JP2002194298A - Water-based luster coating material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based luster coating material composition which totally improves the adhesion to put polyolefin based floor materials in perspective while maintaining all performances required for a floor polishing agent and is particularly strong against the influence by water and has excellent wear resistance and adhesion. SOLUTION: The water-based luster coating material composition comprises (a) an emulsion of a polyurethane containing no hydroxyl group in the molecule, (b) an emulsion of an acrylic polymer having a carboxyl group in the molecule and a glass transition temperature (Tg) of -10 deg.C to +25 deg.C, (c) an emulsion of an acrylic polymer having a carboxyl group in the molecule and a Tg of higher than 25 deg.C, and (d) a polyvalent metal complex as the essential components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous glazing coating composition, and more particularly to an aqueous glazing coating composition having particularly excellent adhesion to plastic materials, water resistance and abrasion resistance.

[0002]

2. Description of the Related Art Aqueous glazing compositions are used as glazing agents for floors of buildings and condominiums, and also for furniture and housing. These polishes are applied to the surface of floors and furniture to protect them and maintain their aesthetic appearance. In particular, the coating layer formed on the flooring material plays a role of maintaining aesthetics and cleanliness by a glazing effect and the like, and also prevents wear of the flooring material, adhesion of dirt, and prevention of slip accidents.

[0003] Typical performances required of the floor polish include the ability to form a clear and tough film on the flooring material, the ability to develop gloss, and the difficulty of being stained by walking. , Non-slip, and easy removal with a special release agent.

As a conventional floor polish, an aqueous polymer type is predominantly used, and specific examples thereof are also disclosed in JP-B-44-24407 and JP-B-49-1458. As described above, a homopolymer of a polymer of acrylic acid or methacrylic acid or a derivative thereof, a copolymer thereof, and a copolymer thereof with another vinyl monomer such as styrene (hereinafter, these are referred to as acrylic polymers). And an aqueous emulsion-type polishing agent containing a crosslinking agent, a polyethylene wax, an alkali-soluble resin, a plasticizer, a film-forming aid, and the like. Generally, an acrylic polymer having a carboxy group in the molecule and having a glass transition temperature of more than 25 ° C. is used as the acrylic polymer as a main component of the above-mentioned conventional floor polish, Metal complexes such as zinc are used as agents.

[0005] Further, as means for improving the abrasion resistance of the above-mentioned floor glazing agent, polyurethane has been mixed, for example, as disclosed in Japanese Patent Publication No. 64-112367. In addition, a technique for blending a polyurethane emulsion having a carboxy group in the molecule is known. With these in mind,
Having a carboxy group in the molecule and having a glass transition temperature of 25
Emulsion of acrylic polymer exceeding ℃, emulsion of polyurethane having a carboxy group in the molecule,
Floor polishes comprising a polyvalent metal complex capable of acting on a carboxy group are sold and put into practical use.

[0006] By the way, major places where a large amount of floor polish is used include department stores, mass retailers, small shops, hospitals, schools, office buildings, and the like. Such polishes are applied and used, and satisfy desired requirements. On the other hand, in contrast to such general places, special places in which environmental conditions are severe for floor polishes, for example, fresh food counters in supermarkets, concourses in train stations, near office building entrances, and the like. Even if it is indoors, the place is often in contact with water, has a chance to be exposed to excessive water, and can be said to be a special place where a large amount of people walk in particular. In addition to the most common polyvinyl chloride-based flooring materials, stone-based flooring materials to which a floor polisher hardly adheres are often used. Furthermore, recently, due to the dioxin problem, instead of polyvinyl chloride flooring,
Flooring materials mainly composed of polyolefin have been developed.

[0007] When a conventional floor polish is applied to such a place, peeling and whitening of the film due to the influence of water, and abrasion of the film due to human walking are likely to occur, which is problematic.
Also, in the conventional technology of blending a polyurethane emulsion or a polyvalent metal complex with an acrylic polymer emulsion, the polyvalent metal complex acts on both carboxy groups of the acrylic polymer and the polyurethane (double cross-linking). Although the abrasion resistance is good, the adhesiveness is insufficient, and especially the adhesiveness when immersed in water is poor, and the improvement has been demanded in the industry. In particular, a polyurethane containing a carboxy group is poor in adhesion to a floor material mainly composed of polyolefin, and hinders the development of floor materials mainly composed of polyolefin instead of a polyvinyl chloride floor material. Will be.

