JPH10330645A - Extender pigment and water-based coating composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an extender pigment useful for esp. water-based coating compositions, and to obtain a water-based coating composition good in dispersibility of the extender pigment, holding its gloss retainability and excellent in durability and contamination resistance, by compounding the above extender pigment. SOLUTION: This extender pigment is obtained by surface treatment of an extender pigment with at least one kind of substance X selected from the group consisting of polymerized products from at least one kind of monomer selected from β-unsaturated monocarboxylic acids, α,β-unsaturated dicarboxylic acids, (meth)acrylic alkyl esters, etc., and products obtained by partially or fully neutralizing the above polymerized products with an alkali metal, ammonium and amine, and at least one kind of substance Y selected from the group consisting of compounds selected from alkyl ether sulfates, alkyl ether phosphates, alkyl aryl ether sulfates, etc., and their alkali metal, ammonium and amine salts. The other objective water-based coating composition is obtained by compounding the above extender pigment. It is preferable that the original extender pigment to be subjected to surface treatment is precipitated calcium carbonate 0.01-0.5 μm in average particle size.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel extender pigment, and more particularly to a water-based paint composition which is particularly useful for a water-based paint composition and has excellent gloss, weather resistance and storage stability. The present invention relates to an extender pigment that can be used and a water-based coating composition using the pigment.

[0002]

2. Description of the Related Art In recent years, the problem of resource saving and environmental protection has been taken up on a global scale. In the field of paints, a large amount of organic solvent discharged from organic solvent type paints is not only a work environment but also a global environment. The need for low-emission paints such as water-based, powdery, and high-solid paints has been rapidly increasing. Among them, water-based paints can significantly reduce problems such as air pollution, fire danger, and toxicity of organic solvent-based paints.
It is attracting attention as an environmentally friendly paint. In addition, the switch to water-based paints is being accelerated from the perspective of solvent regulations by the revision of the Fire Service Law and the strengthening of the standards of the Industrial Safety and Health Law. In addition, the recent trend toward high-grade paints represented by fluorine-based and silicone-based paints is also due to soaring labor costs,
It is rapidly spreading, and rapid progress is being made in making these resins water-based paints. In consideration of these circumstances, studies have been made to impart various functionalities to paints. In recent years, paints that are less likely to be stained and have excellent so-called stain resistance have been becoming popular.

[0003] However, these water-based paints have a drawback that the finished feeling of the coating film and the durability of the coating film are inferior to those of the solvent-based coating materials, and they are inferior to the solvent-based coatings in the sense of quality. 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. For example, by adding an extender such as silica having strong surface hydrophilicity, the stain resistance can be improved to some extent, but under the current usage conditions, the gloss is greatly reduced and the water resistance is also deteriorated.

[0004] As extenders in water-based paints, titanium, barium sulfate, kaolin clay, silica, talc,
At present, calcium carbonate and the like are used, and various uses are made according to various uses. At present, calcium carbonate, which is most widely used, will be described as an example to explain the present situation of extender pigments. It has been widely known that calcium carbonate is used as an extender in water-based paints, and various types of calcium carbonate are used depending on applications such as particle size, particle shape, particle size distribution, presence / absence of surface treatment, type and amount, and the like. Is used. When calcium carbonate is used as the extender pigment, heavy calcium carbonate, light calcium carbonate having coarse primary particles having an average primary particle size of more than 0.5 μm and a broad particle size distribution exceeding 2 μm, primary particle size In the case of colloidal calcium carbonate, which is present as secondary aggregated particles exceeding 0.5 μm at the finest, the performance of the coating film is remarkably reduced, and only the role of a bulking agent such as undercoating or intermediate coating is maintained, and the high-grade feeling of the coating film is maintained. It is far from.

[0005] Further, in order to prevent agglomeration between the calcium carbonate particles during dry powderization of the colloidal calcium carbonate,
Although a method of surface-treating the calcium carbonate slurry with a higher fatty acid, a resin acid, and an alkali metal salt thereof has been adopted, such a method still does not provide sufficient dispersibility, resulting in gloss and other particles. At present, physical properties expected from the diameter are not exhibited, and they do not contribute to stain resistance. Furthermore, even if the particles are dispersed by applying a large amount of energy mechanically, the dispersion stability over time is poor, and physical properties such as viscosity increase of the paint and decrease in gloss of the paint after storage are caused. Other extender pigments have the same problem as the above calcium carbonate, and extender pigments having high functions such as excellent coating surface gloss, weather resistance, storage stability, and stain resistance have not yet been obtained. .

