JP2978577B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coating composition, and more particularly, to a method for producing a stable coating composition capable of forming a tough and glossy film when applied to a floor surface. It relates to a manufacturing method.

[0002]

2. Description of the Related Art A coating composition for coating floors such as wood, concrete, vinyl tiles, rubber tiles, linoleum tiles, etc. has good workability at the time of application, and a film obtained after drying has excellent gloss. In addition, it is required that black heel marks are not easily formed by shoes when walking, and that the shoes have excellent durability. In addition to these performances, in addition to detergent resistance that can maintain gloss with ordinary detergent care, removability that can be easily removed by chemical means instead of physical removal when stains and damage become severe is necessary. For the purpose of achieving these reciprocal properties at the same time and forming a tough film having excellent removability and excellent removability, a coating material composition in which a polyvalent metal ion or a polyvalent metal complex is blended with an emulsion copolymer has been proposed. (Japanese Unexamined Patent Publication (Kokai) No. 2-2198163 and Japanese Patent Publication No. 47-15597). However, if the polyvalent metal ion is directly added to the polymer emulsion, the aggregation of the emulsion is likely to occur when the metal ion is added, so that there is a problem that a large amount of an emulsifier is required. However, when the complex is decomposed by drying after coating, amine and ammonia which are ligands of the complex are volatilized to generate an amine odor and an ammonia odor.

As a method for solving the smell of ammonia and amine when applying a coating composition, a method of dispersing zinc oxide in a polymer emulsion has been proposed (JP-A-57-117552). According to this method, for example, by stirring and mixing to disperse zinc oxide in an emulsion containing an acrylic copolymer, a coating material composition that is stable and does not have an ammonia odor or an amine odor during drying can be obtained. However, since zinc oxide is extremely insoluble in water, it is difficult for zinc oxide to migrate into polymer oil droplets in the emulsion, and there is a problem that zinc oxide precipitates when the emulsion is left for a long time. In order to solve this problem, there has been proposed a composition obtained by reacting a transition metal with a polymer at a specific temperature (Japanese Patent Application Laid-Open No. 2-21986).
No. 3), a large energy loss due to the need to heat the glass transition temperature (Tg) or higher of the resin, and when a metal such as zinc is reacted at a temperature higher than the Tg, the polymer is formed between the oil droplets of the emulsion. Since crosslinks are formed, there is a problem in that the stability of the emulsion is impaired.

[0004]

Accordingly, the present invention can complete the reaction of the cross-linking agent with the polymer at a relatively low temperature, and can form a tough film free of ammonia odor or amine odor during coating and drying. An object of the present invention is to provide a method for producing a coating composition which provides a stable coating composition to be formed.

[0005]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, before reacting a polyvalent metal cross-linking agent such as zinc in the polymer emulsion, the polymer emulsion was coated with a film. When the emulsion oil droplets are swollen by adding a forming agent and / or a plasticizer, the reaction between the polyvalent metal and the polymer occurs very quickly, and a stable coating material composition capable of forming a tough film after coating and drying. They found that a product could be obtained, and completed the method of the present invention. That is, the present invention relates to a method of adding a film-forming agent and / or a plasticizer to a polymer emulsion containing a polymer having an acid value of 20 to 130, which is produced by polymerization of an ethylenically unsaturated monomer. Another object of the present invention is to provide a method for producing a coating composition, which comprises reacting 0.05 to 0.9 chemical equivalents of a polyvalent metal.

The polymer used in the present invention is a polymer produced by polymerization of an ethylenically unsaturated monomer,
Any material can be used as long as it can be dissolved or dispersed in water, has an acid functional group and has an acid value in the range of 20 to 130. Generally, a polymer produced by using an ethylenically unsaturated monomer such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, or vinyl phenol, which is an acidic monomer, at 3 to 20% by weight based on all monomers. Coalescing can be used. The monomers used in addition to the above-mentioned monomers are appropriately selected by those skilled in the art so as to provide various properties according to the application, but for example, a polymerizable polymer capable of forming a soft polymer or a hard polymer in the presence of a radical catalyst Comonomers can be mentioned.