[0008] Therefore, in the industry, such places are particularly resistant to the influence of water, and have excellent wear resistance.
Development of floor polishes having excellent adhesion to a wide range of flooring materials including polyolefin flooring materials has been demanded. Furthermore, when turning to environmental issues, it goes without saying that a non-phosphorus-based water-based glazing coating agent for solving the nutrient enrichment of rivers and lakes is required.

[0009]

DISCLOSURE OF THE INVENTION The present invention is to improve the adhesiveness of a polyolefin flooring material from the viewpoint of the whole while maintaining all the performance required for floor glazing agents. An object of the present invention is to provide an aqueous glazing coating composition which is resistant to the influence of water and has excellent abrasion resistance and adhesion. Another object of the present invention is to develop an aqueous glazing coating composition capable of eliminating phosphorus in consideration of environmental issues.

[0010]

Means for Solving the Problems The present inventors blended an emulsion of an acrylic polymer having a carboxy group in the molecule and having a glass transition temperature of more than 25 ° C. with an emulsion of a polyurethane having a carboxy group in the molecule. In this case, it is considered that excessive cross-linking due to double cross-linking causes a decrease in adhesion, and a polyurethane emulsion having no carboxy group in the molecule was searched for, and as one of them, a polyurethane emulsion having a sulfonate group in the molecule was searched. An acrylic polymer emulsion having a carboxy group in the molecule and having a glass transition temperature of more than 25 ° C. and a polyvalent metal complex, which have been conventionally used, were blended with this. However, at this stage, although the abrasion resistance was improved, the adhesion to a wide range of flooring materials including polyolefin flooring materials was still insufficient, and did not reach the target level.

The inventors of the present invention have conventionally used a coating material for a paint to further improve the adhesiveness. However, the water-based glossy coating agent has the disadvantages of adhesion of dirt and insufficient heel mark property. The film is soft for use as a floor glazing agent, and cannot be used as a floor glazing agent from the viewpoint that the antifouling performance is extremely poor by itself. An emulsion of an acrylic polymer having a carboxy group and a glass transition temperature in the range of −15 ° C. to + 25 ° C. is used as an emulsion of a polyurethane having no carboxy group in a molecule, particularly, an emulsion of a polyurethane having a sulfonate group in a molecule. And a carboxyl group in the molecule, and a glass transition temperature of more than 25 ° C when blended into an emulsion of an acrylic polymer, significantly improving water resistance and adhesion Have found an improved is that. Furthermore,
It has been discovered that it exhibits excellent adhesion to the pending polyolefin flooring.

[0012] These findings have solved the initial problem, and have further discovered that a citrate compound effectively acts as a plasticizer on this aqueous polishing coating composition. The present invention was also completed by finding a water-based glazing coating composition capable of eliminating phosphorus in consideration of environmental problems.

That is, the present invention provides (a) a polyurethane emulsion having no carboxy group in the molecule;
(B) an emulsion of an acrylic polymer having a carboxy group in the molecule and a glass transition temperature in the range of -10 ° C to + 25 ° C, and (c) an emulsion of a carboxy group in the molecule and having a glass transition temperature of 25 ° C. SUMMARY OF THE INVENTION The gist of the present invention is an aqueous polisher coating composition containing an emulsion of an acrylic polymer and a polyvalent metal complex capable of acting on a carboxy group (d) as essential components. Further, in the aqueous glazing coating composition of the present invention, the mixing ratio of the above (a), (b) and (c) is as follows:
(A) is 10 to 50% by mass as a solid material,
(B) is 10 to 30% by mass, (c) is 20 to 80% by mass.
Wherein the compounding ratio of (d) is 0.1 to 1 equivalent in terms of the number of ions of the metal of (d) per the total amount of carboxy groups of the acrylic polymer of (b) and (c). And

Further, the present invention further provides a method for preparing a citrate compound based on the solids 100 of the above (a), (b) and (c).
The gist of the present invention is an aqueous glazing coating composition containing 5 to 25 parts by mass per part by mass. In addition, the aqueous glazing coating composition of the present invention comprises the above (a)
Is an emulsion of polyurethane obtained by using polyether polyol or polyester polyol and aliphatic diisocyanate as main raw materials and having a sulfonate group at a molecular terminal.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION An emulsion of a polyurethane (a) having no carboxy group in the molecule (hereinafter referred to as polyurethane a) used in the present invention (hereinafter referred to as a carboxy-free urethane Em or component (a)). Is a polyurethane emulsion having an anionic charge excluding carboxy groups. These are usually obtained by polymerizing a polyol component in which a functional group having an anionic charge is introduced on the polyol side and a polyisocyanate compound in a solvent to obtain the polymer (polyurethane) and, if necessary, extending the chain with a diamine. It can be produced by adding a neutralizing agent and water to self-emulsify and removing the solvent by azeotropic distillation. Examples of the neutralizing agent include alkali metals, low molecular weight diamines such as triethylamine, and ammonia.

