JP2916019B2 - Method for producing coating material 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 material composition, and more particularly to a method for forming a tough and glossy film having no amine odor or ammonia odor when applied to a floor surface. And a method for producing a stable coating material composition.

[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).

The inventor of the present invention has proposed that when a polyvalent metal compound is reacted with a polymer in the presence of a base such as an amine or ammonia, the reaction between the polyvalent metal and the polymer occurs very quickly, and the toughness is increased. They found that a coating composition capable of providing a film could be obtained, and filed a patent application (Japanese Patent Application No. 0155/1991).
No. 11). However, even in the coating composition, the pH is 9.
When it exceeds 5, the amine odor and the ammonia odor may become noticeable. In addition, when a polyvalent metal complex is used as a polyvalent metal ion source, a large amount of amine or aqueous ammonia is used when the polyvalent metal complex is required, so that an excess amine or Ammonia remains, and there is a problem that these are volatilized at the time of coating to emit an amine odor or an ammonia odor. In addition, when the coating material composition dries after application to decompose the complex, there is a problem that amine and ammonia, which are ligands of the complex, are volatilized to generate an amine odor and an ammonia odor. There was a problem that the working conditions of the country worsened.

[0004]

Accordingly, an object of the present invention is to provide a method for producing a coating material composition which has no ammonia odor or amine odor at the time of coating or drying and gives a tough resin film.

[0005]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, after adding a polyvalent metal compound such as zinc to a polymer emulsion containing an amine or ammonia, the emulsion was added to the emulsion. By adding the acid, the ammonia odor and the amine odor of the coating composition can be efficiently eliminated, and no odor is generated even when the obtained coating composition is applied and dried as a floor coating. This led to the completion of the present invention.

That is, the present invention is characterized in that an acid is added to an emulsion obtained by reacting a polymer with a polyvalent metal compound in the presence of an amine or ammonia to adjust the pH of the emulsion to 6 to 9.5. After adding an aqueous solution containing a polyvalent metal compound and an amine and / or ammonia to an emulsion containing a polymer, and then adding an acid to adjust the pH of the emulsion to 6 to 9.5
It is intended to provide a method for producing a coating material composition, characterized in that:

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 The number of carbon 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.

As the polymerizable ethylenically unsaturated monomer which gives a hard polymer by polymerization, alkyl methacrylate having an alkyl group having 4 or less carbon atoms, alkyl acrylate having an alkyl group having 2 or less carbon atoms, tert- 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 a block copolymer, a random copolymer, a graft copolymer, or a core-shell polymer 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 1, 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) methyl methacrylate of 50% as monomer components.
(C) 20 to 40% by weight of an alkyl acrylate having an alkyl group having 2 to 8 carbon atoms
And those obtained by adding an emulsifier and a polymerization initiator known to those skilled in the art and subjecting them to emulsion polymerization.

Examples of the polyvalent metal compound used for producing the coating material composition include zinc, calcium, aluminum, zirconium, magnesium, nickel, cobalt, beryllium, bismuth, lead, copper, iron and the like. . Salts or complexes of these metals can also be used, for example, hydroxides, oxides, chlorides, sulfides,
Carbonate, acetate, formate, glutamate, salicylate, glycolate, octonate, benzoate, gluconate, oxalate, lactate, citrate, malate, glycine, alanine Salts, β-alanine salts, or mixtures thereof, and complexes of these metals, such as ammonia and amine complexes, can also be used. Examples of the amine capable of forming a complex include morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine. When a polyvalent metal complex is used, at least a part of the ligand is volatilized during film formation, so that the polyvalent metal complex is decomposed and the polyvalent metal can react with the polymer. Preferably, the ligand is a volatile ligand. An example of such a ligand is ammonia. As the above-mentioned polyvalent metal compound, a commercially available powdery compound may be used, but preferably a fine-grade compound having a particle size of 0.2 to 0.5 micron is used. When a polyvalent metal compound having a volatile ligand such as ammonia is used, the polyvalent metal compound may be separately produced in an aqueous solvent and used. 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.

According to the first aspect of the present invention, an acid is added to an emulsion obtained by reacting a polymer with a polyvalent metal compound in the presence of an amine or ammonia to adjust the pH of the emulsion to 6 to 9. 5 is provided. The polyvalent metal compound suitably used in the method is, for example, a polyvalent metal compound such as a polyvalent metal salt or a polyvalent metal oxide. As a preferred embodiment of the method, an emulsion containing a polymer is used. Amine and / or
Alternatively, a method of reacting a polyvalent metal compound after addition of ammonia can be mentioned. More specifically, a pH of the polymer emulsion is preferably from 8 to 9.5 by adding an amine or ammonia to the polymer emulsion, preferably. Is pH 8.5
After adjusting the pH value to 9.0, a polyvalent metal compound is reacted with the polymer, and an acid is added to the obtained emulsion to adjust the pH of the reaction solution to 6 to 9.5. be able to.