Examples of comonomers that give a soft polymer by polymerization include primary and secondary alkyl acrylates, primary and secondary alkyl methacrylates, and vinyl esters of saturated monocarboxylic acids. Saturated compounds include acrylates, itaconates and methacrylates, and preferred esters include those having an alkyl group having 8 or less carbon atoms. Specifically, the monomer giving the soft polymer is represented by the following formula: H ₂ C = C (R ¹ ) —COOR ² (wherein R
¹ is hydrogen or a methyl group; when R ¹ is a methyl group, R ² represents a primary or secondary alkyl group having 5 to 18 carbon atoms; when R ¹ is hydrogen, R ² represents a carbon atom The number of atoms is 18 or less, preferably 2 to 8, particularly preferably 2 to
Which represents four alkyl groups), and more specifically, ethyl acrylate,
Propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, sec-
Butyl acrylate, amyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5
-Trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, cetyl acrylate, octadecyl acrylate, octadecenyl acrylate,
n-amyl methacrylate, sec-amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, and butoxyethyl acrylate Or those having a substituted alkyl group such as butoxyethyl methacrylate can be mentioned. Further, examples of the monomer which gives a soft polymer include ethylene, propylene, butadiene, chloroprene, isobutene, and isoprene.

Examples of the polymerizable ethylenically unsaturated monomer which gives a hard polymer by polymerization include an alkyl methacrylate having an alkyl group having 4 or less carbon atoms, an alkyl acrylate having an alkyl group having 2 or less carbon atoms, and tert-alkyl. Amyl methacrylate, tert-butyl or
tert-amyl acrylate, cyclohexyl, benzyl, or isobornyl acrylate or methacrylate, acrylonitrile, or methacrylonitrile,
Styrene, vinyl chloride, chlorostyrene, vinyl acetate,
And α-methylstyrene. More specifically, the following _{formula: H 2 C = C (R} 3) -X ( wherein, R ³ is hydrogen or methyl group, X is a nitrile, phenyl, methylphenyl, and ester-forming group, - COOR ⁴ (but
R ⁴ is cyclohexyl, methyl, ethyl, or tert-alkyl having 4 to 5 carbon atoms) or, when R ³ is methyl, an alkyl group having 2 to 4 carbon atoms). And more specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate. Acrylamide and methacrylamide are also useful.

The polymers used in the present invention include, in addition to the above polymers, vinyl formate, vinyl acetate,
Mention may be made of polymers of esters of vinyl alcohol, such as vinyl propionate, vinyl butyrate, and vinyl vergitate. For example, poly (vinyl acetate) and vinyl acetate, vinyl chloride, vinylidene chloride, styrene, vinyl toluene, acrylonitrile,
Copolymers with methacrylonitrile, acrylate or methacrylate ester can be mentioned.

These polymers can be produced, for example, as block copolymers, random copolymers, graft copolymers, and core-shell polymers in the presence of water or an organic solvent, for example, by emulsion polymerization or solution polymerization. it can. In order to emulsify a monomer in emulsion polymerization, for example, US Pat. Nos. 2,754,280 and 2,795,564
And the like. An anionic, cationic, or nonionic emulsifier, preferably an anionic or nonionic emulsifier may be used as the emulsifier. For example, alkyl sulfonic acids, aryl sulfonic acids, alkyl aryl sulfonic acids, alkyl sulfates, aryl sulfates, and alkali metal salts, ammonium salts and amine salts of alkyl aryl sulfates can be suitably used.
These emulsifiers may be used at a ratio of 0.5 to 10% by weight based on the total amount of the monomers. When a radical initiator such as ammonium persulfate or potassium persulfate is used as the polymerization initiator, it may be used alone or in combination with an accelerator such as potassium disulfite or sodium thiosulfate. These initiators and accelerators are usually used in an amount of 0.1 to 5.0% by weight based on the total amount of the monomers. Further, a chain transfer agent containing mercaptan, polymercaptan, and polyhalide may be used. These are generally used in an amount of 0.01 to 1.0% by weight based on the total amount of the monomers.

The polymer preferably used in the present invention is a copolymer having a molecular weight of about 10,000 to 1,000,000 and an acid value of 20 to
130, preferably 30 to 80. These polymers are prepared as aqueous emulsions by the above-mentioned method so that the pH is usually in the range of 2 to 4. Examples of aqueous acrylic copolymer emulsions obtained by emulsion copolymerization include (a) 6 to 10% by weight of α, β-unsaturated carboxylic acid and (b) 50 to 50% of methyl methacrylate as monomer components.
74% by weight, (c) 20 to 40% by weight of an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms, and adding an emulsifier and a polymerization initiator known to those skilled in the art to carry out emulsion polymerization. What was manufactured by making it do.