As the polyurethane a, in particular, it is desirable to use a polyurethane obtained by using a polyether polyol or polyester polyol and an aliphatic diisocyanate as main raw materials and having a sulfonate group at a molecular terminal. This emulsion is preferably a polyether polyol or a polyester polyol. , A sulfo group (—SO ₃ H) is introduced into all or part of the sulfonate group, a chain is extended as required after the urethanation reaction with the aliphatic diisocyanate, and a neutralizing agent and water are added to self-emulsify to form a sulfonate group. (−SO ₃
M. However, after M is converted to a metal, an amino group, an ammonium group, or the like), it can be produced in the same manner as described above. As the neutralizing agent used at this time, low-molecular diamines such as triethylamine, ammonia and the like are preferable from the viewpoint of water resistance, abrasion resistance, and adhesion to a wide range of flooring materials including polyolefin flooring materials.

As a carboxy-free urethane Em,
When a polyurethane emulsion having a sulfonate group at the molecular terminal as described above is used, water resistance, abrasion resistance,
It is preferable in terms of adhesion to a wide range of flooring materials including polyolefin flooring materials. Such urethane Em is commercially available and can be used. As a commercially available product, manufactured by Dainippon Ink and Chemicals, Inc., trade name: Hydran H
W-950, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Superflex 410, manufactured by Takeda Pharmaceutical Co., Ltd., trade name: Takelac W-635, and the like.

The emulsion (b) of an acrylic polymer (hereinafter referred to as acrylic polymer a) having a carboxy group in the molecule and having a glass transition temperature of -10 ° C. to + 25 ° C. used in the present invention. , Soft acrylic E
m or component (b). ) And (c) an emulsion of an acrylic polymer (hereinafter, referred to as acrylic polymer b) having a carboxy group in the molecule and having a glass transition temperature of more than 25 ° C (hereinafter, referred to as hard acrylic Em or component (c)). ) Is one or more acrylic monomers selected from acrylic acid or methacrylic acid or derivatives thereof such as esters, amides, and nitriles, and α, β such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. -An emulsion of a polymer obtained by emulsion copolymerization with a monoethylenic carboxylic acid monomer. As the acrylic monomer, an alkyl ester of acrylic acid or methacrylic acid having 1 to 10 carbon atoms is particularly preferred. In the above copolymerization, vinyl monomers such as styrene, α-methylstyrene, acrylonitrile, and vinyl acetate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, vinyl chloroacetate, allyl alcohol, divinylbenzene, ethylene glycol (meth) ) One or more reactive monomers having no carboxy group such as acrylate may be selected and used for copolymerization.

The glass transition temperature of the acrylic polymer a and the acrylic polymer b can be measured by a differential thermal analysis or a viscoelastic spectrometer on a film formed by drying the soft acrylic Em and the hard acrylic Em, or It can be known and determined by referring to the analysis table attached to the commercial product, the numerical values described in the technical data, and the like. The acrylic polymer a and the acrylic polymer b each have a carboxy group in the molecule.
-Based on the total amount of monoethylenic carboxylic acid monomers,
α, β-monoethylenic carboxylic acid monomer is 0.1 to
It is preferable to use one manufactured using an amount such that it is in the range of 30% by mass. When the amount of the α, β-monoethylenic carboxylic acid monomer is less than 0.1% by mass, the crosslinking with the polyvalent metal complex which is one component of the composition of the present invention is insufficient, and the water resistance,
When the abrasion resistance is reduced, and when the content exceeds 30% by mass, the hydrophilicity is increased, the water resistance tends to be reduced, and since the crosslinking is excessive, excellent adhesion to a wide range of flooring materials including polyolefin flooring materials is achieved. Properties tend to decrease.

