JP3421561B2 - Water-based paint composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an excellent coated surface gloss,
The present invention relates to a water-based glossy coating composition having weather resistance and storage stability, which comprises an extender pigment.

[0002]

2. Description of the Related Art In recent years, the problems of resource saving and environmental protection have been taken up on a global scale. In the paint field as well, a large amount of organic solvent discharged from an organic solvent type paint is not only a work environment but also a global environment scale. Air pollution has become a problem until now, and the needs for low-pollution paints such as water-based paints, powders, and high solid paints are rapidly increasing. Among them, water-based paints can significantly reduce the problems of organic solvent-based paints such as air pollution, fire risk, and toxicity.
It is attracting attention as an environmentally friendly paint. In addition, the conversion to water-based paints is becoming more and more accelerated in terms of solvent regulations due to the revision of the Fire Service Law and strengthening the standards of the Industrial Safety and Health Law. In addition, the recent trend toward high-grade paints, typified by fluorine-based and silicone-based paints, is due to soaring labor costs.
It is rapidly becoming popular, and rapid progress is being made in making these resins into water-based paints. In addition to these situations, studies have been made to provide paints with various functionalities, and recently paints that are less likely to become dirty and have excellent so-called stain resistance are becoming popular.

However, these water-based paints have the drawback of being inferior in the finish feeling of the coating film, the durability of the coating film, etc., as compared with the solvent-type coating material, and the high-grade feeling is inferior to the solvent-type coating material. The stain resistance can also be dealt with by using a resin such as fluorine or silicone, but it is still difficult to maintain high gloss in a water-based paint using an extender pigment. For example, by adding an extender pigment such as silica having a strong surface hydrophilicity, the stain resistance can be improved to some extent, but in the current usage conditions, the gloss is largely reduced and the water resistance is deteriorated.

Extending pigments in water-based paints include titanium, barium sulfate, kaolin clay, silica, talc,
The present situation is that calcium carbonate and the like are used, and different types are properly used according to various uses, but the present state of the extender pigment will be described by taking the most widely used calcium carbonate as an example. It has been widely known that calcium carbonate is used as an extender pigment in water-based paints, and various calcium carbonates can be used depending on the application such as particle diameter, particle shape, particle size distribution, presence or absence of surface treatment, and type and amount thereof. Is used. When calcium carbonate is used as an extender pigment, heavy calcium carbonate, light calcium carbonate, and primary particle diameters having coarse primary particles with an average primary particle diameter exceeding 0.5 μm and a particle size distribution broadly exceeding 2 μm. Colloidal calcium carbonate, which is present as secondary agglomerated particles exceeding 0.5 μm, significantly reduces coating film performance and can only serve as an extender for undercoating and intermediate coating, maintaining high quality of coating film. It's a long way off.

Further, in order to prevent the agglomeration of the calcium carbonate particles during dry powdering of the colloidal calcium carbonate,
A method of surface-treating the calcium carbonate slurry with a higher fatty acid, a resin acid, an alkali metal salt thereof, or the like is adopted, but such a method still fails to obtain sufficient dispersibility, and gloss or other particles thereof. At present, the physical properties expected from the diameter are not exerted, and they do not contribute to stain resistance. Further, even if dispersed mechanically by applying a large amount of energy, the dispersion stability with time is poor, and the physical properties of the coating material such as thickening and deterioration of the gloss of the coating material after storage are caused. Other extender pigments also have the same problems as the above calcium carbonate, and extender pigments having excellent functions such as excellent coating surface gloss, weather resistance, storage stability and stain resistance have not yet been obtained. .

In order to improve these points, the present inventors have
Already disclosed in JP-A-61-69872 and JP-A-61-6987.
3, JP-A-62-212479, JP-A-62-21224
No. 80, a surface treatment agent for an extender pigment containing calcium carbonate, a surface treatment method, etc. are proposed, but at present the finish feeling and durability of the coating film are inferior to those of solvent-based paints. However, the stain resistance has not yet been improved. As a compounding agent in the water-based paint, a wetting agent, a dispersant, etc. may be mentioned as a compounding agent for enhancing the function of the pigment, but these are generally titanium white, which has an important role as a white pigment, or other materials. However, it is insufficient for enhancing the function of the extender pigment and compensating for the above-mentioned drawbacks.

[0007]

In view of the above situation, the present invention solves the above problems, has excellent dispersibility of extender pigment, retains gloss retention, and is excellent in durability and stain resistance. An object is to provide an aqueous coating composition.

[0008]

Means for Solving the Problems As a result of intensive investigations aimed at solving the above problems, the present inventors have found that in an aqueous paint containing an extender pigment, two or more specific substances are combined in the paint. It has been found that, by virtue of the above, it is possible to obtain a coating film having good affinity with the surface of the extender pigment and the resin, maintaining the dispersibility of the particles for a long period of time and maintaining high glossiness, and having excellent durability and stain resistance. The present invention has been completed.