The present inventors have attempted to improve these points.
JP-A-61-69872 and JP-A-61-6987
3, JP-A-62-212479, JP-A-62-21242
As in the case of 80, surface treatment agents and surface treatment methods for extender pigments containing calcium carbonate have been proposed. However, it is still inferior in finish feeling, durability, etc. of coating films as compared with solvent-based paints. Yes, and furthermore, it has not been possible to improve the stain resistance. As a compounding agent in the water-based paint, a compounding agent for enhancing the function of the pigment includes a wetting agent, a dispersing agent, and the like. In general, these are titanium white, which has an important role as a white pigment, and other materials. However, it is insufficient to enhance the function of the extender pigment and compensate for the above-mentioned disadvantage.

[0007]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention solves the above-mentioned problems, and provides an extender pigment having good dispersibility, good gloss retention, excellent durability and stain resistance. An object of the present invention is to provide a water-based coating composition using the same.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the extender which has been surface-treated in advance by combining two or more kinds of specific substances has a dispersibility, a gloss retention and a durability. Excellent in pigmentation and stain resistance. By blending it in the paint, it has good affinity with the extender pigment surface and resin, maintains the dispersibility of particles for a long time, maintains high gloss, and is durable. The present inventors have found that a coating film having excellent properties and stain resistance can be obtained, and have completed the present invention.

That is, the first invention in the present invention is:
The extender pigment includes at least one compound (X) selected from the group consisting of 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 an amine. ) And the following [Group B]
And a body pigment obtained by subjecting at least one compound (Y) selected from the group consisting of an alkali metal, ammonium, an amine salt and a halide thereof to a surface treatment. . [Group A] (I) α, β unsaturated monocarboxylic acid, (II)
α, β unsaturated dicarboxylic acid, (III) (a) alkyl (meth) acrylate, (b) (meth) acryl 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 Acid ester, (j) vinyl ether, (k) conjugated diene, chain olefin, cyclic olefin (IV) sulfo group-containing monomer [Group B] (I) (a) alkyl ether sulfate, (b) alkyl ether phosphoric acid, (C) alkyl aryl ether sulfate, (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) alkylsulfonic acid, (b) alkylbenzenesulfonic acid, (c) alkylnaphthalenesulfonic acid,
(D) sulfosuccinic acid, (e) sulfosuccinate, (f) α-olefinsulfonic acid, (g) N-acylsulfonic acid, (IV) (a) N-acylamino 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) alkylamine, (e) sorbitan derivative, (f) polycyclic phenyl ether, (g) fatty acid ester, (VIII) (A) fluoroalkyl carboxylic acid, (b) perfluoroalkyl carboxylic acid, (c) perfluoroalkyl sulfonic acid,
(IX) (a) acetylene alcohol, (b) acetylene glycol.

[0010] A second invention is directed to a water-based coating composition containing the above extender. In the present invention, the “average particle diameter” refers to an average value of diameters obtained assuming that inorganic particles confirmed by an electron microscope are spherical particles.

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

(III) in Group A includes (a) methyl (meth) acrylate, ethyl, propyl, isobutyl,
Alkyl acrylates and methacrylates exemplified by ethylhexyl and the like; (b) acrylates and methacrylates having an alkoxy group exemplified by methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; (c) cyclohexyl ( (D) 2 acrylates and methacrylates having a cyclohexyl group, such as meth) acrylates;
Α, β monoethylenically unsaturated hydroxy esters exemplified by -hydroxyethyl (meth) acrylate and the like;
(E) polyalkylene glycol monoacrylates and methacrylates exemplified by polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc .; (f) vinyl esters such as vinyl acetate and vinyl stearate; (g) styrene Vinyl aromatics such as vinyl toluene, (h) unsaturated nitriles exemplified by acrylonitrile, methacrylonitrile, etc .; (i) unsaturated dicarboxylic acid esters such as monomethyl maleate and dibutyl itaconate; (j) methyl vinyl ether; Vinyl ethers exemplified by butyl vinyl ether and the like, (k) conjugated dienes exemplified by butadiene, isobutene, ethylene, propylene, n-butene, n-pentene and cyclobutene, chain olefins and cyclic olefins, Increasing the compatibility with the quality pigment and a resin,
Maintains a long-term stable dispersion state, high gloss, durability,
Contributes to stain resistance.