The emulsifier used in the emulsion copolymerization of the acrylic monomer and the α, β-monoethylenic carboxylic acid monomer is not limited, but is preferably as small as possible.
Soap-free acrylic polymer emulsions stabilized by using a reactive emulsifier or using a basic compound such as ammonia also have excellent water resistance and excellent adhesion to a wide range of flooring materials including polyolefin flooring materials. preferable.

Soft acrylic Em and hard acrylic E
For m, commercially available products can be used. For example, as soft acrylic Em, trade names: A-304, A, manufactured by Sansui Co., Ltd.
-208, A-523, product names manufactured by Rohm and Haas Japan Ltd .: Primal AC-22, Primal AC-261, etc., and as hard acrylic Em, product names manufactured by Rohm and Haas Japan Co., Ltd. : Primal B-924, Primal B-832, Primal B-
1604, Primal HPDR, trade name: A manufactured by Sansui Corporation
-733, A-923, A-995 and the like.

The aqueous glazing coating composition of the present invention contains the above-mentioned components (a), (b) and (c) as essential components. (A) is preferably 10 to 50% by mass, (b) is preferably 10 to 30% by mass, (c) is preferably 20 to 80% by mass, more preferably (a) is 20 to 40% by mass, and (b)
Is 15 to 25% by mass, and (c) is 35 to 65% by mass. When the component (a) is less than 10% by mass, the abrasion resistance of the aqueous glazing coating composition becomes insufficient, and
If it exceeds 300, the removability of the film of the composition will be insufficient. If the component (b) is less than 10% by mass, the water resistance and adhesion of the composition will be insufficient, and if it exceeds 30% by mass, the heel mark resistance of the composition will be insufficient. When the component (c) is less than 20% by mass, the heel mark resistance of the composition becomes insufficient, and when it exceeds 80% by mass, the abrasion resistance, water resistance and adhesiveness of the composition become insufficient.

The aqueous glazing coating composition of the present invention further contains a polyvalent metal complex capable of acting on a carboxy group. The polyvalent metal complex that can be used generally contains an alkaline residue when the polyvalent metal residue, the organic bidentate amino acid ligand residue and the chelate are added to the above emulsions in a solubilized state. Examples of polyvalent metal ions include ions of beryllium, cadmium, copper, calcium, magnesium, zinc, zirconium, barium, strontium, aluminum, titanium, bismuth, antimony, lead, cobalt, iron, nickel, and the like. These ions can be used as oxides, hydroxides or basic, acidic or neutral salts with significant solubility in water, such as at least about 1% by weight. The alkaline residue can be provided by ammonia or an amine. The organic bidentate amino acid ligand is preferably an aliphatic amino acid, but may be a heterocyclic amino acid.

Representative organic bidentate amino acid ligands include glycine (aminoacetic acid), alanine (α-aminopropionic acid), β-alanine (β-aminopropionic acid), and valine (α-isopropylaminoacetic acid). , Norvaline (α
-N-propylaminoacetic acid), α-aminobutyric acid, leucine (2-amino-4-methylpentanoic acid), norleucine (2-aminohexanoic acid), N-methylaminoacetic acid,
N-ethylaminoacetic acid, dimethylaminoacetic acid, diethylaminoacetic acid, Nn-propylaminoacetic acid, N-isopropylaminoacetic acid, N-butylaminoacetic acid, phenylalanine, N-phenylaminoacetic acid, N-benzylaminoacetic acid, proline, nicotine Acid and tetrahydronicotinic acid.

Preferred polyvalent metal complexes include cadmium glycinate, nickel glycinate, zinc glycinate, zirconium glycinate, cobalt alanate,
Includes copper alanate, zinc alanate, copper β-alanate, zinc β-alanate, nickel norvalinate, zinc barinate and copper dimethylaminoacetate.

The compounding ratio of the polyvalent metal complex is based on the total amount of carboxy groups of the acrylic polymers (above acrylic polymer a and acrylic polymer b) of the above components (b) and (c). 0.1
It is preferable to set the range so as to be equivalent to 1 time equivalent. If the compounding ratio is less than 0.1 equivalent, the crosslinking of the acrylic polymer a and the acrylic polymer b tends to be insufficient, so that the water resistance and abrasion resistance decrease. Excellent adhesion to a wide range of flooring materials, including system flooring materials, tends to decrease. Since the polyvalent metal complex is blended with the commercial products of the above-mentioned hard acrylic Em usually used for aqueous glazing coating agents, analysis of these commercial products, analysis tables and technical data attached to the commercial products, What is necessary is just to know the content of groups, and to make it the said compounding ratio based on them.