That is, the present invention relates to a water-based paint prepared by blending an extender pigment, which is a polymer of at least one monomer selected from the following [Group A], and a partial or complete mixture thereof with an alkali metal, ammonium and amine. At least one kind (X) selected from the group consisting of neutralized products, and [B
A group selected from the group] and at least one (Y) selected from the group consisting of alkali metal salts, ammonium salts, amine salts and halides thereof. It is what [Group A] (I) α, β unsaturated monocarboxylic acid, (II)
α, β unsaturated dicarboxylic acid, (III) (a) (meth) acrylic acid alkyl ester, (b) alkoxy group-containing (meth) acrylic ether, (c) cyclohexyl group-containing (meth) acrylate, (d) α, β monoethylenically unsaturated hydroxy ester, (e) polyalkylene glycol mono (meth) acrylate, (f) vinyl ester, (g) vinyl aromatic, (h) unsaturated nitrile, (i) unsaturated dicarboxylic acid Acid ester, (j) vinyl ether, (k) conjugated diene, chain olefin, cyclic olefin (IV) sulfo group-containing monomer [B group] (I) (a) alkyl ether sulfuric acid, (b) alkyl ether phosphoric acid, (C) Alkyl aryl ether sulfuric acid, (d) Alkyl aryl ether phosphoric acid, (II)
(A) alkyl sulfate, (b) alkyl phosphate, (c) alkyl aryl sulfate, (d) alkyl aryl phosphate, (e) alkyl amide sulfate, (II)
I) (a) alkyl sulfonic acid, (b) alkyl benzene sulfonic acid, (c) alkyl naphthalene sulfonic acid,
(D) sulfosuccinic acid, (e) sulfosuccinic acid ester, (f) α-olefin sulfonic acid, (g) N-acyl sulfonic acid, (IV) (a) N-acyl amino acid,
(B) alkyl ether carboxylic acid, (c) acylated peptide, (V) (a) aliphatic amine, (b) aliphatic quaternary ammonium, (c) aromatic quaternary ammonium, (d)
Heterocyclic quaternary ammonium, (VI) (a) betaine,
(B) aminocarboxylic acid, (c) imidazoline derivative,
(VII) (a) alkyl ether, (b) alkyl allyl ether, (c) alkyl ester, (d) alkyl amine, (e) sorbitan derivative, (f) polycyclic phenyl ether, (g) fatty acid ester, (VIII ) (A) Fluoroalkylcarboxylic acid, (b) perfluoroalkylcarboxylic acid, (c) perfluoroalkylsulfonic acid,
(IX) (a) acetylene alcohol, (b) acetylene glycol

In the present invention, the "average particle size" means the average value of the diameters obtained by assuming that the inorganic particles confirmed by an electron microscope are spherical particles.

The substances used in the present invention and their roles in the water-based paint will be described in detail. (I) in the group A constituting (X) is a homopolymer or copolymer of α, β unsaturated monocarboxylic acid exemplified by acrylic acid, methacrylic acid, crotonic acid and the like, and alkali metals thereof. Ammonium, a partially or completely neutralized product with an amine,
It has a function of stabilizing the extender pigment in the paint in a dispersed state. (II) in group A is a homopolymer or copolymer of α and β dicarboxylic acids exemplified by maleic acid, itaconic acid and fumaric acid, and their partial or complete neutralization with alkali metals, ammonium and amines. Similar to (I), it has the function of stabilizing and stabilizing the extender pigment in the paint, and is particularly useful for fine particles of 0.3 μm or less.

(III) in Group A is (a) methyl (meth) acrylate, ethyl, propyl, isobutyl, 2-
Acrylic acid alkyl esters and methacrylic acid alkyl esters exemplified by ethylhexyl, etc., (b) Methoxyethyl (meth) acrylate, acrylates and methacrylates having an alkoxy group exemplified by ethoxyethyl (meth) acrylate, etc., (c) cyclohexyl ( Acrylates and methacrylates having a cyclohexyl group exemplified by (meth) acrylate and the like, (d) 2
Α, β monoethylenically unsaturated hydroxy ester exemplified by hydroxyethyl (meth) acrylate,
(E) Polyalkylene glycol monoacrylate and methacrylate exemplified by polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate, (f) vinyl esters such as vinyl acetate and vinyl stearate, and (g) styrene. Vinyl-based aromatics such as vinyltoluene, (h) unsaturated nitriles exemplified by acrylonitrile, methacrylonitrile, etc., (i) monomethyl maleate, unsaturated dicarboxylic acid esters such as dibutyl itaconate, (j) methyl vinyl ether, Vinyl ethers exemplified by butyl vinyl ether etc., (k) butadiene, isobutene, ethylene, propylene, n-butene, conjugated dienes exemplified by n-pentene, cyclobutene etc., chain olefins, cyclic olefins, Increasing the compatibility with the quality pigment and a resin,
Maintains a stable dispersed state for a long time, and has high gloss, durability of the coating film,
Contributes to stain resistance.