The method of the present invention is characterized in that a film-forming agent and / or a plasticizer are added to the polymer emulsion produced as described above, and thereafter, the polymer is reacted with a polyvalent metal. . In the present invention, the film-forming agent exhibits a plasticizing function only at the time of film formation to assist in the formation of a polymer film, and after the film is formed, evaporates relatively quickly to evaporate and mechanical strength of the film and the film. Plasticizers have the function of improving hardness, and plasticizers have little volatility per se, but have the effect of imparting plasticity to a rigid polymer to improve workability, and all of them have a floor coating composition. It is commonly used for things.

As the film-forming agent, for example, a compound represented by the general formula AO-
[—RO-] _n -A ′ (where A and A ′ may be the same or different and each have a hydrocarbon group of 1 to 8 carbon atoms,
Oxyalkylene glycol derivatives represented by the following formulas: (a) to (c) represent an acyl group, a hydrogen atom, R represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 3, for example, methyl carbitol, ethyl carbitol , Butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether,
Propylene glycol dibutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol tertiary butyl ether, dipropylene glycol methyl ether, dipropylene Propylene glycol ethyl ether, dipropylene glycol tertiary butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether , Tripropylene glycol dibutyl ether, propylene glycol dimethyl ether acetate, propylene glycol diethyl ether acetate, propylene glycol dibutyl ether acetate, dipropylene glycol dimethyl ether acetate, dipropylene glycol diethyl ether acetate, dipropylene glycol dibutyl ether acetate Over DOO, 3-methyl-3-methoxybutyl acetate, can be used ethylene glycol or N- methyl-2-pyrrolidone.

As the plasticizer, for example, monobutoxymethyl phosphate, monobutoxyethyl phosphate, monobutoxybutyl phosphate, dibutoxymethyl phosphate, dibutoxyethyl phosphate, dibutoxybutyl phosphate, tributoxymethyl phosphate , Tributoxyethyl phosphate, tributoxybutyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibenzyl phthalate, ε-caprolactam, 2-pyrrolidone, 2,2,4-trimethylpentadiol-1,3 -Monoisobutyrate and the like.

The film-forming agent and the plasticizer are not limited to the above, and any film-forming agent and plasticizer known to those skilled in the art can be used. Among these, methyl carbitol, ethyl carbitol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tripropylene glycol methyl ether, ethylene glycol, propylene Preference is given to using glycols, particularly preferably ethyl carbitol, and tributoxyethyl phosphate, dibutyl phthalate, 2-pyrrolidone as plasticizer. The amount of these film-forming agents and / or plasticizers varies depending on the Tg of the polymer and the minimum film-forming temperature.
Used at 100% by weight, preferably 25-50% by weight
It is. When these are added to the polymer emulsion, they may be added during the emulsion polymerization of the polymer, but it is preferable to add them to the produced polymer emulsion. For example, a film-forming agent or a plasticizer may be dissolved in water twice or more (volume) and added with good stirring, or they may be added in several portions. The addition may be performed over 5 to 15 minutes by a method such as dropping. After the addition of the film-forming agent and / or the plasticizer, the polymer emulsion is further stirred for 30 minutes to 2 hours, whereby the polymer oil droplets in the emulsion swell, and the acid functional group of the polymer becomes a surface of the micelle. The acid functional group is easily cross-linked by the polyvalent metal added thereafter. In the stirring operation, the minimum film formation temperature of the polymer emulsion after the addition of the film-forming agent and / or the plasticizer is set to 5 lower than the minimum film formation temperature of the polymer emulsion before the addition of the film-forming agent and / or the plasticizer. The temperature may be lower than or equal to 0 ° C., preferably, so that the minimum film forming temperature of the polymer emulsion after adding the film forming agent and / or the plasticizer is equal to or lower than room temperature.