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

[0014]

Embedded image

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

Examples of the 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, benzyloxy polyether 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, as well as a terminal group of a polyalkylene glycol chain having 4 to 30 carbon atoms
Alkyl group, alkenyl group, aryl group, alkyl group having an aryl group as a substituent, cyclic alkyl group, cyclic alkenyl group, ether-terminated polyalkylene glycol mono having a monovalent organic group derived from a heterocyclic compound (Meth) acrylate is an example.

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

Further, (I) in Group B constituting (Y) is (a) an alkyl ether sulfate exemplified by polyoxyethylene alkyl ether sulfate 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 alkali metal salts, ammonium salts and amine salts thereof, (c) alkyl aryl ether sulfuric acid exemplified by polyoxyethylene alkyl phenyl ether sulfuric acid and the like, and Examples thereof include alkali metal salts, ammonium salts, amine salts, (d) alkyl aryl ether phosphoric acids exemplified by polyoxyethylene alkylphenyl ether phosphoric acid, and alkali metal salts, ammonium salts, amine salts, and the like.

(II) in Group B includes (a) alkyl sulfates exemplified by polyoxyalkyl sulfates and the like, and alkali metal salts, ammonium salts and amine salts thereof, and (b) polyoxyalkyl phosphates and the like. Alkyl phosphates exemplified, and alkali metal salts, ammonium salts, and amine salts thereof, (c) alkylaryl sulfates exemplified by polyoxyalkylphenyl sulfate, and the like, and alkali metal salts, ammonium salts, and amine salts thereof. (D) Alkyl aryl phosphates exemplified by polyoxyalkylphenyl phosphates and the like, and alkylamide sulfates exemplified by alkali metal salts, ammonium salts and amine salts thereof, and (e) sulfates of fatty acid alkylolamides and the like , And its alkali metal salts, Moniumu salts, amine salts as an example.

(III) in Group B is (a) an alkylsulfonic acid exemplified by polyoxyethylene alkylsulfonic acid and the like, and an alkali metal salt and an ammonium salt thereof;
Amine salts, (b) alkylbenzene sulfonic acids and their alkali metal salts, ammonium salts, amine salts, (c)
Alkyl naphthalene sulfonic acid and its alkali metal salt, ammonium salt, amine salt, (d) sulfosuccinic acid and its sulfo succinic acid ester exemplified by 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 And amine salts.

(IV) in group B includes (a) N-acylamino acids and their alkali metal salts and ammonium salts;
Amine salts, (b) alkyl ether carboxylic acids and their alkali metal salts, ammonium salts, amine salts, (c)
Acylated peptides. (V) in group B
Are (a) aliphatic amine halides, (b) aliphatic quaternary ammonium halides, (c) aromatic quaternary ammonium halides, and (d) heterocyclic quaternary ammonium halides. can give. (VI) in Group B includes (a) betaines exemplified by carboxybetaine, sulfobetaine and the like, (b) aminocarboxylic acid,
(C) imidazoline derivatives.