The aqueous glazing coating composition of the present invention can further contain a plasticizer. As the plasticizer, tributoxyethyl phosphate, tributyl phosphate, phosphate esters such as triphenyl phosphate, dibutyl phthalate, phthalate esters such as di-2-ethylhexyl phthalate, citrate esters such as tributyl acetyl citrate, dimethyl adipic acid, And adipic acid esters such as dibutyladipate.
Conventionally, tributoxyethyl phosphate has been widely used as a plasticizer generally used for floor polishes, but in the direction of avoiding the use of such phosphorus compounds for environmental reasons (ie, In the present invention, it is particularly preferable to use citrate esters among the above-mentioned plasticizers. The mixing ratio of the plasticizer is usually preferably from 5 to 25 parts by mass per 100 parts by mass of the solids of the components (a), (b) and (c).

The aqueous glazing coating composition of the present invention, in addition to the above-mentioned components, is usually blended with a conventional aqueous polisher for flooring, that is, a wax emulsion, an alkali-soluble resin, a film-forming auxiliary, etc. Can be similarly compounded. As the wax of the wax emulsion, a natural wax, a synthetic wax, and a modified product thereof can be widely used. Examples of natural waxes include hydrogenated hardened waxes such as beef tallow and lard, animal waxes such as lanolin and beeswax, hydrogenated waxes such as soybean oil and castor oil, carnauba wax, candelilla wax, vegetable waxes such as wax and bran wax. Mineral waxes such as wax, montan wax, sericin wax, paraffin wax, and microcrystalline wax can be used.

The synthetic wax may have a molecular weight of 500-500.
About 5,000 polyethylene wax, polypropylene wax, Fischer-Tropsch wax and the like can be mentioned. Emulsions of these waxes can be produced by known methods such as emulsification by adding an emulsifier to these waxes.

As the alkali-soluble resin, styrene-
(Anhydride) maleic acid copolymer resin, styrene-acrylic acid copolymer resin, acrylic acid resin, rosin-maleic acid adduct modified with a polyol, rosin-fumaric acid adduct, and the like can be used.

Benzyl alcohol,
Examples thereof include alcohols such as 3-methoxy-3-methylbutanol, and glycols such as diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol ethyl ether, and dipropylene glycol methyl ether.

In addition to these wax emulsions, alkali-soluble resins, and film-forming auxiliaries, it may contain, as trace components, wetting agents, defoamers, preservatives, and the like.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. Parts and% in Examples and Comparative Examples are based on mass. The above components and other components used in Examples and Comparative Examples are as follows.

A carboxy group-free urethane Em manufactured by Dainippon Ink and Chemicals, trade name: Hydran HW-
950 (solid content 30%), manufactured by Soft Acrylic Em Sansui Co., Ltd., trade name: A-304 (glass transition temperature 8 ° C,
Hard Acrylic Em Rohm & Haas Japan Ltd., trade name: Primal B-924 (glass transition temperature 45 ° C, solid 38)
%) Carboxy group-containing urethane Em An emulsion of a polyurethane containing a carboxy group.
Product name: Neoretz R-9637 (solids 36%) Plasticizer Tributoxyethyl phosphate (TBEP) Tributyl acetylcitrate (ACTB) Film-forming aid Diethylene glycol monoethyl ether alkali-soluble resin Gifu Shellac Manufacturing Co., Ltd. , Trade name: Acrys GSA-4
04 solution in ammonia water (solid content 25%) wax emulsion manufactured by Toho Chemical Industry Co., Ltd., trade name: Hitec E-7102S
(35% solids) Wetting agent Ciba Geigy Co., Ltd., trade name: Rhodine S-100 is diluted with water so that the active ingredient becomes 1%.

(Examples 1 to 6) (Comparative Examples 1 to 7) The components shown in Tables 1 and 2 and water were blended in the proportions shown in Tables 1 and 2 (total of 100 parts) to provide glazing for floors. An agent composition was prepared. In Tables 1 and 2, numerical values in parentheses () are parts by mass as a solid. The performance of each of the obtained compositions was evaluated as follows, and the results are shown in Tables 3 and 4.
It was shown to. In the following, those marked with a circle are the lowest practical limits.