The amine added to the polymer emulsion includes methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine,
Dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, diethylaminoethanol, monoethanolamine, ethylenediamine and the like can be mentioned, and ammonia includes ammonia water containing 10% by weight or less of ammonia. it can. Of these, it is preferable to use diethylaminoethanol. For example, when adding aqueous ammonia, the entire amount of aqueous ammonia containing 10% by weight or less of ammonia is added at a time so that the pH of the polymer emulsion becomes 6 to 9.5, or the required amount is added several times. What is necessary is just to add in divisions. 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,
The swelling of the polymer oil droplets in the emulsion becomes remarkable, and the acid functional group of the polymer is oriented on the surface of the micelle, whereby the polyvalent metal compound easily forms crosslinks.

As a method of reacting the polyvalent metal compound with the polymer, a method of adding a predetermined amount of a powdery polyvalent metal compound to the polymer emulsion and stirring and mixing the mixture, and an aqueous solution or aqueous solution of the polyvalent metal compound are used. A method in which a dispersion is separately produced and added to a polymer emulsion can be mentioned.
The aqueous solution or the aqueous dispersion used in the latter method is prepared by adding the polyvalent metal compound to the aqueous solvent in an amount of 10 to 50% by weight.
And then dissolving with stirring or dispersing with stirring. The stirring may be performed using a homomixer, a kneader, or the like, and the stirring can be performed at any temperature from room temperature or under heating.

The reaction between the polyvalent metal compound and the polymer is preferably carried out while maintaining the temperature of the polymer emulsion to which the polyvalent metal compound has been added at or below the glass transition temperature (Tg) of the polymer. . 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 may be continued until the polyvalent metal compound used no longer precipitates from the coating composition in the form of an emulsion, that is, until a coating composition in the form of a uniform emulsion is obtained. The minimum film formation temperature of the coating material composition, 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 reacting the polyvalent metal compound with the polymer, the reaction may be carried out in the presence of a film forming agent and / or a plasticizer. 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 effect of improving hardness, and plasticizers have little volatility per se, but have the effect of imparting plasticity to rigid macromolecules to improve workability. 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.

Examples of the plasticizer include monobutoxymethyl phosphate, monobutoxyethyl phosphate, monobutoxybutyl phosphate, dibutoxymethyl phosphate, dibutoxyethyl phosphate, dibutoxybutyl phosphate, and 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 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 process of the polymer, but it is preferable to add them to the produced polymer emulsion before the reaction with the polyvalent metal compound. 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 method is 5 to 1 depending on the method such as dropping.
It may be performed for 5 minutes. 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.

An emulsion, which is a reaction solution obtained by reacting a polymer with a polyvalent metal compound as described above, generally has a pH of 8.
Since the emulsion is prepared as about 5 to 10 emulsions, it emits an amine odor or an ammonia odor. By adding an acid to the emulsion so that the pH of the emulsion becomes 6 to 9.5, preferably 7 to 8.5, a coating composition having no amine odor or ammonia odor can be produced. Acids used include carbon dioxide, formic acid, acetic acid, propionic acid, butyric acid, citric acid, oxalic acid, malic acid, tartaric acid,
Lactic acid, gluconic acid, benzoic acid, salicylic acid, organic carboxylic acids such as glutamic acid, hydrochloric acid, and mineral acids such as sulfuric acid can be mentioned.Of these, it is preferable to use carbon dioxide. Either solid carbon dioxide (dry ice) or liquid carbon dioxide can be used. Particularly preferably, carbon dioxide gas is used, and a necessary amount of carbon dioxide gas may be blown into an emulsion obtained by reacting a polyvalent metal compound with a polymer. When carbon dioxide gas is blown into the reaction solution, the pH of the reaction solution rapidly decreases, and a coating material composition in which amine odor and ammonia odor have disappeared is produced.

