment dispersants. Mixing active agents with strong acid groups such as molecular surfactants causes shock and cannot be used. On the other hand, nonionic or carboxylate type surfactants such as polyoxyethylene type nonionic surfactants, nonionic-anionic surfactants, and carboxylate type anionic surfactants have the same type of carboxyl group as the maleated alkyd resin emulsion. It is important to note that it is possible to alleviate the shock caused by the mixture of the nonionic type or the nonionic type. It has been recognized that oligomer or polymer type surfactants have a slow adsorption and desorption rate to emulsion particles, and as a result, they have excellent mixing stability with emulsions. 9. Coating 1III formed from the aqueous coating composition of the present invention uses an oxidized crosslinked resin emulsion as a vehicle, resulting in a dense coating; the dispersant does not overwhelm the coating, so it has excellent water resistance. It is.

The coating formed from the nine-bond coating composition obtained by the present invention is sufficiently crosslinked and cured at room temperature, but when heated in the presence or absence of an amino resin, etc., it cures in a short time and exhibits water resistance, corrosion resistance, etc. <A good coating pattern can be obtained.

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples. Hereinafter, parts and % indicate parts by weight and % by weight.

Production example of maleated alkyd resin emulsion (4) Tall oil fPi! Linoleic acid (trade name manufactured by Arayo Forest Products Industry Co., Ltd., Kan-Etol FAX) 40% linoleic acid, 3.2% linolic acid
, oleic 5232%, other 24.8%, iodine value 1
51) 497 parts of pentaerythritol, 204 parts of iso-7 tar acid, and 229 parts of benzoic acid were stirred in the presence of an esterification catalyst and subjected to a dehydration bonding reaction at about 240°C for about 10 hours to form an alkyd with an acid value of 1.5. m fat was obtained.

Subsequently, the temperature was cooled to about 200° C., 42 parts of maleic anhydride was added, and the maleation reaction was carried out for about 3 hours to obtain a maleated alkyd *i having a Gardner viscosity of Z4 (75% butyl cellosolve solution). Furthermore, this product was cooled to room temperature, water was added, and a sipping reaction was performed. 30 parts of isopropyl alcohol was added to 100 parts of the maleated alkyd resin to obtain a maleated alkyd resin solution having a total acid value of 37.1" and a donor viscosity of V (60% butyl cellosol solution). Next, the solution was heated at 40°C. After neutralizing the resin solution with 1.0 equivalent of triethylamine, deionized water was added dropwise to perform emulsification and dispersion, and the aqueous dispersion was heated at 40°C.
Then, the isopropyl alcohol is distilled off under reduced pressure to obtain a maleated alkyd resin emulsion (2).

The obtained emulsion (2) had a heating residue of 40.0%,
Amount of inpropyl alcohol relative to resin solid content: 1.0
%, viscosity *1 0.8 5 voids, P H 8.5 9
, 90 maleated alkyd + M fat emulsion with an average particle size of 0.14 μm (1 m (7)
Production example Linseed oil fatty acid 449 parts, pentaerythritol 212 parts
6 parts, 184 parts of iso-7 tar acid, and 260 parts of benzoic acid at about 240°C with stirring in the presence of an esterification catalyst.
An alkyd resin with an acid value of 2.9 was obtained by performing a dehydration bonding reaction for a period of time. Continue to lower the temperature to about 200℃ and make it waterless! 39 parts of reishic acid was added and a maleation reaction was carried out for about 3 hours to obtain a maleated alkyd resin having a Gardner viscosity of Z3 (75% butyl cellosolve solution). This product was further cooled to room temperature and subjected to a ring-opening reaction with water. 30 parts of isopropyl alcohol was added to 100 parts of the maleated alkyd resin to give a total acid value of 35.7 and a Gardner viscosity of U-V (60
% butyl cellosolve solution) to obtain a maleated alkyd resin solution. Next, in the same manner as in the preparation of the maleated alkyd m-fat emulsion (4), a maleated alkyd resin emulsion (yield) was obtained. The proportion of inpropyl alcohol per minute is 1.2%, the viscosity is 11 voids, the pH is 8.5 and 4, and the average particle size is 0.0 to 1μ.