The polyvalent metal compound used in the production of the coating composition is, for example, a hydroxide of a metal such as zinc, calcium, aluminum, zirconium, magnesium, nickel, cobalt, beryllium, bismuth, lead, copper, iron and the like. , Oxide, chloride, sulfide, carbonate, acetate, formate, glutamate, salicylate, glycolate, octonate, benzoate, gluconate, oxalate, lactate, citric acid Salts, malate salts, glycine salts, alanine salts, β-alanine salts may be mentioned, and mixtures thereof may be used. The above polyvalent metal compound may be in the form of a commercially available powder, but preferably has a particle size of 0.2.
What is necessary is just to use the thing of fine grade of 0.5 micron. The amount of the polyvalent metal compound to be used is 0.05 to 0.9 chemical equivalent, preferably 0.3 to the acid value of the above polymer.
The chemical equivalent may be up to 0.6. When the content of the polyvalent metal compound falls below the above range, there is a problem that the toughness of the obtained film is lost, and when the content of the polyvalent metal compound exceeds the above range, the product stability and leveling property are reduced. Problem. As a method of dispersing the above polyvalent metal compound in the polymer emulsion after the addition of the film-forming agent and / or the plasticizer, and reacting the polyvalent metal compound with the polymer, a predetermined amount of the powdery polyvalent metal compound is used. Can be added to the polymer emulsion, followed by stirring and mixing, or a method in which an aqueous solution or dispersion of the polyvalent metal compound is separately prepared and added to the polymer emulsion. The aqueous solution or dispersion used in the latter method, after adding the polyvalent metal compound to the aqueous solvent at 10 to 50% by weight,
What is necessary is just to dissolve with stirring or disperse with stirring. A homomixer, a kneader or the like may be used for stirring.

The step of reacting the polymer with the polyvalent metal compound can be carried out at any temperature between room temperature and heating. Preferably, the temperature of the polymer emulsion to which the polyvalent metal compound is added is adjusted to the temperature of the polymer. Glass transition temperature (Tg)
It may be performed while maintaining the following. If the reaction temperature is too low, it is difficult for the polyvalent metal compound to be taken into the polymer oil droplets in the emulsion, and there occurs a problem that the polyvalent metal compound does not react with the polymer and precipitates in the polymer emulsion. The reaction is preferably performed at a temperature of 0 ° C. or higher. On the other hand, if the reaction temperature is higher than the decomposition temperature of the polymer emulsion, the production of the coating material composition becomes difficult, which is not preferable. The reaction is continued until the polyvalent metal compound used does not precipitate from the coating composition in emulsion form.
That is, the process may be continued until a coating material composition in the form of a uniform emulsion is obtained. More specifically, the minimum film formation temperature of the obtained coating material composition is determined by setting the film forming agent and / or
Or, after the addition of the plasticizer, the minimum film formation temperature of the polymer emulsion containing no polyvalent metal compound is 5 ° C or more,
It is preferable to carry out continuously so as to increase the temperature by 10 ° C. or more. Generally, when 40% or more of the acid functional groups in the polymer are crosslinked with a polyvalent metal, the minimum film formation temperature is 1
0 ° C or higher.

In the above manufacturing process, a film forming agent and / or
Alternatively, the base may be added to the polymer emulsion to which the plasticizer has been added to adjust the pH to 6 to 9, preferably 7.5 to 8.5, and then reacted with the polyvalent metal compound. As the base to be used, for example, ammonia and amine can be exemplified, and as the amine, diethylaminoethanol, monoethanolamine, diethylamine, triethylamine and the like can be used. Of these, it is preferable to use diethylaminoethanol. For example, when adding aqueous ammonia, aqueous ammonia containing 10% by weight or less of ammonia is added to the polymer emulsion.
The whole amount may be added at a time so that the pH becomes 6 to 8, or the necessary amount may be added in several portions. The addition may be performed over 5 to 15 minutes by a method such as dropping. When a highly hydrophobic polymer emulsion is used, the pH is preferably set to 8 to 9, and when a highly hydrophilic polymer emulsion is used, the pH is preferably set to 6 to 8. After adding the base, the polymer emulsion is further stirred for 30 minutes to 2 hours,
In combination with the action of the film-forming agent and / or the plasticizer, the swelling of the polymer oil droplets in the emulsion becomes remarkable, and the acid functional groups of the polymer are oriented on the micelle surface to easily form crosslinks by the polyvalent metal compound. It will be done. If the pH of the polymer emulsion after the addition of the base exceeds 9, it is not preferable because the odor of ammonia or amine used as the base becomes noticeable.