Particularly, in the polyalkylene glycol mono (meth) acrylate of Group A (III) (e), the following formula

[0014]

[Chemical 2]

(Wherein R ₁ is hydrogen or a methyl group, Z is a ring-opened and added divalent alkylene oxide residue having 2 to 4 carbon atoms, n is an average of 1 to 30 and R ₂ is Carbon number 4
To 30 alkyl groups, alkenyl groups, aryl groups, alkyl groups having an aryl group as a substituent, cyclic alkyl groups, cyclic alkenyl groups, or monovalent organic groups derived from heterocyclic compounds. ), By adding the above-specified components to R ₂ , the affinity with the coating vehicle is maintained for a long time, the high gloss is maintained for a long time, and the durability of the coating film, It is preferable because the stain resistance becomes good.

Examples of this monomer include butoxy polyethylene glycol (meth) acrylate, butoxy polypropylene glycol (meth) acrylate, octyloxy polyethylene glycol (meth) acrylate, octyloxy polyethylene glycol-polypropylene glycol (meth) acrylate, and phenoxy. Polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, naphthoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, naphthoxy polyethylene glycol-polypropylene glycol (meth) acrylate, p-methylphenoxy polyethylene Glycol (meth) acrylate, benzyloxypolyene Glycol (meth) acrylate, cyclohexoxy polyethylene glycol (meth)
Acrylate, cyclopentenoxy polyethylene glycol (meth) acrylate, pyridyloxy polyethylene glycol (meth) acrylate, thienyloxy polyethylene glycol (meth) acrylate, and the like, having 4 to 30 carbon atoms as the end group of the polyalkylene glycol chain.
-Terminated ether-type poly (alkylene glycol) monoalkyl groups, alkenyl groups, aryl groups, alkyl groups having aryl groups as substituents, cyclic alkyl groups, cyclic alkenyl groups, and monovalent organic groups derived from heterocyclic compounds (Meth) acrylate is mentioned as an example.

(IV) in Group A is a homopolymer or copolymer of a sulfo group-containing monomer exemplified by hydroxyethylacrylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and the like. It is a partially or completely neutralized product of an alkali metal, ammonium, or amine, which also has the function of stabilizing the extender pigment in the paint in a dispersed state, but the inclusion of a sulfo group causes steric hindrance between particles. It is preferable because it has a function of preventing aggregation of particles.

Further, (I) in the group B constituting (Y) is (a) an alkyl ether sulfuric acid exemplified by polyoxyethylene alkyl ether sulfuric acid and the like, and an alkali metal salt, an ammonium salt, an amine salt thereof, ( b) Alkyl ether phosphoric acid exemplified by polyoxyethylene alkyl ether phosphoric acid and the like, and its alkali metal salts, ammonium salts, amine salts, (c) alkyl aryl ether sulfuric acid exemplified by polyoxyethylene alkylphenyl ether sulfuric acid, and the like, and Examples thereof include alkali metal salts, ammonium salts, amine salts, (d) polyoxyethylene alkylphenyl ether phosphoric acid and other alkylaryl ether phosphoric acids, and alkali metal salts, ammonium salts, amine salts and the like thereof.

(II) in group B is (a) an alkyl sulfuric acid ester exemplified by polyoxyalkyl sulfuric acid ester, and its alkali metal salt, ammonium salt, amine salt, (b) polyoxyalkyl phosphoric acid ester, etc. Alkyl phosphoric acid esters exemplified, and their alkali metal salts, ammonium salts, amine salts, (c) alkylaryl sulfuric acid esters exemplified by polyoxyalkylphenyl sulfuric acid esters and the like, and their alkali metal salts, ammonium salts, amine salts, (D) Alkylaryl phosphates exemplified by polyoxyalkylphenyl phosphates and the like, and alkali amide salts, ammonium salts, amine salts thereof, and alkylamide sulfates exemplified by (e) fatty acid alkylolamide sulfates. , And their alkali metal salts, Moniumu salts, amine salts as an example.

(III) in Group B is (a) an alkyl sulfonic acid exemplified by polyoxyethylene alkyl sulfonic acid and the like, and alkali metal salts and ammonium salts thereof.
Amine salt, (b) alkylbenzene sulfonic acid, and its alkali metal salt, ammonium salt, amine salt, (c)
Alkylnaphthalenesulfonic acid and its alkali metal salt, ammonium salt, amine salt, (d) sulfosuccinic acid, and its alkali metal salt, ammonium salt, amine salt, (e) dialkyl sulfosuccinic acid ester, and the like. And its alkali metal salt, ammonium salt, amine salt, (f) α-olefin sulfonic acid, and its alkali metal salt, ammonium salt, amine salt, (g) N-acyl sulfonic acid, and its alkali metal salt, ammonium , Amine salts.