Production side of the maleated alkyd resin emulsion (0) A maleated alkyd resin emulsion <0 was obtained using exactly the same method except that the degree of vacuum distillation was changed in the production of the maleated alkyd resin emulsion described above. 7 to the emulsion (Q is heating residue 44, 3%, ifjIi
The amount of inglovir alcohol based on the solid content of fat should be 1% or less, and the average particle size should be 0001 μm.Production Example of Pigment Dispersant (B) 350 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C. Next, 113 parts of glycidyl methacrylate-safflower fatty acid adductor was added to this solution.
A mixture of 126 parts of N-vinylpyrrolidone, 11 parts of acrylic acid, and 17.5 parts of azobisdimethylvaleronitrile was then added dropwise over about 2 hours.

1 hour after completion of dropping, add azobisisobutyronitrile 2.
5 parts of azobisisobutyronitrile were added to the reaction vessel after 1 hour, and after heating for an additional 2 hours,
Unreacted Zuma and n-butyl cellosolve were distilled off by vacuum distillation, resulting in a resin with an acid value of 35.8 and a Gardner viscosity of 0.
A copolymer of P (40% butyl cellosolve solution) for use as a pigment dispersant was obtained. Furthermore, the copolymer is triethylamine 1
A pigment dispersant (B) with a heating residue of 50% was obtained by neutralizing with a neutralization equivalent of 0.

Pigment dispersant (Preparation example) 325 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C.Next, 2-(1-aziridinyl)ethyl methacrylate and safflower oil fatty acid addition charge were added to this solution. 113 parts of Zummar, 126 parts of N-vinylpyrrolidone
A mixture of 11 parts of acrylic acid and 17.5 parts of azobisdimethylvaleronitrile was dissolved in 62.5 parts of butyl cellosolve, and the following were simultaneously added dropwise from a separate dropping port over about 2 hours to obtain the ratio. 30 minutes after completion of the dropwise addition, 1.25 parts of azobisisobutyronitrile was added and heated for an additional 30 minutes.

This operation of adding azobisisobutyronitrile was repeated 4 times, and a total of 5 parts of azobisisobutyronitrile was added.
Heat it for another 2 hours just to be sure. Next, after completing the following operations described above, unreacted monomers and n-butyl cellosolve were distilled off by vacuum distillation, resulting in a resin acid value of 53.7 and a Gardner viscosity of 0 (
A copolymer for a pigment dispersant (40% butyl cellosolve solution) was obtained.

The copolymer was also neutralized with 1.0 neutralization equivalent of triethylamine to obtain a pigment dispersant (E) with a heating residue of 50%.

Production example of pigment dispersant (C) 350 parts of n-butyl cellosolve was placed in a reaction vessel and heated to 120°C. Next, 113 parts of solution monomer (monomer obtained by adding 1 mole of 2-hydroxyethyl methacrylate and 1 mole of oleyl alcohol to 1 mole of tolylene diisocyanate), 126 parts of N-vinylpyrrolidone, ``A mixture of 11 parts of acrylic acid;
Dissolve 17.5 liters of azobisdimethylvaleronitrile in 60 parts of 7' til cellosolve, and add the following one drop at the same time from another dripping port over about 2 hours. One hour after the completion of the dropwise addition, 2.5 parts of azobisvaleronitrile was added, and after another 1 hour, 2.5 parts of azobispareronitrile was added, and after further heating for 2 hours, unreacted monomers and n-butyl cellosolve were distilled off under reduced pressure. A copolymer for a pigment dispersant having a resin acid value of 39.1 and a Gardner viscosity of 0-P (40% butyl cellosolve solution) was obtained. Furthermore, the copolymer was neutralized with 1.0 neutralization equivalent of triethylamine, and the heating residue was 50%.
Pigment dispersant (with special emphasis on O).

Production example of aqueous pigment dispersion ■ ~ [phase] 13 parts of titanium white, 10 parts of deionized water, and Noigeshi E
A mixture of 0.5 parts of A80 was dispersed using a Red Devi 1 separator for 40 minutes to obtain an aqueous pigment dispersion (9). Pigment dispersion was carried out in the same manner using the formulations shown in Table 1 below to obtain aqueous pigment dispersions (1) to (2).

Examples 1 to 16 Nine pieces obtained in the above production example 4! A water-based paint was prepared by mixing the pigment dispersions ■~■ and the maleated alkyd fat emulsion shown in Table 2, and the water-based paints of Examples 1 to 16 were applied to P4.The results are shown in Table 2 below. .