In addition to the above-mentioned components, the coating material composition produced in this manner includes known components such as waxes such as paraffin, montan and polyethylene wax; rosin-modified maleic resin, styrene-maleic resin. Alkali-soluble resin such as fluorinated surfactants and the like. Of these, the wax and the alkali-soluble resin component are used at about 5 to 70% by weight based on the polymer. Further, the above-mentioned film-forming agent and plasticizer may be further added to the coating composition produced as described above. The amount of the film-forming agent and / or plasticizer to be added is 50% by weight or less, preferably 10% by weight or less based on 100% by weight of the polymer. These components are directly mixed into the polymer emulsion or added as an aqueous dispersion alone or together with the polyvalent metal compound. It is preferable that the coating material composition produced in this way is prepared so that the final pH is in the range of 6 to 8. When the pH is lower than 6, the stability of the product and the leveling property of the film formed after coating tend to decrease, and when the pH is higher than 8, the re-coating property of the coating composition and the ammonia odor and amine odor upon drying are reduced. It is not preferable because it is strong. In adjusting the pH of the coating composition, in addition to the above-described base, an alkali metal hydroxide, or an acid such as carbon dioxide or acetic acid may be used, and these may be used during the reaction step between the polyvalent metal compound and the polymer. Or after the completion of the reaction, the necessary amount may be appropriately added.

When using the coating composition produced according to the present invention, wood, concrete, rubber tile,
The polymer content was adjusted to 3 to 40% by weight and the total resin content to 5 to 50% by weight based on the total weight of the coating composition on the floor surface of a vinyl tile, a linoleum tile, or the like. The composition may be applied once or more than once and dried at a temperature not lower than the minimum film formation temperature. By such an application method, a resin film having excellent gloss and durability can be obtained. In addition, when removing the formed film, an electric polisher equipped with a pad and the like is applied to a coating surface from which a remover obtained by dissolving an amine, an alkali metal hydroxide, a chelating agent, a surfactant, etc. in water is removed. The film can be easily removed by rubbing and washing with the like.

[0021]

The coating composition produced according to the present invention is stable for a long time and does not contain heavy metals, so that there is no concern about environmental pollution. Further, since no metal complex is used, there is no unpleasant smell of ammonia due to decomposition of the complex during coating and drying. The dried film obtained from the coating material composition is tough because the main component polymer is crosslinked with a polyvalent metal, and is also extremely excellent in various properties such as gloss, leveling property, and removability. So useful.

[0022]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following Examples, Comparative Examples, and Reference Examples, the “active ingredient” indicates the content (concentration) of each resin (unit:% by weight).

Reference Example 1 Production of Aqueous Acrylic Resin After nitrogen was charged into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube, deionized water was added.
The emulsifier was added and then warmed to 60 ° C. in a water bath. During the stirring, in addition to the catalyst and the monomer, if necessary, a molecular weight regulator (see Table 1) was gradually added dropwise over 2 hours to complete the polymerization, and an acrylic resin emulsion (AF) containing 40% of the active ingredient was used. I got

[0024]

[Table 1]

Embodiment

[Table 2]

[0026]

[Table 3] (Note 4) Solvents (2, 2, 2) manufactured by Eastman Kodak Company
(2-trimethylpentanediol-1,3-monoisobutyrate) (Note 5) To 49.0 g of deionized water, 10 g of zinc oxide was added and dispersed by stirring. 22.0 g of 28% in the dispersion
Add ammonia water and stir, then add 19.0 glycine
g, and stirred until a clear solution was obtained to produce a glycine zinc ammonia complex (zinc content: 8.03%). (Note 6) 10 g of zinc oxide was added to 55.0 g of deionized water, and dispersed by stirring. Was. 18.0 g of 28% in the dispersion
Add ammonia water and add 17.0 g of ammonium carbonate
In addition, the mixture was stirred until a clear solution was obtained to produce a zinc carbonate ammonia complex (zinc content: 8.03%). (Note 7) Low-molecular-weight acrylic emulsion manufactured by Rohm and Haas (product name: Primal B-644, effective) (Ingredient 43%) (Note 8) A low molecular weight polyethylene wax (Ac-392) manufactured by Allied Chemical Co., Ltd. emulsified with a nonionic surfactant by Toho Chemical Industry Co., Ltd. (Active ingredient 40%) (Note 9) Fluorosurfactant manufactured by Dainippon Ink Industries, Ltd. (Product name: Megafac F-812, active ingredient 15)
%)