(VII) in Group B is (a) an alkyl ether exemplified by polyoxyethylene alkyl ether, etc .; (b) an alkyl allyl ether exemplified by polyoxyethylene nonylphenyl ether; etc .; Alkyl esters such as ethylene oleate, (d) alkyl amines such as polyoxyethylene alkylamine, (e) sorbitan derivatives such as sorbitan laurate, (f) polycyclic phenyl ethers, g) Fatty acid esters. (VIII) in Group B includes (a) a fluoroalkyl carboxylic acid and its alkali metal salt, ammonium salt and amine salt, (b) a perfluoroalkyl carboxylic acid and its alkali metal salt, ammonium salt and amine salt, c) Perfluoroalkylsulfonic acids and their alkali metal salts, ammonium salts and amine salts. (IX) in group B is (a) 3-methyl-1-pentin-3-
Acetylene alcohol exemplified by oar, etc., (b)
Acetylene glycol exemplified by 3,6-dimethyl-4-octyne-3,6-diol and the like can be mentioned. At least one type (Y) selected from the group B (I) to (IX) increases the dispersion stability of the resin, and together with at least one type (X) selected from the group A (I) to (IV). By using, the dispersion stability of the extender pigment and the resin is further improved,
High gloss and weather resistance of the coating film are dramatically improved. The alkyl group referred to herein is, for example, a higher alcohol exemplified by hexyl, octyl, lauryl, and seryl, but is not limited thereto. In particular, when the purpose is workability at the time of forming a paint, select from (I), (II), (III), and (IX), in which the viscosity at the time of preparing the mill base is extremely low and the work time and dispersion cost are reduced. Good to do.

When the effect of the polymer selected from Group A constituting (X) is expected to be larger,
It is preferable to use a copolymer of the monomers belonging to (II), (III) and (IV), and the copolymerization ratio is not particularly limited, but is preferably a monomer belonging to (I). 0 to 100 parts by weight of the monomer belonging to (II), 5 to 300 parts by weight of the monomer belonging to (III), and (IV)
It is preferable that the monomer belonging to the above is used in an amount of 0 to 100 parts by weight.
As described above, the components (II) and (IV) are effective for particularly fine regions of the extender pigment. Therefore, when the type of the extender pigment, the particle diameter, the viscosity of the final paint, and the like are considered, the component (II) and (IV) Although it may be 0 parts by weight, if it exceeds 100 parts by weight, for example, when it is blended into a coating material, the coating material may be gelled depending on the kind of a film-forming aid or the like, which may hinder use. Therefore, from the viewpoint of paint design, it is more preferably 2 to 70 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the component (I). In addition, the component (III)
When less than 5 parts by weight per 100 parts by weight of component (I),
Even if a paint using this copolymer is prepared, the effect may not be sufficient, and if it exceeds 300 parts by weight, foaming may be remarkable at the time of dispersing the extender, and the workability may be reduced. In some cases, the solubility of the polymer in water is significantly reduced, and it may be difficult to uniformly adsorb the polymer on the surface of the extender.

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

These homopolymers or copolymers can be obtained by a conventionally known method. For example, polymerization in a solvent such as water, an organic solvent, or a mixture of a water-soluble organic solvent and water can be mentioned. In this case, for polymerization in an aqueous medium, a persulfate or a peroxide is used as a polymerization initiator. Hydrogen oxide or the like is used, and an accelerator such as sodium bisulfite or ascorbic acid can be used. For polymerization in an organic solvent, an azo compound or an organic peroxide is used as a polymerization initiator, and an accelerator such as an amine compound can be used in combination. For the polymerization in a mixed solvent of a water-soluble organic solvent and water, any of the above various polymerization initiators or a combination of a polymerization initiator and a promoter can be appropriately selected and used. The polymer thus obtained can be neutralized or partially neutralized with an alkali metal such as sodium, an alkali substance such as ammonium or an amine depending on the case.

The compound belonging to the group B constituting (Y) is
It can be obtained by a conventionally known method. For example, sulfuric acid esterification of higher alcohols with concentrated sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfurous acid, etc., phosphorus pentoxide, phosphorus oxychloride, phosphorus trioxide, etc., esterification of aliphatic alcohol with ethylene oxide After etherification by addition polymerization, a method of obtaining each ester using the above-mentioned sulfating agent, phosphorylating agent, etc. may be mentioned, and if necessary, it may be neutralized with an alkali metal, ammonium, an organic amine or the like. .

The extender in the present invention is titanium, barium sulfate, kaolin clay, silica, talc, calcium carbonate, mica, etc., as described above. These may be used alone or in combination of two or more. In order to further enhance the effect of the above, it is preferable to use calcium carbonate. Among them, precipitated calcium carbonate having an average particle diameter of 0.01 to 0.5 μm is preferably used. Precipitated calcium carbonate is relatively inexpensive, has a lower specific gravity than barium sulfate, not only has a greater compounding effect, but also easily controls the particle size and easily obtains a sharp particle size distribution.