According to a second aspect of the present invention, a polyvalent metal compound and an amine and / or
Alternatively, there is provided a method for producing a coating material composition, which comprises adding an aqueous solution containing ammonia and then adding an acid to adjust the pH of the emulsion to 6 to 9.5. The polyvalent metal compound suitably used in the method is a polyvalent metal complex having one or more ligands, and more preferably a polyvalent metal complex containing an amine and / or ammonia as a ligand. In a preferred embodiment of the method, an amine and / or
Or a method in which a polyvalent metal complex containing ammonia as a ligand is prepared as an aqueous solution when necessary, added to the polymer emulsion, and an acid is added to the obtained emulsion to adjust the pH of the emulsion to 6 to 9.5. Can be mentioned. The method for producing the polyvalent metal complex solution will be described by taking a zinc carbonate ammonia complex as an example. After adding 18 ml of 28% aqueous ammonia to an aqueous suspension containing about 10% by weight of zinc oxide in 55 ml of water, , 17 g of ammonium carbonate may be added to produce an aqueous solution having a pH of 10 or more containing a zinc carbonate ammonium complex. As a method of adding the aqueous solution to the polymer emulsion, 0.05 to 0.5 with respect to the acid value of the polymer.
A polyvalent metal complex solution containing 9 chemical equivalents of a polyvalent metal complex is
A method of gradually dropping the polymer emulsion over 5 to 30 minutes, preferably 10 to 20 minutes while stirring the polymer emulsion can be mentioned. Before or after adding the aqueous solution to the polymer emulsion, the above-mentioned film-forming agent and / or plasticizer may be added to the polymer emulsion. The film forming agent and / or the plasticizer is used in an amount of 2 to 100% by weight of the polymer.
Used at 100% by weight. Since the pH of the emulsion obtained as described above is generally about 8.5 to 10,
The emulsion has an amine odor and an ammonia odor. By adding an acid to the emulsion so that the pH of the emulsion becomes 6 to 9.5, preferably 7 to 8.5, a coating composition having no amine odor or ammonia odor can be produced. As the acid, the above-mentioned acids can be used. For example, by blowing carbon dioxide gas into the emulsion, the pH of the emulsion is rapidly lowered, and a coating material composition in which the amine odor has disappeared is produced.

In the first and second embodiments of the present invention, waxes such as paraffin, montan, and polyethylene wax, which are known components, are added to the obtained emulsion before adding an acid; rosin-modified maleic acid Resins, alkali-soluble resins such as styrene-maleic acid resins, and fluorine-based surfactants may be further added. Of these, the wax and the alkali-soluble resin component are used at about 5 to 70% by weight based on the polymer. Further, a film forming agent or a plasticizer may be added. The film-forming agent and / or plasticizer is added in an amount of about 10 to 100% by weight, preferably 25 to 40% by weight, based on 100% by weight of the polymer. When a film-forming agent or a plasticizer has already been added during the production process of the coating composition, the film-forming agent and / or the plasticizer to be further added is 50% by weight based on 100% by weight of the polymer. Or less, preferably 10% by weight or less.
These components are directly mixed into the polymer emulsion or added as an aqueous dispersion alone or together with the polyvalent metal compound. These components may be added to the coating composition produced according to the first and second aspects of the present invention described above, in which case the coating composition after adding these components The pH of the coating composition may fluctuate. In such a case, an acid or a base is further added to finally adjust the pH of the coating composition to a range of 6 to 9.5. Is preferred. If the pH is lower than 6, the stability of the product and the leveling property of the film formed after coating tend to decrease. If the pH is higher than 9.5, the recoating property of the coating composition and the ammonia odor and amine during drying are reduced. It is not preferable because it has a strong odor. After adding these components, examples of the base used to adjust the pH of the coating material composition include the above-described amines and ammonia, and bases such as alkali metal hydroxides. The above acids may be used.

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 or 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.

[0026]

The coating composition produced according to the present invention has no amine odor at the time of application and after drying, does not impair the health of workers at the time of application, and does not pollute the environment. Further, the coating composition is stable for a long period of time, and the dried film obtained by the coating composition is tough because a polymer as a main component is crosslinked with a polyvalent metal, and has a gloss, leveling property, It is useful because it has extremely excellent properties such as removability.

[0027]

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 filling nitrogen into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction tube, deionized water,
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

[0028]

[Table 1]

