JPS6323972A - Coating agent composition for floor - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has excellent adhesion, film-forming properties and resistance to wear and black heel mark and is strippable, by blending a specified aq. emulsion resin with wax and a polyvalent metal complex. CONSTITUTION:A prepolymer obtd. by subjecting a diisocyante (e.g., 4,4'- dicyclohexylmethane diisocyanate), a glycol (e.g., polypropylene glycol) and a polyhydroxycarboxylic acid (e.g., 2,2-dimethylolpropionic acid) to a urethane forming reaction is neutralized and subjected to a chain-lengthening reaction. Water is then added thereto to obtain an aq. urethane (b). A readical polymerizable monomer (b) is polymerized in the component (b) in the presence of 0.1-5wt% [based on the amount of the component (a)] radical polymn. initiator at 40-80 deg.C to obtain an aq. emulsion resin (A) having carboxyl groups and/or carboxylic salt groups and an acid value of not lower than 3. The component A is blended with wax (B) and 0.05-1.0 equivalent (based on the amount of carboxyl groups in the component A) of a polyvalent metal complex (C) (e.g., ammonium zinc carbonate).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to floor coating compositions. For more details,
By adding wax and a polyvalent metal complex to an aqueous emulsion resin having a carboxyl group and/or its salt, which is obtained by polymerizing a radically polymerizable monomer in the presence of an aqueous polyurethane, adhesion, film-forming properties, abrasion resistance, and resistance are improved. The present invention relates to a removable floor coating composition with improved black heel mark properties.

[Industrial application field]

Floor coating compositions are used to form a film by applying and drying on the floor surface to maintain the beauty of the floor, prevent water stains, and protect the base material. It can be widely used as a coating material for chemical flooring materials using synthetic resin raw materials.

[Conventional technology]

In the past, floor coatings were commonly used by applying wax components such as paraffin wax and carnauba wax dissolved in turpentine oil to the wooden floor, and then wiping the surface after drying. However, those using wax wax have the disadvantage that the desired performance cannot be obtained at all in terms of durability. Therefore, synthetic resins that have been created through the development of chemical technology in recent years, such as styrene resins, acrylic resins, vinyl chloride resins, polyester resins, epoxy resins, and various copolymers thereof, have been developed as floor covering materials that can improve these defects. A method in which a resin is dissolved in a solvent such as thinner and applied to the floor using a roll, spray coating, etc. is becoming widely used. On the other hand, the progress and development of flooring materials to be coated was remarkable, and from the early 1950s there was a change from wooden flooring materials to chemical flooring materials using synthetic resin additives in homes and commercial buildings such as offices. At present, more than 90% of flooring materials are chemical flooring materials. However, since the main raw materials for chemical flooring materials are synthetic resins such as vinyl asbestos resin, vinyl chloride resin, and asphalt, the solvents in the floor coating composition, i.e., petroleum-based,
Naphthenic solvents have the disadvantage of dissolving and degrading chemical flooring materials. Furthermore, due to the toxicity to workers during work and the danger of fire, floor coating compositions changed to emulsion-based compositions that use water-based solvents. For this reason, the progress and development of synthetic resin emulsion floor coating compositions began in the mid-1930s, with improvements being made to styrene resin emulsions, styrene-acrylic copolymer resin emulsions, and acrylic resin emulsions. However, these emulsion-based coatings have the disadvantage of poor adhesion and abrasion resistance, requiring frequent reapplication.

In order to improve these drawbacks, a floor coating composition has been developed in which an aqueous polyurethane is added to the above emulsion. This is due to the excellent wear resistance of water-based urethane.
This took advantage of its adhesion and slipperiness. but,
Floor coating compositions simply mixed with water-based polyurethane have poor black heel mark resistance, and increasing the film strength to improve black heel mark resistance results in a decrease in adhesion, which is a characteristic of urethane resins. The problem was that elongation and modularity also decreased in inverse proportion to hardness.