The calcium carbonate used is a specific X
Those having a line diffraction intensity ratio (I ₁ / I ₀ ) are preferable. Here, the diffraction intensity ratio means that the diffraction intensity of the 108 surface of calcite calcium carbonate is I ₀ , and the diffraction intensity of the 116 surface is I ₁
And the range is 80 ≦ (I ₁ / I
₀ ) ≦ 140, preferably 90 ≦ (I ₁ / I ₀ ) ≦ 13
0 is more preferred. If this intensity ratio is less than 80, it may be difficult to obtain a good dispersion state in the paint,
If it exceeds 140, the particles may agglomerate over time in the paint, and in any case, the gloss may be reduced.

The production of the precipitated calcium carbonate used in the present invention is carried out, for example, by passing a carbon dioxide-containing gas (hereinafter, referred to as carbon dioxide) to an aqueous suspension of calcium hydroxide (hereinafter, referred to as lime milk), or It may be carried out by a known method such as a method of spraying a mixture of lime milk or calcium hydroxide and precipitated calcium carbonate into a gas. Preferably, the calcium carbonate particles are dispersed as much as possible. As a method, for example, the carbonation reaction is stopped at a pH of 7.5 to 10.0 in the reaction system, and the calcium carbonate particles are stirred to obtain calcium carbonate. It is easily achieved by eluting the alkali remaining in the system, adding or conducting milk of lime and carbon dioxide into the system as necessary, and controlling the pH of the system at 9.0 to 12.0 for 5 hours or more. .

The method of adding (X) and (Y) (hereinafter, referred to as a surface treating agent) to an extender and adsorbing it to obtain a surface-treated powder can be carried out by a conventional method. The obtained average primary particle size of 0.01 to 0.5 μm
Of the precipitated calcium carbonate slurry, uniformly mixed by stirring or the like to adsorb the surface treatment agent to the calcium carbonate particles, and then dehydrated, dried and powdered by a filter press or the like. Alternatively, it can be obtained by temporarily dehydrating a carbonated calcium carbonate slurry, adding the surface treating agent to a calcium carbonate press cake, stirring vigorously, and then drying and powdering with a spray drier or the like. Further, as a method of firmly fixing the calcium carbonate on the surface of the calcium carbonate, it is also effective to disperse the calcium carbonate slurry to which the surface treating agent has been added using a continuous wet disperser such as a sand grinder before drying.

The amount of the surface treating agents (X) and (Y) added and adsorbed to the extender is not particularly limited, but both (X) and (Y) are preferably added to 100 parts by weight of the extender. The amount is preferably 0.01 to 20 parts by weight, 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 addition amount is less than 0.01 part by weight, the surface treatment effect is hardly remarkable as compared with the untreated product, and if it exceeds 20 parts by weight, the excess adsorption rate decreases and the surface treatment agent becomes more remarkable. The effect is unlikely to be expected and is often economically disadvantageous.

These specific surface treatment agents (X),
For example, when the extender pigment surface-treated in (Y) is blended into a water-based paint, it is preferable that the extender be finally blended as a powder because the degree of freedom in paint design is increased. In order to reduce the energy cost of powdering, the surface treating agent may be added to the water suspension of the extender pigment and blended with the aqueous paint as it is. (X),
When surface-treating (Y), other dispersants and wetting agents such as sodium hexametaphosphate and potassium tripolyphosphate may be used in combination, if necessary.

The extender pigment of the present invention obtained as described above has good dispersibility, good affinity with resin, high gloss, and excellent durability and stain resistance. Although it is used in various fields, the above-mentioned characteristics are effectively exhibited especially when used in water-based paints. The types of water-based paint resins to which the extender is blended include alkyd, acrylic,
Vinyl acetate, urethane, silicone, fluorine,
Emulsion resins for general coatings such as styrene, melamine, and epoxy, water-soluble resins for general coatings such as alkyd, amine, styrene-allyl alcohol, aminoalkyd, and polybutadiene, emulsion resins and water-soluble resins Blended dispersion resin for paint,
It can be appropriately selected from a dispersion resin using a crosslinked water-soluble resin as an emulsifier, an acrylic hydrosol and the like, and it is also possible to use a combination of two or more of these resin components.