Example

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

(In Tables 2 to 4, Me represents a polyvalent metal.) (Note 4) 10 g of zinc oxide was added to 49.0 g of deionized water 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 transparent solution was obtained to produce a glycine zinc ammonia complex (zinc content: 8.03%). (Note 5) 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 transparent solution was obtained to produce a zinc carbonate ammonia complex (zinc content: 8.03%). (Note 6) 10 g of zinc oxide was added to 60.35 g of deionized water and dispersed by stirring. . 7.64 g of ethylenediamine and 7.72 g of 28% aqueous ammonia were added to the dispersion, and 14.29 g of ammonia carbonate was further added thereto. The mixture was stirred until it became transparent to produce a zinc carbonate ethylenediamine / ammonia complex ( (Zinc content: 8.03%) (Note 7) 10 g of zinc oxide was added to 60.0 g of deionized water and dispersed by stirring. 50.0 g of 28% in the dispersion
Manufactured by adding aqueous ammonia (zinc content: 8.03
(Note 8) Low-molecular-weight acrylic emulsion manufactured by Rohm and Haas (Product name: Primal B-644, active ingredient 43%) (Note 9) Low-molecular-weight polyethylene wax (Ac-392) manufactured by Allied Chemical Co., Ltd. Emulsified with a nonionic surfactant by Chemical Industry Co., Ltd. (active ingredient 40%) (Note 10) Fluorosurfactant manufactured by Dainippon Ink Industries, Ltd. (Product name: Megafac F-812, effective Ingredient 15
%)

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7]

Performance evaluation

[0038]

[Table 8]

[0039]

[Table 9]

Evaluation Method (1) For Note 11 to Note 18, performance was evaluated in accordance with the Japan Floor Polishing Industry Association Standard (JFPA). Product stability: JFPA standard -13 (storage stability, water-based floor polish) Leveling property: JFPA reference standard (1) Gloss (%): JFPA standard -10 (measure the gloss of three coats:%) : JFPA standard -13 (Evaluated by the presence or absence of whitening phenomenon) Detergent resistance: JFPA standard -14 Removability: JFPA standard -15 Recoatability: JFPA reference standard (2) Black heel mark resistance: JFPA standard -11 ( (Evaluate the amount of black heel mark adhered by observing it with the naked eye.) (2) For Note 19 to Note 21, performance was evaluated as follows.

The abrasion resistance was evaluated by measuring the abrasion degree with a taper tester after leaving a test piece coated five times by the same working method as in JFPA standard -10 at room temperature for 168 hours, and Abrasion wheel: CS-17, 200 rotations, abrasion amount unit: g) The film hardness was determined by a Knoop hardness tester after a test piece coated five times by the same working method as in JFPA standard-10 was allowed to dry at room temperature for 168 hours. Was measured.

The odor evaluation was applied at a rate of each composition per liter 100 m ² at room 165m ^2, it was evaluated by scoring measurer 10 Review (Evaluation Criteria, 3: smell not; 2: Normal ; 1: smell). Compositions 1 to 10 of the present invention exhibited excellent properties in all evaluation items, and were excellent coating compositions in all aspects such as floor polish performance and odor.

Claims (31)