Therefore, the present inventors have conducted research to provide a floor coating composition that maintains the excellent performance of water-based polyurethane and has excellent adhesion, film-forming properties, abrasion resistance, and black heel mark resistance. Ta. As a result, it was discovered that the above problems could be solved by not simply mixing acrylic resin emulsion and water-based polyurethane, but by functionally linking the two and further adding wax to the mixture. The application was filed as No.-73594.

[Problem that the invention seeks to solve]

By the way, coated floor surfaces are exposed to a large number of pedestrians, so no matter how durable the coating material is, over a long period of time it will be scratched, stained, and gradually worn away, and yellowing and deterioration caused by ultraviolet rays will occur. I can't do it.

Therefore, from the viewpoint of aesthetics and protection of the floor, it is absolutely necessary to remove, ie, peel off, the coating layer.

However, after a floor coating composition containing wax and an aqueous emulsion resin obtained by polymerizing a radically polymerizable monomer in the presence of an aqueous polyurethane is applied to a floor surface and completely cured, the coating and coating are not applied to the floor surface. It has excellent performance in terms of adhesion, gloss, toughness, etc. However, on the other hand, it is not easy to remove it from the floor using chemical action).

If an attempt is made to remove the coating using a solvent with strong dissolving power, the chemical flooring material will also be dissolved. Also,
Removal of the coating by mechanical abrasive force inevitably results in damage to the flooring. Furthermore, when a water-based polyurethane resin with a high acid value that can be peeled is used, there is a drawback that water resistance deteriorates.

Therefore, the present inventors conducted various studies in order to maintain the excellent performance of the coating material made of water-based emulsion TXT fat and wax and to obtain a coating material that has the following characteristics (1) to (3). I did it.

(1) It is easy to apply to various objects, especially floors, and the formed film is strong and has excellent durability. (2) If the film becomes slightly dirty, use a weak alkaline detergent. (3) If dirt has been incorporated into the coating after a long period of time, or if the coating has yellowed. The material must be able to be washed and removed using a strong alkaline detergent containing caustic soda, caustic potassium, ammonia, amine, or a chelating agent.

As a result, it was discovered that a removable floor coating composition can be obtained by adding a polyvalent metal complex to an aqueous emulsion resin having a carboxyl group and/or a salt thereof, leading to the present invention.

[Means for solving problems]

The present invention relates to a floor coating composition containing an aqueous emulsion resin having a carboxyl group or a salt thereof obtained by polymerizing a radically polymerizable monomer in the presence of an aqueous polyurethane, a wax, and a polyvalent metal complex.

The present invention will be explained in detail below.

The "aqueous polyurethane" used in the present invention is produced, for example, as follows. That is, first, a prepolymer is prepared by reacting a diisocyanate, a glycol, and a polyhydroquine carboxylic acid to form a urethane.

Diisocyanates used at this time include aliphatic and cycloaliphatic or aromatic diisocyanates, examples of which include 2.4-) lylene diisocyanate,
2.6-) lylene diisocyanate, 4.4'-diphenylmethane diisocyanate, m-fuynylene diisocyanate, xylylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate ester, 1.4-cyclohexylene diisocyanate), 4.4'-dicyclohexylmethane diisocyanate, 3.3'-dimethyl-4,
4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1
．． Examples include 5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, and isophorone diisocyanate.

Glycols include ethylene glycol, ethylene glycol, triethylene glycol 1, 2-propylene glycol, trimethylene glycol 1,
3-butylene glycol, tetramethylene glycol,
Hexamethylene glycol, hydrogenated bisphenol A1 Low molecular weight glycols such as ethylene oxide or propylene oxide adducts of bisphenol A, or polyether necks such as polyethylene glycol and polypropylene glycol, ethylene glycol and adipic acid, hexanediol and adipic acid ,
Examples include polyesters, which are condensates of ethylene glycol and phthalic acid, and polycaprolactone.

Examples of polyhydroxycarboxylic acids include 2,2-dimethylolpropionic acid, 12,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid.

The reaction is dioxane, acetone, methyl ethyl ketone, N
- Organic solvents such as methylpyrrolidone and tetrahydrofuran that are inert to incyanate groups and have a high affinity for water can be used.