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, per 100 parts by weight of the resin solids. Parts by weight. If the amount is less than 5 parts by weight, the desired effect is hardly exhibited sufficiently, which is disadvantageous in terms of cost. If the amount exceeds 150 parts by weight, the gloss may be remarkably lowered. Also, when making water-based paints, color pigments for paints and other extenders, defoamers, non-adhesives, wetting agents, dispersants, curing accelerators, preservatives, fungicides, film-forming aids, antifreezing agents One or more kinds of additives usually used in this field can be added and used as needed in the coating composition of the present invention.

[0035]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited by these.

Examples 1 to 3 Milk of lime having a specific gravity of 1.07 was prepared at 15 ° C., and carbon dioxide gas (30% / min.
CO ₂ ) was conducted to carry out a carbonation reaction, and the pH of the system was 8.0.
At which time the carbonation reaction was stopped at 50 ° C. PH10.
The mixture was stirred for 15 hours at 2, and when the viscosity of the system reached 2300 cp, carbon dioxide gas was passed 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, which is extremely small in aggregate particles, was obtained. The X-ray intensity ratio of this calcium carbonate was 120. The calcium carbonate slurry was dehydrated with a filter press to obtain a press cake having a solid content of 60% by weight. Substances (X) and (Y) selected from Group A and Group B shown in Table 1 are added to the press cake having a solid content of 60% by weight obtained by the above method,
By vigorous stirring, it was sufficiently adsorbed on the surface of calcium carbonate, and then dried by a spray drier to obtain a powdery extender. Using the extender pigment thus obtained, an acrylic emulsion coating composition was prepared based on the following composition table and preparation method. Table 4 shows the evaluation results.

(Paint Formulation Table) a. Acrylic / styrene resin (solid content 50%) 200.00 parts by weight (solid 100.00) b. Dispersant (Discoat N-14, Daiichi Kogyo Seiyaku) 4.85８５ c. Antifreeze (ethylene glycol) 4.39３９ d. Defoamer (NOPCO 8034L, San Nopco) 4.39３９ e. Titanium (R-930, Ishihara Sangyo) 44.04 f. Extender pigment described in the separate table g. (X) See the attached table h. (Y) See the attached 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 (ADEKANOL UH420 / Asahi Denka Kogyo) 10.22〃 l. Preservative (Mornon # 800, Katayama Chemical Research Laboratory) 0.42 m. Water Appropriate (Coating preparation method) Above b to h and m are all about 500cc
Each compounding agent is put into a 1 liter container sequentially with gentle stirring using a 6 cm dissolver blade, and after all the compounding agents have been added, 3000 rpm while cooling externally.
For 20 minutes to prepare a mill base. Next, the remaining ingredients were gradually added to the mill base with gentle stirring. After the addition, the mixture was stirred at 3000 rpm for 5 minutes to obtain a test paint.

The properties of the obtained coating composition were measured by the following methods. Table 4 shows the results. (Initial paint physical properties) The paint was allowed to stand in a constant temperature bath at 20 ° C for 48 hours and defoamed, and the initial paint physical properties were evaluated using this. (Average paint physical properties) The paint was left standing and defoamed at 50 ° C. for 10 days in a constant temperature bath, and the paint physical properties of the paint over time were evaluated using this. Viscosity: values at 2 rpm and 20 rpm by a B-type viscometer. Gloss; 6 g 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 6 months outdoor exposure test using the initial coating film as a standard.

Examples 4 to 6, 10 The same amount of the above-mentioned lime milk was added to the 0.1 μm calcium carbonate slurry before dehydration obtained by the same carbonation method as in Example 1, and carbon dioxide gas was passed again. To perform a carbonation reaction, and the reaction was stopped at PH 6.9. Thereby, a calcium carbonate slurry having an average primary particle diameter of 0.3 μm with few aggregate particles was obtained. After the calcium carbonate slurry was dehydrated by a filter press, the obtained press cake (concentration of figure content: 60% by weight) was selected from the groups A and B shown in Tables 1 and 2 and contained substances (X) and (Y). Was added, and the mixture was vigorously stirred to be sufficiently adsorbed on the surface of calcium carbonate, and then dried with a spray drier to obtain a powdery extender. The X-ray diffraction intensity ratio of the calcium carbonate was 110. Using the extender pigment thus obtained, an acrylic emulsion coating composition was prepared based on the above-mentioned composition table and preparation method. Table 4 shows the evaluation results.