(IV) in group B is (a) N-acyl amino acid, and its alkali metal salt, ammonium salt,
Amine salts, (b) alkyl ether carboxylic acids, and their alkali metal salts, ammonium salts, amine salts, (c)
Examples include acylated peptides. (V) in group B
Are, for example, (a) an aliphatic amine halide, (b) an aliphatic quaternary ammonium halide, (c) an aromatic quaternary ammonium halide, and (d) a heterocyclic quaternary ammonium halide. can give. (VI) in the group B is (a) betaine exemplified by carboxybetaine, sulfobetaine, etc., (b) aminocarboxylic acid,
(C) Examples include imidazoline derivatives.

(VII) in Group B is (a) an alkyl ether exemplified by polyoxyethylene alkyl ether, (b) an alkyl allyl ether exemplified by polyoxyethylene nonylphenyl ether, and (c) polyoxy. Alkyl ester exemplified by ethylene oleate and the like, (d) alkylamine exemplified by polyoxyethylene alkylamine and the like, (e) sorbitan derivative exemplified by sorbitan laurate and the like, (f) polycyclic phenyl ether, ( g) Fatty acid esters. (VIII) in Group B is (a) fluoroalkylcarboxylic acid and its alkali metal salt, ammonium salt, amine salt, (b) perfluoroalkylcarboxylic acid and its alkali metal salt, ammonium salt, amine salt, ( c) Perfluoroalkylsulfonic acid, and its alkali metal salts, ammonium salts, and amine salts. (IX) in group B is (a) 3-methyl-1-pentyne-3-
Acetylene alcohol exemplified by oar etc., (b)
An acetylene glycol exemplified by 3,6-dimethyl-4-octyne-3,6-diol and the like can be mentioned. At least one kind (Y) selected from (I) to (IX) of group B enhances the dispersion stability of the resin, and at least one kind (X) selected from (I) to (IV) of group A together with By using it, the dispersion stability of the extender pigment and the resin becomes even better,
The high gloss and weather resistance of the coating film are dramatically improved. The alkyl group mentioned here includes, for example, higher alcohols such as hexyl, octyl, lauryl and ceryl, but is not limited thereto. Further, particularly when the purpose is workability at the time of coating, the viscosity is extremely low when the mill base is made, and the work time and dispersion cost are reduced (I), (II), (III), (IX). Good to do.

When at least one kind (X) selected from the group A and at least one kind (Y) selected from the group B are compounded in the water-based paint, the compounding amount is not particularly limited. Each of (X) and (Y) is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the extender pigment to be blended. If the blending amount of (X) and (Y) is less than 0.01 parts by weight, the effect is less prominent as compared with the case of no addition, and even if the blending amount exceeds 10 parts by weight, it is more remarkable. Since it is difficult to expect such an effect, it is economically disadvantageous. In some cases, the free additive may hinder the film-forming property of the coating film, which may have an adverse effect.

When the effect of a polymer selected from the group A constituting (X) is expected to be greater, (I) of group A,
It is preferable to use a copolymer of monomers belonging to (II), (III) and (IV), and the copolymerization ratio is not particularly limited, but preferably the monomer belonging to (I) 0 to 100 parts by weight of the monomer belonging to (II), relative to 100 parts by weight,
It is preferable to use 5 to 300 parts by weight of the monomer belonging to (III) and 0 to 100 parts by weight of the monomer belonging to (IV). (II),
As described above, the component (IV) has an effect on a particularly fine region of the extender pigment, and therefore, in consideration of the type of extender pigment, the particle size, the viscosity of the final paint, etc., 0 part by weight in the copolymer. However, if the amount exceeds 100 parts by weight, the paint may gel and it may hinder the use depending on the kind of film-forming auxiliary compounded in the paint. Therefore, in terms of paint design, it is more preferable that the amount is 2 per 100 parts by weight of component (I).
To 70 parts by weight, more preferably 5 to 50 parts by weight. When the amount of the component (III) is less than 5 parts by weight with respect to 100 parts by weight of the component (I), the effect may not be sufficient even if a coating material using this copolymer is prepared.
If it exceeds 0 parts by weight, foaming may be significantly reduced when dispersing the extender pigment, and the solubility of the copolymer in water may be significantly lowered, so that the extender pigment may be uniformly adsorbed on the surface. It can be difficult.