The prepolymer is then neutralized and chain extended, and distilled water is added to obtain an aqueous polyurethane. As a chain extender,
Polyol necks such as ethylene glycol and propylene glycol, ethylene diamine, propylene diamine, hexamethylene diamine, tolylene diamine, xylylene diamine, diphenyl diamine, diaminodiphenylmethane, diaminocyclohexylmethane, piperazine, 2
-Aliphatic, cycloaliphatic and aromatic diamines such as methylpiperazine, inphorondiamine, and water.

As a neutralizing agent, trimethylamine, triethylamine,
Examples include amines such as tri-n-propylamine, tributylamine, and triethanolamine, sodium hydroxide, potassium hydroxide, and ammonia.

The amount of carboxyl groups and/or their salts in the aqueous polyurethane can be expressed as the acid range.

In the present invention, the acid value of the aqueous polyurethane is 10 to 200 per resin solid content, preferably 20 to 200.
It is. By setting the acid value to 10 or more, the formed coating film can be easily peeled off, and the polymerization stability when polymerizing the aqueous emulsion resin is also improved. Further, by setting the acid value to 200 or less, the physical properties such as water resistance of the coating formed from the aqueous emulsion resin and the polyvalent metal complex can be maintained in good condition. Note that the acid value here refers to K per 1 g of resin solid content.
It is the number of mg of OH.

Examples of the "radically polymerizable monomer" used in the present invention include acrylic acid esters (methinobe ethyl, propyl, butinobe!-butinobe t-butinobecyclohexinobe2-
acrylic esters such as ethylhexynovelauryl, dodecinopestearyl), methacrylic esters (methinopethyl, propyl, butyl, l-butinobe, t-butyl, cyclohexyl, 2-ethylhexyl, lauryl, dodecinopestearyl, etc.) acrylic acid ester), 2
- Hydroxyl group-containing vinyl monomers such as hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, aromatic unsaturated hydrocarbons such as styrene, α-methylstyrene, and vinyltoluene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Monoesters of unsaturated dicarboxylic acids and monohydric alcohols such as maleic acid, fumaric acid, monomethyl itaconate, diesters of unsaturated dicarboxylic acids and monohydric alcohols such as dimethyl itaconate, vinyl benzoate vinyl acetate Nitrogen-containing vinyl monomers such as acrylonitrile, methacrylonitrinopeacrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, or vinyl chloride, vinylidene fluoride, or vinylidene chloride.

A radically polymerizable monomer is polymerized in the presence of an aqueous polyurethane to obtain an aqueous emulsion resin having a carboxyl group and/or a salt thereof.

As the radical polymerization initiator used in the polymerization reaction, not only water-soluble initiators used in ordinary emulsion polymerization but also oil-soluble initiators can be used. Examples include potassium persulfate, ammonium persulfate, azobiscyanovaleric acid, t-butyl hydroperoxide, and azobisisobutyronitrile. Furthermore, so-called redox catalysts made of a combination of these radical generators, sulfites, and sulfoxylates, in that order, can be used.

The amount of the radical polymerization initiator used is suitably 0.1% to 5% by weight based on the total amount of radically polymerizable monomers. More preferably 0.2% to 3%.

The radical polymerization initiator can be added by a conventional method. For example, it can be added all at once or continuously or in divided portions.

The radically polymerizable monomer or radically polymerizable monomer mixture can be added by dropping all at once, continuously, or in portions, but continuous dropping is preferable in view of control of polymerization heat and polymerization stability.

Furthermore, it is also possible to add a chain transfer agent such as a mercaptan, if necessary.

Although the reaction temperature varies depending on the type of monomer used, the type of polymerization initiator, etc., a temperature range of 40°C to 80°C is usually suitable. If the temperature is below 40°C, the polymerization rate will be slow;
When the temperature exceeds 0°C, more resin adheres to the inner wall of the pot.

The acid value of the aqueous emulsion resin is 3 or more, preferably 4 to 150. It varies depending on the acid value.

The composition of the present invention is obtained by adding a wax and a polyvalent metal complex to the aqueous emulsion resin described above.