Examples 7 to 9, 11 to 13 The extender was kaolin clay (average particle size 0.8 μm),
Barium sulfate (average particle diameter 0.2 μm), heavy calcium carbonate (average particle diameter 3.0 μm, X-ray diffraction intensity ratio 75)
Then, substances (X) and (Y) selected from the groups A and B shown in Tables 1 and 2 are added, and the mixture is sufficiently stirred to be sufficiently adsorbed on the surface. An extender was obtained. Using the extender pigment thus obtained, an acrylic emulsion coating composition was prepared based on the above-mentioned composition table and preparation method. Table 4 shows the evaluation results.

Comparative Examples 1 to 4 The same procedures as in Example 1 were carried out except that a press cake of calcium carbonate obtained in the same manner as in Example 1 was used, and the surface treatment agents shown in Table 3 were changed. A powdery extender was obtained by the method. Using the extender pigment thus obtained, an acrylic emulsion coating composition was prepared based on the above-mentioned composition table and preparation method. Table 5 shows the evaluation results.

Comparative Examples 5 to 7 Using kaolin clay, barium sulfate and heavy calcium carbonate used in Examples 7 to 9, substances (X) or (Y) selected from Group A and Group B shown in Table 3 Was added, and the mixture was vigorously stirred to be sufficiently adsorbed on the surface to obtain an extender pigment.
Using the extender pigment thus obtained, an acrylic emulsion paint was prepared based on the above composition table and preparation method. Table 5 shows the evaluation results.

Comparative Examples 8 to 10 Using the kaolin clay, barium sulfate and heavy calcium carbonate used in Examples 7 to 9 as shown in Table 3, without the surface treatment agent, based on the above-mentioned composition table and preparation method An acrylic emulsion paint was made. Table 5 shows the evaluation results.
It describes in.

Examples 14 to 17 Using the 0.1 μm calcium carbonate press cake used in Example 1, the substances (X) and (Y) selected from Group A and Group B shown in Table 6 were changed. Except for this, a powdery extender was obtained in the same manner as in Example 1. Using the extender pigment thus obtained, an acrylic emulsion paint was prepared based on the above-mentioned composition table and preparation method. Table 7 shows the evaluation results.

Examples 18 and 22 Milk of lime having a specific gravity of 1.07 was prepared at 15 ° C., and carbon dioxide gas (30% / min.
CO ₂ ) was conducted to carry out a carbonation reaction, and the pH of the system was 8.0.
At which time the carbonation reaction was stopped,
The mixture was stirred at 0.2 for 10 hours. When the viscosity of the system reached 3100 cp, carbon dioxide gas was passed 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 0.07 μm, which is extremely small in aggregate particles, was obtained. The calcium carbonate slurry was dehydrated with a filter press to obtain a press cake having a solid content of 60% by weight. A powdery extender was obtained in the same manner as in Example 1 except that this press cake was changed to the substances (X) and (Y) selected from Group A and Group B shown in Table 6. The X-ray diffraction intensity ratio of the calcium carbonate was 120. Using the extender pigment thus obtained, an acrylic emulsion paint was prepared based on the above-mentioned composition table and preparation method. Table 7 shows the evaluation results.

Examples 19 and 20 The presscake of 0.3 μm calcium carbonate used in Example 4 was used and the substances (X) and (Y) selected from Group A and Group B shown in Table 11 were changed. Example 4 except that
A powdery extender was obtained in the same manner as described above. Using the extender pigment thus obtained, an acrylic emulsion paint was prepared based on the above-mentioned composition table and preparation method. Table 7 shows the evaluation results.