(57) [Claims] (1) a molecular weight of 10,000 to 10,000 in an emulsion;
A polymer having an acid value of 20 to 130 having 1,000,000 and a polyvalent metal or a polyvalent metal compound is reacted in the presence of an amine or ammonia to obtain a polyvalent metal of the polymer. A method for producing a floor covering material composition, which comprises forming a salt and then adjusting the pH of the obtained emulsion to 6 to 9.5. 2. The polyvalent metal is zinc, calcium, aluminum, zirconium, magnesium, nickel,
The metal is at least one metal selected from the group consisting of cobalt, beryllium, bismuth, lead, copper and iron.
The manufacturing method as described. 3. The hydroxide of at least one metal selected from the group consisting of zinc, calcium, aluminum, zirconium, magnesium, nickel, cobalt, beryllium, bismuth, lead, copper and iron. , Oxides, chlorides, sulfides, carbonates, acetates, formates, glutamates, salicylates, glycolates,
Octonate, benzoate, gluconate, oxalate, lactate, citrate, malate, glycinate,
The production method according to claim 1, wherein the production method is at least one compound selected from the group consisting of alaninate, β-alaninate, an ammonia complex, and an amine complex. 4. The method according to claim 1, wherein the polyvalent metal or the polyvalent metal compound is used in an amount of 0.05 to 0.9 chemical equivalent to the acid value of the polymer. . 5. The method according to claim 1, wherein a polyvalent metal or a polyvalent metal compound is reacted after adding an amine and / or ammonia to the emulsion containing the polymer. 6. The method according to claim 1, wherein the amine is methylamine, ethylamine, propylamine, butylamine, dimethylamine,
Diethylamine, dipropylamine, dibutylamine,
Trimethylamine, triethylamine, tripropylamine, tributylamine, diethylaminoethanol,
The method according to claim 5, wherein the method is selected from the group consisting of monoethanolamine and ethylenediamine. 7. The method according to claim 5, wherein said ammonia is aqueous ammonia containing 10% by weight or less of ammonia. 8. The method according to claim 5, wherein the reaction between the polyvalent metal or the polyvalent metal compound and the polymer is carried out while the pH of the emulsion is in the range of 6 to 9.5. 9. The method according to claim 5, wherein the reaction is carried out while maintaining the temperature of the emulsion containing the polymer at or below the glass transition temperature of the polymer. 10. The method according to claim 5, wherein the reaction between the polyvalent metal or the polyvalent metal compound and the polymer is performed in the presence of a film forming agent and / or a plasticizer. 11. A film-forming agent represented by the general formula AO-[— RO
-] NA '(wherein A and A' may be the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 1 to 4 carbon atoms, a hydrogen atom, The method according to claim 10, which is an oxyalkylene glycol derivative represented by the following formula (2), wherein n is an integer of 1 to 3. 12. The plasticizer 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,
The method according to claim 10, wherein the method is selected from the group consisting of 2-pyrrolidone and 2,2,4-trimethylpentadiol-1,3-monoisobutyrate. 13. The method according to claim 10, wherein the film-forming agent and / or the plasticizer is added in an amount of 2 to 100% by weight based on 100% by weight of the polymer. 14. The method according to claim 14, wherein the acid is carbonic acid, formic acid, acetic acid, propionic acid, butyric acid, citric acid, oxalic acid, malic acid, tartaric acid,
The method according to any one of claims 1 to 12, wherein the method is selected from the group consisting of lactic acid, gluconic acid, benzoic acid, salicylic acid, glutamic acid, hydrochloric acid, and sulfuric acid. 15. The method according to claim 1, wherein the acid is carbonic acid generated by blowing carbon dioxide gas. 16. The method according to claim 1, wherein waxes and / or alkali-soluble resins are added to the emulsion before adding the acid. 17. The method according to claim 16, further comprising adding a surfactant to the emulsion before adding the acid. 18. A molecular weight of 10,000 to 1,000,000.
An aqueous solution containing a polyvalent metal or a polyvalent metal compound and an amine and / or ammonia is added to an emulsion containing a polymer having an acid value of 20 to 130, and then an acid is added to the emulsion. The pH of the emulsion is 6-9.5
A method for producing a floor covering material composition, comprising: 19. The method according to claim 18, wherein said polyvalent metal or polyvalent metal compound is used in an amount of 0.05 to 0.9 chemical equivalent based on the acid value of said polymer. 20. The amine according to claim 1, wherein the amine is methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, diethylaminoethanol, monoethanolamine, ethylenediamine. 19. The method of claim 18, wherein the method is selected from the group consisting of: 21. The polyvalent metal compound is a metal complex selected from the group consisting of zinc, calcium, aluminum, zirconium, magnesium, nickel, cobalt, beryllium, bismuth, lead, copper, and iron.
8. The method according to 8. 22. The method according to claim 21, wherein the complex is a complex containing one or more amines or ammonia as ligands. 23. The method of claim 22, wherein said amine is selected from the group consisting of morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine. 24. The method according to claim 18, wherein a film-forming agent and / or a plasticizer are added to the emulsion containing an aqueous solution containing a polyvalent metal or a polyvalent metal compound and an amine and / or ammonia before adding the acid. Method. 25. A film-forming agent represented by the general formula AO-[-RO
-] NA '(wherein A and A' may be the same or different and represent a hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 1 to 4 carbon atoms, a hydrogen atom, and R represents a carbon atom. 25. The method according to claim 24, wherein the oxyalkylene glycol derivative is represented by the following formula: 26. The method according to claim 26, 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,
The method according to claim 24, wherein the method is selected from the group consisting of 2-pyrrolidone and 2,2,4-trimethylpentadiol-1,3-monoisobutyrate. 27. The method according to claim 24, wherein the film-forming agent and / or the plasticizer is added in an amount of 2 to 100% by weight based on 100% by weight of the polymer. 28. The acid is selected from the group consisting of carbonic acid, formic acid, acetic acid, propionic acid, butyric acid, citric acid, oxalic acid, malic acid, tartaric acid, lactic acid, gluconic acid, benzoic acid, salicylic acid, glutamic acid, hydrochloric acid, and sulfuric acid. A method according to any one of claims 18 to 27. 29. The method according to claim 18, wherein the acid is carbonic acid produced by blowing carbon dioxide gas. 30. A wax and / or alkali-soluble resin is added to an emulsion containing an aqueous solution containing a polyvalent metal or a polyvalent metal compound and an amine and / or ammonia before adding an acid. 28. The method according to any one of claims 27 to 27. 31. The method according to claim 30, wherein a surfactant is further added to the emulsion to which an aqueous solution containing a polyvalent metal or a polyvalent metal compound and an amine and / or ammonia has been added before adding the acid.