Examples of waxes that can be used in the floor coating composition of the present invention include natural waxes, synthetic waxes, polymeric resins such as olefinic unsaturated polymers, and slip agents. may contain one or more of the above-mentioned natural waxes and slip agents as wax components.

Typical examples of natural waxes and synthetic waxes include carnauba wax, rice bran wax, beeswax, spermaceti wax, candelilla wax, wood wax, monk wax, ceresin wax, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and the like.

Further, the polyvalent metal in the polyvalent metal complex compound used in the composition of the present invention is a divalent or higher valent metal, such as calcium, magnesium, zinc, barium, aluminum,
Zirconium, nickel, iron, cadmium, strontium, bismuth, beryllium, cobalt, lead, copper and antimony can be used. In particular, calcium, zinc, and aluminum exhibit favorable performance.

In addition, the amount of polyvalent metal complex added to the aqueous polyurethane resin is 0% relative to the carboxylic acid group of the polyurethane resin.
It is preferable to use a polyvalent metal complex containing a polyvalent metal having a chemical equivalent of .05 to 1.0.

In addition, as a ligand for forming a polyvalent metal complex,
For example, carbonate ion, acetate ion, oxalate ion, malate ion, hydroxyacetate ion, tartrate ion, acrylate ion, lactate ion, ophtonate ion, formate ion, salicylate ion, benzoate ion, gluconate ion, and glutamate ion. , glycine, alanine, ammonia, morpholine, ethylenediamine, dimethylaminoethanol, diethylamineethanolinopemonoethanolamine, jetanolamine, triethanolamine, or similar inorganic acids, organic acids, amino acids, amines, etc. can be used. .

Examples of polyvalent metal complexes that can exhibit preferable performance in the present invention include zinc carbonate ammonia, calcium carbonate ethylenediamine-ammonia, zinc acetate ammonia,
Zinc ammonia acrylate, zinc ammonia phosphonate,
Examples include zirconium malate ammonia, zinc aminoacetate ammonia, alanine calcium ammonia butyrate.

The composition of the present invention can be prepared, for example, by stirring and mixing an aqueous solution containing the aqueous emulsion resin, the wax and the polyvalent metal complex aqueous solution at room temperature and pressure.
It can be easily manufactured.

Note that it is essential that the polyvalent metal in the present invention forms a complex.

That is, when a polyvalent metal that does not form a complex, such as a hydroxide of a polyvalent metal, is added to an aqueous emulsion resin containing a carboxylic acid, carboxyl groups and/or their salts are crosslinked by the polyvalent metal. It becomes easier.

As a result, various problems arise.

For example, water-based emulsion resins become difficult to stably emulsify or dissolve, and their viscosity increases over time, making the applicator heavy during application, resulting in poor workability. Furthermore, since the temperature required for film formation (minimum film formation temperature) also increases, it is not possible to form a continuous, uniform film when coating at a low temperature. For this reason, it is only possible to obtain products with poor adhesion to the floor surface, gloss, water resistance, detergent resistance, durability, leveling property, etc.

On the other hand, in the composition of the present invention, by containing the polyvalent metal used as a metal crosslinking agent as a polyvalent metal complex, the aqueous emulsion resin can be made to exist in an extremely stable state.

In other words, although I do not intend to be bound by theory, when a polyvalent metal complex is added to an aqueous emulsion resin in an aqueous solution state, the polyvalent metal forms a complex, and a crosslinking reaction between the polyvalent metals and the carboxyl groups occurs. The composition of the present invention does not undergo changes such as thickening and is stable.

On the other hand, when the composition of the present invention is applied to a floor surface, two or more carboxyl groups in the aqueous emulsion resin are crosslinked by the action of polyvalent metal ions due to the inevitable evaporation of volatile components, forming a tough coating. It is thought that it forms.

Furthermore, an alkali-soluble resin can be further added to the floor coating composition of the present invention, if necessary. Representative examples of alkali-soluble resins include styrene-maleic acid copolymer resins, rosin-maleic acid copolymer resins, water-soluble acrylic resins, water-soluble urethane resins, and the like.