Number average molecular weight of homopolymer or copolymer used in the present invention (measured by gel osmotic pressure chromatography)
Varies depending on constituent components, constituent ratios, etc. and cannot be specified unconditionally, but is usually 500 to 50,000, preferably 2,000 to
It is good to set it to about 30,000. If the molecular weight is less than 500, the adsorption rate tends to decrease, and if it exceeds 50,000, it becomes difficult to produce the homopolymer or copolymer itself.
The paint viscosity may increase significantly.

These homopolymers or copolymers can be obtained by a conventionally known method. Examples thereof include polymerization in a solvent such as water, an organic solvent, or a mixture of a water-soluble organic solvent and water. At this time, for polymerization in an aqueous medium, a persulfate or a persulfate is used as a polymerization initiator. Hydrogen oxide or the like is used, and a promoter such as sodium bisulfite or ascorbic acid can be used. For polymerization in an organic solvent, an azo compound, an organic peroxide or the like is used as a polymerization initiator, and an accelerator such as an amine compound can be used in combination. For polymerization in a mixed solvent of a water-soluble organic solvent and water, it is possible to appropriately select and use from the above various polymerization initiators or a combination of a polymerization initiator and an accelerator. The polymer thus obtained can be optionally neutralized or partially neutralized with an alkali metal such as sodium or an alkaline substance such as ammonium or amine.

The compounds belonging to the group B constituting (Y) are
It can be obtained by a conventionally known method. For example, a method of converting a higher alcohol into a sulfuric acid ester with concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfurous acid, etc., a method of converting the higher alcohol into a phosphoric acid ester with phosphorus pentoxide, phosphorus oxychloride, phosphorus trioxide, etc. Examples include a method of obtaining each ester by using the above-mentioned sulfating agent and phosphorylating agent after addition polymerization and etherification, and may be neutralized with an alkali metal, ammonium, organic amine or the like, if necessary. .

The extender pigment in the present invention is titanium, barium sulfate, kaolin clay, silica, talc, calcium carbonate, mica, etc. as mentioned above, and these may be used alone or in combination of two or more. It is preferable to use calcium carbonate to further enhance the effect. Among them, it is preferable to use precipitated calcium carbonate having an average particle diameter of 0.01 to 0.5 μm. Precipitated calcium carbonate is relatively inexpensive, has a smaller specific gravity than barium sulfate, and has a large compounding effect. In addition, it is easy to control the particle size and obtain a sharp particle size distribution. Further, it is preferable that the calcium carbonate used has a specific X-ray diffraction intensity ratio (I ₁ / I ₀ ). The term "diffraction intensity ratio" as used herein means a ratio when the diffracted intensity on the 108th face and the diffracted intensity on the 116th face of calcite-based calcium carbonate are I ₀ and I ₁ , respectively, and the range is 80≤ (I ₁ / I ₀ ) ≦ 140
Is preferable, and 90 ≦ (I ₁ / I ₀ ) ≦ 130 is more preferable. If this strength ratio is less than 80, it may be difficult to obtain a good dispersion state in the paint, and if it exceeds 140, particle agglomeration of the paint may occur over time. May lead to a decrease in

The precipitation-produced calcium carbonate used in the present invention can be produced by, for example, a method of passing a carbon dioxide gas-containing gas (hereinafter, carbon dioxide gas) through a calcium hydroxide aqueous suspension (hereinafter, lime milk), or carbon dioxide. A known method such as a method of spraying lime milk or a mixed solution of calcium hydroxide and precipitated calcium carbonate into the gas may be used. Further, it is preferable to disperse the calcium carbonate particles as much as possible. As a method for this, for example, the carbonation reaction is stopped at pH of the reaction system at 7.5 to 10.0 and stirring is carried out in the calcium carbonate. It is easily achieved by eluting the residual alkali content in the solution and adding or conducting lime milk and carbon dioxide gas into the system as needed to control the pH of the system at 9.0 to 12.0 for 5 hours or more. .

In the present invention, the above-mentioned (X) and (Y) are added at the time of compounding of the water-based paint, but the composition at the time of compounding and (X) and / or (Y) is preliminarily surface-treated. It may be used in combination as a pigment addition, and this combination is particularly effective when using a fine particle extender pigment in which agglomeration during drying is a problem. Examples of the combined use include addition of (X) and (Y) at the time of compounding, combination of an extender pigment surface-treated with (X) and (Y), and addition of (X) at the time of compounding and (Y). Combined use with surface-treated extender pigment, addition of (Y) at the time of compounding and (X)
Any of these may be used in combination with the extender pigment whose surface has been treated with.