Example 21 The barium sulfate of 0.2 μm used in Example 8 was added to Table 6
A powder extender was obtained in the same manner as in Example 8, except that the substances (X) and (Y) selected from the groups A and B described above were changed. Using the extender pigment thus obtained, an acrylic emulsion paint was prepared based on the above-mentioned composition table and preparation method. The results of this evaluation are shown in Appendix Table 7.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

[0052]

[Table 5]

[0053]

[Table 6]

[0054]

[Table 7]

[0055]

As described above, the specific substance (X),
The extender pigment which has been surface-treated in advance (Y) has good affinity between the extender pigment and the vehicle in the paint over a long period of time by being blended into the water-based paint composition, and as a result, the disperse of the extender pigment The state is stable, the gloss retention is good, and the extender pigment is uniformly present on the coating film surface, and a remarkable antifouling effect is obtained as compared with a paint using a conventionally known extender pigment. Can be Conventionally, gloss, weather resistance,
Sufficient effects can be expected even in water-based paints in which the extender could not be used due to reduced stain resistance.

Claims (7)

[Claims] The extender is selected from the group consisting of 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 an amine. At least one (X)
And a compound selected from the following [Group B] and at least one type (Y) selected from the group consisting of alkali metals, ammonium, amine salts and halides thereof, which is surface-treated. . [Group A] (I) α, β unsaturated monocarboxylic acid, (II) α, β unsaturated dicarboxylic acid, (III) (a) alkyl (meth) acrylate,
(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 sulfate, (b) alkyl ether phosphoric acid, (c) alkyl aryl ether sulfate,
(D) alkyl aryl ether phosphate, (II) (a) alkyl sulfate, (b) alkyl phosphate, (c) alkyl aryl sulfate, (d) alkyl aryl phosphate, (e) alkyl amide sulfate, (III) (A) alkylsulfonic acid, (b) alkylbenzenesulfonic acid, (c) alkylnaphthalenesulfonic acid, (d) sulfosuccinic acid, (e) sulfosuccinate, (f) α-olefinsulfonic 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
(VI) (a) betaine, (b) aminocarboxylic acid,
(C) imidazoline derivative, (VII) (a) alkyl ether, (b) alkyl allyl ether, (c) alkyl ester, (d) alkylamine, (e) sorbitan derivative, (f) polycyclic phenyl ether, (g ) Fatty acid esters, (VIII) (a) fluoroalkyl carboxylic acid, (b) perfluoroalkyl carboxylic acid, (c) perfluoroalkyl sulfonic acid, (IX) (a) acetylene alcohol, (b) acetylene glycol 2. The copolymerization ratio of the copolymer in Group A of (X) is based on 100 parts by weight of the monomer belonging to (I).
0 to 100 parts by weight of a monomer belonging to (II), 5 to 300 parts by weight of a monomer belonging to (III), and 0 to 100 parts by weight of a monomer belonging to (IV)
The extender pigment according to claim 1, which is 100 parts by weight. 3. The extender according to claim 1, wherein the polyalkylene glycol mono (meth) acrylate belonging to Group A (III) (e) of (X) is represented by the following formula. Embedded image (Wherein, R ₁ is a hydrogen or methyl group, Z is a ring-opened divalent alkylene oxide residue having 2 to 4 carbon atoms, n is an average of 1 to 30 and R ₂ is a carbon atom having 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.) 4. The extender pigment according to claim 1, wherein the extender pigment to be surface-treated is precipitated calcium carbonate having an average particle diameter of 0.01 to 0.5 μm. 5. The amount of the surface treatment agent for pre-treating the extender pigment is 0.01 to 20 parts by weight in total of (X) and (Y) with respect to 100 parts by weight of the extender pigment, provided that
(X) and (Y) the surface treatment amount of the substance belonging to each of the components is 10 parts by weight or less], the extender pigment according to any one of claims 1 to 4. 6. An extender to be blended is calcite calcium carbonate, and its X-ray diffraction intensity I ₀ (108)
The extender according to any one of claims 1 to 5, wherein a ratio (I ₁ / I ₀ ) of I ₁ (116 surface) to I ₁ (116 surface) satisfies the following expression. 80 ≦ I ₁ / I ₀ ≦ 140 7. A water-based coating composition comprising the extender according to any one of claims 1 to 6.