Furthermore, various additives can be added to the floor coating composition of the present invention, if desired. For example, if the minimum film formation temperature of the composition of the present invention, which is mainly composed of a polymer obtained by polymerizing a radically polymerizable monomer in the presence of an aqueous polyurethane, is room temperature or higher, film formation at room temperature is possible. It is preferable to add a coalescing agent, a plasticizer, etc. to achieve this.

Examples of coalescents and plasticizers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, N-methyl-2-pyrrolidone, dibutyl phthalate, and tributoxyethyl phosphatide. Fete etc. can be mentioned.

However, if a film can be formed at room temperature, it is needless to say that there is no need to use these coalescing agents and plasticizers.

Furthermore, if it is desired to improve the stability of the floor coating composition of the present invention and the wettability when applied to a substrate, a surfactant or the like may be used as appropriate. Furthermore, if it is necessary to improve black heel mark resistance, etc., additives such as slip agents and leveling agents may be added.

Furthermore, the coating formed using the composition of the present invention can be easily removed chemically without using a fraudulent polishing method. That is, the coating can be easily removed by treatment with a removal solution.

A removal solution that can be used in the present invention is an alkaline solution containing the ligand. Here, the ligands are ethylenediaminetetraacetic acid, N-hydroxyethylenediamine-N,
N', N'-triacetic acid, diethylenetriaminepentaacetic acid, N
, N, N', N'-tetrakis-(2-hydroxypropyl)-ethylenediamine, ethylenediamine-N,N
'-Diacetic acid, 1-hydroxyethylenethene-1,1-diphosphoric acid, tetraethylenetetramine-N,N'.

N', N', N', N'-hexaacetic acid,
Examples include citric acid, oxalic acid, gluconic acid, glycolic acid, malic acid, ammonia, monoethanolamine, jetanolamine, triethanolamine, homophorine, diethylaminoethanol, dimethylaminoethanol, and ethylenediamine. In addition, alkaline solution includes alkaline substances such as ammonia, amine, caustic soda, caustic potassium, sodium metasilicate, sodium orthosilicate, potassium silicate, sodium pyrophosphate, potassium birophosphate, sodium triphosphate, potassium triphosphate, etc. It is something to do.

Furthermore, the alkaline solution containing the above-mentioned ligands may further be anionic (higher alcohol sulfate ester salt, fatty acid salt,
(alkylbenzene sulfonate, polyoxyethylene ether sulfate salt, etc.), nonionic (polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene acyl ether, etc.), and amphoteric (alkyl betaine, etc.) surfactants. can include. Containing a surfactant is preferable because it tends to improve the adhesion and dispersibility of the aqueous emulsion resin coating. In addition, alkaline solutions containing the above-mentioned ligands include alcohols (ethyl alcohol/lz, ethylhexyl alcohol, basil alcohol, butyl alcohol, etc.), ethers (diethyl-rubitonobediethyl heptarosol, butyl ether, etc.), ethers, etc. Alcohols (isopropyl cellosolve, calpitol,
cellosolve, glycol ether, benzyl cellosolve, butyl carbi)-/peptyl cellosolve, methyl calpitol, methyl cellosolve, triethylene glycol monoethyl ether, etc.), ester ethers (butyl calpitol acetate, butyl cellosolve acetate, carpitol acetate, cellosolve acetate) , 3-methoxybutyl acetate, methyl calpitol acetate, methyl cellosolve acetate, etc.), ketones (acetone, diethyl ketone, methyl butyl ketone, etc.), esters (acetate esters, propionate esters, etc.), N-methyl- It may also contain solvents such as 2-pyrrolitone, 2-pyrrolidone, dimethylformamide, tetrahydrofuran, and dimethylsulfoxide. The solubility of the aqueous emulsion resin coating can be accelerated by adding a solvent.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, the "active ingredient" in Examples, Comparative Examples, and Reference Examples indicates the content (concentration) of each resin, and its unit is weight %.