A method of adding (X) and / or (Y) (hereinafter referred to as a surface treatment agent) to an extender pigment and adsorbing it to obtain a surface-treated powder can be carried out by a conventional method, for example, as described above. The average primary particle diameter obtained by the production method is 0.01 to 0.
It is produced by adding to a calcium carbonate slurry for precipitation of 5 μm, uniformly mixing by stirring or the like to adsorb the surface treating agent on the calcium carbonate particles, and then dehydrating, drying and powdering with a filter press or the like. It is also possible to dehydrate the carbonated calcium carbonate slurry once, add the surface treatment agent to the calcium carbonate press cake, stir vigorously, and then dry and pulverize with a spray dryer or the like. . Further, as a method of firmly adhering to the surface of calcium carbonate, it is effective to disperse the calcium carbonate slurry to which the surface treating agent is added by a continuous wet disperser such as a sand grinder before drying.

The amount of the surface treatment agent (X) and / or (Y) added to and adsorbed on the extender pigment is not particularly limited, but both (X) and (Y) are preferably 100 weight% of the extender pigment. The amount is preferably 0.01 to 20 parts by weight, and more preferably 0.1 to 10 parts by weight.
However, it is preferable that the surface treatment amount of the composition belonging to each of (X) and (Y) does not exceed 10 parts by weight. If the amount added is less than 0.01 parts by weight, the surface treatment effect is less prominent as compared to the untreated product, and if the amount added exceeds 20 parts by weight, the adsorption rate for the excess is reduced and the surface treatment agent is more remarkable. It is difficult to expect an effect and is often economically disadvantageous.

These specific surface treatment agents (X) and / or
It is preferable that the extender pigment surface-treated with (Y) is finally blended as a powder in the water-based paint because the degree of freedom in paint design increases, but if there is no problem in paint design, the energy of drying and powdering is preferable. In order to reduce the cost, the surface treatment agent may be added to the water suspension of the extender pigment and blended as it is in the water-based paint. When surface-treating (X) and / or (Y), other dispersants and wetting agents such as sodium hexametaphosphate and potassium tripolyphosphate may be used in combination, if necessary.

The types of water-based paint resins include alkyd-based, acrylic-based, vinyl acetate-based, urethane-based, silicone-based, fluorine-based, styrene-based, melamine-based, epoxy-based general-use paint emulsion resins, alkyd-based resins, and the like. Amine-based, styrene-allyl alcohol-based, aminoalkyd-based, polybutadiene-based, etc. water-soluble resins for general paints, dispersion resins for paints in which emulsion resins and water-soluble resins are blended, and dispersions using cross-linked water-soluble resins as emulsifiers It can be appropriately selected from resins, acrylic hydrosols and the like, and it is also possible to use two or more kinds of these resin components in combination.

The amount of the extender pigment used in these paints is not particularly limited, but is preferably 5 to 150 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the resin solid content. Parts by weight. If the blending amount is less than 5 parts by weight, the intended effect is not sufficiently exhibited and it is disadvantageous in terms of cost, and if the blending amount exceeds 150 parts by weight, the gloss may be significantly lowered. When making water-based paints, color pigments for paints and other extender pigments, defoamers, non-adhesives, wetting agents, dispersants, curing accelerators, antiseptics, antifungal agents, film-forming aids, antifreeze agents. Etc. One or more of the additives usually used in this field can be added to the coating composition of the present invention, if necessary.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but it goes without saying that the present invention is not limited by these.

Examples 1 to 5, 11 to 13 Lime milk having a specific gravity of 1.07 was prepared at 15 ° C., and 30 liter / min of carbon dioxide gas (25% of which was contained per 1 kg of calcium hydroxide).
CO ₂ ) is conducted to carry out a carbonation reaction, and the pH of the system is 8.0.
The carbonation reaction is stopped when the temperature reaches 50 ° C. and pH is 10.
The mixture was stirred at 2 for 15 hours, and when the viscosity of the system reached 2300 cp, carbon dioxide gas was supplied again to adjust the pH of the system to 6.8. As a result, a calcium carbonate slurry having an average primary particle diameter of 0.1 μm with very few aggregate particles was obtained. The X-ray intensity ratio of this calcium carbonate was 120. This calcium carbonate slurry was dehydrated by a filter press to obtain a press cake having a solid content concentration of 60% by weight. Along with this presscake, the substances (X) and (Y) selected from the groups A and B shown in Tables 1 and 2 were blended, and the acrylic emulsion paint was prepared based on the following formulation table and coating preparation method. A composition was obtained.