Comparative Examples 1-6 Water-based paints were prepared by mixing the aqueous pigment dispersions 0-@ obtained in the above production examples and the maleated alkyd resin emulsions shown in Table 2, and the water-based paints of Comparative Examples 17-22 were obtained. Nine.

The results are shown in Table 2 below.

Comparative Example 7 A mixture of 40 parts of maleated alkyd resin emulsion (A), 8 parts of butyl cellosolve organic solvent, and 13 parts of titanium white R-5N was dispersed using the same disperser as above, and the water-based paint of Comparative Example 7 was prepared. . The thickening of the paint after storage is likely due to swelling of the resin emulsion. A decline in the molecular weight was also observed. The results are shown in Table 2 below.

Comparative Example 8 Maleated Al-+FIlit16 Emulsion (A)
Dispersion was carried out using a mixture of 40 parts of titanium white R-5N and 13 parts of titanium white R-5N.

Comparative Example 9 Maleated alkyd resin! 5 parts of deionized water was added to a mixture of 36 parts of Lution (C) and 13 parts of Titanium White R-5N, and the mixture was dispersed using the same disperser as above, but the mixture agglomerated and dispersion was impossible.

(*1) Value measured with a B-type viscometer at 3 rpm.

(*2) Neugen EA80, 120.1501190D
: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene type nonionic surfactant Hitenol 8: manufactured by @1 Kogyo Seiyaku Co., Ltd., non-iocyanion type surfactant ~ Orotane 731 SD : manufactured by Rohm and Haas Co., Ltd., maleic anhydride - Diisobutene copolymer 5MA1440: Manufactured by ARIOCHEM, styrene-maleic anhydride copolymer Shimolin 0T70: Manufactured by Mitsubishi Kasei, formula RCOO-CH2 RCOO-CH-5Oa Na (Next R is a C8 alkyl group) Compound Tipol B81: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Alky I lepecizenesulfonic acid sorter (*3) Chitashi Shiro: Chikun Shiro R
-5N (product name), manufactured by Sakai Chemical Co., Ltd. Rutile type titanium oxide yellow: Yellow GKZR-8 (product name), manufactured by Kikuchi Shikoku Co., Ltd. IJ-n: fIA7 Russian Nishi Green 6YK (product name), manufactured by Toyo Ink Manufacturing Co., Ltd. Black: Carposi MA (product name), manufactured by Mitsubishi Kasei (Ui 4) (1): Burgescraner 60 (product name), B
Manufactured by URGESS PIGMENT (2): 5M clay (product name), manufactured by Fuji Light Industries (■: Hi-1 Drocarb 90 (product name), PLUSS
5 manufactured by TAUFER Co., Ltd. (*5) The state of the paint after stirring the mixture of the fe lacinized alkyd *i emulsion and the aqueous pigment dispersion as described in Examples or Comparative Examples.

(*6) Paint condition after storage at Jo℃ for 3 months (*7)
0.2 parts of a water-based dryer (trade name: 1 Deiknate "Cobalt Nowg" manufactured by Dainippon Ink Co., Ltd.) was blended with the Kuhonsei paints obtained in Examples 1 to 16 and Comparative Examples 1 to 7, and a maleated alkyd resin emulsion was added. (2) and ■Nike viscosity nWi agent (D) manufactured by Mum and Haas, trade name QR-7
08) was added to adjust the viscosity and then coated on a mild steel plate. After drying at 20°C and 75% relative humidity, it was tested.

Water Resistance: After drying for about a day, soak in tap water at 20°C for 1 day to check the condition of the painted surface. The evaluation criteria are as follows.

O (Good), O (Slight whitening), △ (Whitening), × (Significant whitening) Applicant (140) Kansai Paint Co., Ltd. A.

Claims (1)

[Scope of Claims] (A) 5 to 60% by weight solid content of an emulsion prepared by dispersing a neutralized maleated alkyd resin in water; (B) a polyoxyethylene type nonionic surfactant; 0.001 to 6% by weight of at least one aqueous pigment dispersant selected from anionic surfactants, carboxylate-type anionic surfactants, and oligomer or polymeric surfactants; (C) pigment; 1-70% by weight
, (D) 10 to 80% by weight of an aqueous medium, and (E) 0 to 7% by weight of an amphipathic organic solvent.