Performance evaluation

[Table 4]

Evaluation method (1) For Note 10 to Note 17, performance was evaluated according to the Japan Floor Polishing Industry Association Standard (JFPA). Product stability: JFPA standard -13 (storage stability) Leveling property: JFPA reference standard (1) Gloss (%): JFPA standard -10 (measure the gloss of three coats:%) Water resistance: JFPA standard 13 (Evaluated by the presence or absence of the whitening phenomenon) Detergent resistance: JFPA standard-14 Removability: JFPA standard-15 Recoatability: JFPA reference standard (2) Black heel mark resistance: JFPA standard-11 (black heel mark (Evaluate the amount of adhesion by observing it with the naked eye.) (2) For Note 18 to Note 20, performance was evaluated as follows. The abrasion resistance was evaluated by measuring the degree of abrasion with a taper tester after leaving a test specimen coated five times by the same working method as in JFPA standard-10 at room temperature for 168 hours, and then evaluating it (abrasion wheel: CS-17, 200 rotations, abrasion unit: g) The film hardness was measured with a Knoop hardness tester after a test piece coated five times by the same working method as JFPA standard-10 was left to dry at room temperature for 168 hours. did. The odor evaluation is 1
After application at a rate of 100 m ² per liter of each composition in a room of 65 m ² , evaluation was made by scoring 10 subjects (evaluation criteria, 3: not odor; 2: normal; 1: odor).

The compositions 1 to 10 of the present invention exhibited excellent properties in all evaluation items, and were excellent in all aspects such as floor polish performance and odor.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C09G 1/16 C09D 171/02 C09D 201/08 C09G 1/00

Claims (8)

(57) [Claims] 1. After adding a film-forming agent and / or a plasticizer to a polymer emulsion containing a polymer having an acid value of 20 to 130 produced by polymerization of an ethylenically unsaturated monomer, the acid value of the polymer is reduced. A method for producing a coating composition, comprising reacting 0.05 to 0.9 chemical equivalents of a polyvalent metal compound. 2. The polyvalent metal compound is zinc, calcium, aluminum, zirconium, magnesium, nickel,
Cobalt, beryllium, bismuth, lead, copper, iron hydroxide, oxide, chloride, sulfide, carbonate, acetate, formate, glutamate, salicylate, glycolate,
The method according to claim 1, wherein the method is selected from octonate, benzoate, gluconate, oxalate, lactate, citrate, malate, glycine, alanine, and β-alanine. 3. A film-forming agent represented by the following general formula A-O-[-RO-] _n -A ′ (where A and A ′ may be the same or different and have 1 to 8 carbon atoms). A hydrocarbon group, an acyl group having 1 to 4 carbon atoms, a hydrogen atom, R represents an alkylene group having 2 to 4 carbon atoms,
The method according to claim 1, wherein n is an integer of 1 to 3). 4. The film forming agent is methyl carbitol, ethyl carbitol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, tripropylene glycol methyl ether, ethylene glycol, 4. The method according to claim 3, wherein the method is selected from propylene glycol. 5. The method according to claim 1, wherein the film forming agent is N-methyl-2-pyrrolidone. 6. The method according to claim 1, wherein the plasticizer is monobutoxymethyl phosphate, monobutoxyethyl phosphate, monobutoxybutyl phosphate, dibutoxymethyl phosphate, dibutoxyethyl phosphate, dibutoxybutyl phosphate, tributoxymethyl phosphate, Tributoxyethyl phosphate, tributoxybutyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dibenzyl phthalate, ε-caprolactam, 2-
Pyrrolidone, 2,2,4-trimethylpentadiol-
The method according to claim 1, wherein the method is selected from 1,3-monoisobutyrate. 7. The method according to claim 1, wherein the reaction is carried out at a temperature lower than the glass transition temperature of the polymer. 8. The method according to claim 1, wherein the polymer has a molecular weight of 10,000 to 1,000,000.