(Coating Formulation Table) a. Acrylic / styrene resin (solid content 50%) 200.00 parts by weight (solid 100.00) b. Dispersant (Discoat N-14, Dai-ichi Kogyo Seiyaku Co., Ltd.) 4.85 〃 c. Antifreeze agent (ethylene glycol) 4.39 〃 d. Defoaming agent (Nopco 8034L / San Nopco) 4.39 〃 e. Titanium (R-930 / Ishihara Sangyo) 44.04 〃 f. Extender pigments listed in attached table g. (X) Listed in a separate table h. (Y) Listed in Table i. Film-forming aid 1 (butyl cellosolve) 11.01 parts by weight j. Film-forming aid 2 (CS-12 / Chisso) 9.00 〃 k. Thickener (Adecan UH420 / Asahi Denka Kogyo) 10.22 〃 l. Preservative (Mornon # 800, Katayama Chemical Research Institute) 0.42 〃 m. Water Appropriately (Paint preparation method) The above b to h and m are all about 500cc.
Each compounding agent is sequentially charged into a 1-liter container while gently stirring with a 6 cm dissolver blade, and after all the compounding agents are charged, external cooling is performed at 3000 rpm.
At 20 minutes, it was dispersed and mixed to prepare a mill base. Next, the remaining compounding ingredients were sequentially added to this mill base with gentle stirring, and after the addition, the mixture was stirred at 3000 rpm for 5 minutes to prepare a test paint.

The characteristics of the obtained coating composition were measured by the following methods. The results are shown in Table 4. (Physical properties of initial coating material) The coating material was allowed to stand in a constant temperature bath at 20 ° C for 48 hours for defoaming, and the initial physical properties of the coating material were evaluated using this material. (Physical Properties of Daily Paint) The paint was allowed to stand and defoamed in a constant temperature bath at 50 ° C. for 10 days, and the physical properties of the paint were evaluated using this product. Viscosity: Values at 2 rpm and 20 rpm measured by a B-type viscometer. Gloss: 6 after coating the finished paint on a glass plate with a doctor blade for 4 min and drying at 20 ° C for 2 days
0 ° -60 ° gloss. ΔE: Color difference of the coating film after the 6-month outdoor exposure test with the initial coating film as the standard.

Examples 6 to 10 and 14 to 15 extender pigments are kaolin clay (average particle diameter 0.8 μm),
Barium sulfate (average particle size 0.2 μm), ground calcium carbonate (average particle size 3.0 μm, X-ray diffraction intensity ratio 7
5), light calcium carbonate (average particle size 1.8 μm, X
The line diffraction intensity ratio 95) and the substances (X) and (Y) selected from the A group and the B group are set as shown in Tables 1 and 2, and an acrylic emulsion coating composition is prepared based on the above formulation table and preparation method. Obtained. The evaluation results are shown in Table 4.

Comparative Examples 1 to 5 Using the presscake having a solid content concentration of 60% by weight obtained in Example 1 and the substance (X) or (Y) shown in Table 3, based on the above formulation table and preparation method. An acrylic emulsion coating composition was obtained. The evaluation results are shown in Table 5.

Comparative Examples 6 to 8 Using the kaolin clay, barium sulfate and ground calcium carbonate used in Examples 6 to 9, the substance (X) shown in Table 3 was used.
Alternatively, an acrylic emulsion coating composition was obtained by blending with (Y) at the same time based on the above formulation table and preparation method. The evaluation results are shown in Table 5.

Examples 16 to 18 In a press cake having a solid content concentration of 60% by weight obtained in the same manner as in Example 1, a substance (X) selected from Group A and / or Group B shown in Table 6, (Y) was added, and the mixture was vigorously stirred to be sufficiently adsorbed on the surface of calcium carbonate, and then dried by a spray dryer to obtain a powdery extender pigment. Using the extender pigment thus obtained,
Furthermore, (X) and / or (Y) described in Table 7 was added to the coating material to prepare an acrylic emulsion coating composition based on the above formulation table and preparation method. This evaluation result is shown in Table 8.
Shown in.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

[Table 8]

[0052]

INDUSTRIAL APPLICABILITY The water-based paint according to the present invention has a good affinity between the extender pigment and the vehicle in the paint for a long period of time by incorporating the specific substances (X) and (Y) into the paint. , As a result, the dispersion state of the extender pigment is stable, the gloss retention is good, and the extender pigment is uniformly present on the surface of the coating film, as compared with a coating using a conventionally known extender pigment, A remarkable antifouling effect can be obtained. Further, a sufficient effect can be expected even in a water-based paint in which an extender pigment could not be used because of deterioration in gloss, weather resistance and stain resistance.

Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09D 7/12 C09D 7/12 131/02 131/02 133/02 133/02 133/04 133/04 133/18 133/18 135/00 135/00 141/00 141/00 (56) Reference JP-A-54-23635 (JP, A) JP-A-61-60767 (JP, A) JP-A-59-49836 (JP, A) JP-A 56-104713 (JP, A) JP-A-57-10657 (JP, A) JP-B-46-15771 (JP, B1) JP-B-55-5075 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 129/10 C09C 1/02 C09C 3/08 C09C 3/10 C09D 5/00 C09D 7/12 C09D 131/02 C09D 133/02 C09D 133/04 C09D 133/18 C09D 135 / 00 C09D 141/00

Claims (8)