(Performance Evaluation) Water resistance: conforms to JIS K 3920 (17) ◎: Whitening recovers in less than 1 minute ：: Whitening recovers in less than 5 minutes △: Whitening recovers in 5 minutes or more ×: Whitening does not recover Water resistance: After coating each of the above compositions on a stone floor material to form a film, the film is immersed in water for 24 hours, and the state of peeling of the film is observed. ◎: No change in the state of the film ○: The film floats a little, but returns when dried out of water △: The film is partially peeled off in water ×: The film is completely peeled off in water Heel mark resistance: JIS K 3920 (15)
◎: almost no heel mark ○: heel mark is slightly difficult to attach △: heel mark is slightly easy to attach ×: many heel marks are attached Abrasion resistance: After the above compositions are applied to a polyvinyl chloride flooring material to form a film, the wear loss (mg) of the film is measured by a Taber abrasion tester. 5. Removability: conforms to JIS K 3920 (19). ：: The film is removed when the number of washings is 25 to 50 times. ：: The film is removed when the number of washings is 51 to 100 times. Δ: The number of washings is 101 to 200 times. ×: The film is removed when the number of times of washing is 201 or more. Adhesion to polyolefin flooring: white corona-discharged polypropylene plate (thickness 3.0 mm, 3
0.3 cm square; surface tension of 380 μN / cm)
After coating each composition colored with a red dye to form a film, the film is rubbed with a nail and evaluated according to the following criteria. ：: No peeling even if rubbed 11 times or more with a nail. ○: Peeled after rubbing 10 times with a nail, but the base is difficult to see. △: Easy rubbing with 10 times rubbing with a nail and the base is visible. ×: 9 times with a nail. Easily peels off by rubbing, making the base completely visible

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

As is clear from Tables 3 and 4, the compositions of the present invention obtained in Examples are more resistant to water, water, and heel marks than the corresponding compositions obtained in Comparative Examples. It can be seen that the abrasion resistance and the removability are excellent.
Furthermore, it turns out that the composition which concerns on an Example is very excellent especially the adhesiveness with respect to a polyolefin-type flooring material.

[0042]

EFFECTS OF THE INVENTION The water-based glazing coating composition of the present invention has the following three properties: particularly high water resistance, excellent abrasion resistance, and excellent adhesion to a wide range of flooring materials including polyolefin flooring materials. At a high level. Therefore, the aqueous glazing coating composition of the present invention often comes into contact with water, there is a chance to be exposed to excessive water, and when applied to floor polishes such as places where many people walk, Compared to the case where a conventional floor polish is used, a great effect can be exhibited in both protection of the floor material and maintenance of the aesthetic appearance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09G 1/04 C09G 1/04 F term (Reference) 4J034 BA03 DA01 DB03 DB07 DF01 DF33 DG27 HA01 HA07 HC03 QC05 RA07 4J038 CG001 CG002 DG001 DG002 DG111 DG112 DG131 DG132 DG261 DG262 GA06 GA13 JA56 JC38 MA08 MA10 MA13 NA01 NA05 NA11 NA12 PB02 PB05

Claims (4)

[Claims] 1. An emulsion of (a) a polyurethane having no carboxy group in the molecule, and (b) an acrylic polymer having a carboxy group in the molecule and having a glass transition temperature of -10 ° C. to + 25 ° C. Emulsion, (c) an emulsion of an acrylic polymer having a carboxy group in the molecule and having a glass transition temperature of more than 25 ° C., and (d) an aqueous glazing coating containing a polyvalent metal complex capable of acting on the carboxy group as an essential component Composition. 2. The compounding ratios of the above (a), (b) and (c) are as follows: (a) is 10 to 50% by mass, (b) is 10 to 30% by mass, and (c) is a solid. Is 20 to 80% by mass, and the compounding ratio of (d) is 0.1 to 1 times as the number of ions of the metal of (d) per the total amount of carboxy groups of the acrylic polymer of (b) and (c). The aqueous glazing coating composition according to claim 1, which is in an equivalent amount. 3. The aqueous glazing coating composition further comprises a citrate compound according to the above (a),
3. The aqueous glazing coating composition according to claim 1, wherein the composition contains 5 to 25 parts by mass per 100 parts by mass of the solids of (b) and (c). 4. The method according to claim 1, wherein (a) is an emulsion of a polyurethane obtained by using a polyether polyol or a polyester polyol and an aliphatic diisocyanate as main raw materials and having a sulfonate group at a molecular terminal. The aqueous glazing coating composition according to any one of the above.