(57) [Claims] 1. A water-based coating composition containing an extender pigment, comprising a polymer of at least one monomer selected from the following [Group A], and a partially or completely neutralized product thereof with an alkali metal, ammonium and amine. At least one kind (X) selected from the group consisting of: and a compound selected from the following [Group B], and at least one kind (Y) selected from the group consisting of an alkali metal salt, an ammonium salt, an amine salt and a halide thereof. A water-based coating composition comprising: [Group A] (I) α, β unsaturated monocarboxylic acid, (II) α, β unsaturated dicarboxylic acid, (III) (a) (meth) acrylic acid alkyl ester,
(B) (meth) acrylic ether having an alkoxy group, (c) (meth) acrylate having a cyclohexyl group, (d) α, β monoethylenically unsaturated hydroxy ester, (e) polyalkylene glycol mono (meth)
Acrylate, (f) vinyl ester, (g) vinyl aromatic, (h) unsaturated nitrile, (i) unsaturated dicarboxylic acid ester, (j) vinyl ether, (k) conjugated diene, chain olefin, cyclic olefin ( IV) Sulfo group-containing monomer [Group B] (I) (a) Alkyl ether sulfuric acid, (b) Alkyl ether phosphoric acid, (c) Alkyl aryl ether sulfuric acid,
(D) Alkyl aryl ether phosphoric acid, (II) (a) Alkyl sulfuric acid ester, (b) Alkyl phosphoric acid ester, (c) Alkyl aryl sulfuric acid, (d) Alkyl aryl phosphoric acid, (e) Alkyl amide sulfuric acid ester, (III) (A) alkyl sulfonic acid, (b) alkyl benzene sulfonic acid, (c) alkyl naphthalene sulfonic acid, (d) sulfosuccinic acid, (e) sulfosuccinic acid ester, (f) α-olefin sulfonic acid, (g) N-acyl Sulfonic acid, (IV) (a) N-acyl amino acid, (b) alkyl ether carboxylic acid, (c) acylated peptide, (V) (a) aliphatic amine, (b) aliphatic quaternary ammonium, (c) ) Aromatic quaternary ammonium, (d) heterocycle 4
Quaternary ammonium, (VI) (a) betaine, (b) aminocarboxylic acid,
(C) imidazoline derivative, (VII) (a) alkyl ether, (b) alkyl allyl ether, (c) alkyl ester, (d) alkyl amine, (e) sorbitan derivative, (f) polycyclic phenyl ether, (g) ) Fatty acid ester, (VIII) (a) Fluoroalkylcarboxylic acid, (b) Perfluoroalkylcarboxylic acid, (c) Perfluoroalkylsulfonic acid, (IX) (a) Acetylene alcohol, (b) Acetylene glycol 2. The (X) based on 100 parts by weight of the extender pigment.
Is blended in an amount of 0.01 to 10 parts by weight, and (Y) is blended in an amount of 0.01 to 10 parts by weight. 3. The copolymerization ratio of the polymer in the group A of (X) is 100 parts by weight of the monomer belonging to (I).
0 to 100 parts by weight of monomer belonging to (II), 5 to 300 parts by weight of monomer belonging to (III), 0 to monomer belonging to (IV)
The water-based coating composition according to claim 1, which is 100 parts by weight. 4. The water-based coating composition according to claim 1, wherein the polyalkylene glycol mono (meth) acrylate belonging to group (III) (e) of group (X) is represented by the following formula. object. [Chemical 1] (In the formula, R ₁ is hydrogen or a methyl group, Z is a divalent alkylene oxide residue having 2 to 4 carbon atoms that is ring-opened, n is an average of 1 to 30 and R ₂ is 4 carbon atoms. To 30 alkyl groups, alkenyl groups, aryl groups, alkyl groups having an aryl group as a substituent, cyclic alkyl groups, cyclic alkenyl groups, or monovalent organic groups derived from heterocyclic compounds.) 5. An extender pigment to be blended has an average particle size of 0.
The water-based coating composition according to any one of claims 1 to 4, which is a precipitated calcium carbonate having a diameter of 01 to 0.5 µm. 6. The extender pigment is a calcite-based calcium carbonate, and its X-ray diffraction intensity I ₀ (108 plane) and I ₁
The water-based coating composition according to claim 1, wherein a ratio (I ₁ / I ₀ ) of (116 faces) satisfies the following formula. 80 ≦ I ₁ / I ₀ ≦ 140 7. The water-based coating composition according to claim 1, wherein the extender pigment is an extender pigment that has been surface-treated in advance with at least one member selected from the group consisting of (X) and (Y). object. 8. The amount of the surface-treating agent for preliminarily surface-treating the extender pigment is 0.01 to 20 parts by weight in combination of (X) and (Y) with respect to 100 parts by weight of the extender pigment [however,
The amount of surface treatment of the substances belonging to each of (X) and (Y) is 10 parts by weight or less], The water-based coating composition according to any one of claims 1 to 7.