Reference Example 1 [Production of water-based polyurethane] (1) Polypropylene glycol (molecules 11l10
00) 49 dicyclohexylmethane diisocyanate 1
76 g of dimethylolpropionic acid, 70 g of R-dimethylolpropionic acid, and 196 g of N-methylpyrrolidone were placed in a reactor equipped with a reflux condenser, a thermometer, and a stirring device, and a urethanization reaction was carried out while maintaining the temperature at 80 to 100° C. to prepare a prepolymer. Next, 48 g of triethylamine was added to this prepolymer to neutralize it, and then 5.0 g of hexamethylene diamine was added, and while adding distilled water, the temperature inside the reactor was maintained at 35 ° C. or less to carry out a polymerization reaction. 456 by the end of the reaction
g of distilled water was added to obtain aqueous polyurethane C shown in Table 1.

The acid value per resin solid content of this water-based polyurethane is 98.
Met.

(2) Aqueous polyurethanes ASB and D were prepared in the same manner as in (1) using the raw materials shown in Table 1.

Reference Example 2 [Manufacture of coating composition] (1) 299.2 g of deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, and the aqueous polyurethane system obtained in Reference Example 1 was added. 400g of resin C was charged and heated to 60°C while stirring, and MMA215 was added at 60°C.
A mixed solution consisting of 65 g of g, n-BA, and 08 g of t-DMO was added dropwise over 3 hours. Simultaneously with the dropwise addition of the above monomer mixture, 10 g of a 10% aqueous dispersion of t-butyl hydride peroxide and 10 g of a 10% aqueous solution of sodium formaldehyde sulfoxylate prepared in advance were also added dropwise. After the dropwise addition, the reaction solution was kept at 70°C for 1 hour to complete the polymerization reaction, and the aqueous emulsion resin 1
I got it.

(2) Aqueous emulsion resins 2.3 and 4 were prepared in the same manner as in (1) using the raw materials shown in Table 2, respectively.

Table 2 Reference Example 3 (Manufacture of polyvalent metal complex aqueous solution) (1) Zinc carbonate ammonia aqueous solution Pour 54.0 g of water into a container equipped with a stirrer, gradually add zinc oxide Log while stirring, and add zinc oxide to the water. Dispersed. Next, 18 g of 28% aqueous ammonia and 18 g of ammonia carbonate were sequentially added and stirred until dissolved to obtain an aqueous zinc carbonate ammonia solution.

(2) Carbonic acid': Ruconium ammonia aqueous solution manufactured by Nippon Metal Chemical Co., Ltd. Zirconium carbonate ammonia ZrCh 13%, pH 8,40 specific gravity (20°C N, 235
(3) Zinc acetate ammonia aqueous solution Pour 55 g of water into a container equipped with a stirrer, gradually add 15 g of zinc acetate while stirring, and dissolve the zinc acetate in the water.
30 g of 8% ammonia water was added and stirring was continued until it was dissolved to obtain a zinc acetate ammonia aqueous solution.

(4) Zinc acrylate ammonia aqueous solution Pour 59.4 g of water into a container equipped with a stirrer, add and disperse 7.0 g of zinc oxide in the water while stirring, and then add 12.6 g of acrylic acid.
was added to obtain zinc acrylate, and then 21.0 g of 28% ammonia water was added and stirred until the solution became uniform to obtain a zinc acrylate ammonia aqueous solution.

(5) Aqueous solution of amine ammonium acetate Pour 47.9 g of water into a container equipped with a stirrer, add 10.0 g of zinc oxide to the water while stirring, and disperse.
After adding 23.6 g of 8% aqueous ammonia, 18.5 g of aminoacetic acid was added and stirred until the solution became homogeneous to obtain an aqueous amine-zinc acetate ammonia solution.

(6) Zinc malate ammonia aqueous solution Pour 43.5 g of water into a container equipped with a stirrer, add 10.0 g of zinc oxide to the water while stirring and disperse, then add 16.5 g of malic acid to dissolve malic acid. After making zinc, 2
30.0 g of 8% ammonia water was added and stirred until the solution became homogeneous to obtain a zinc malate ammonia aqueous solution.

1. Zinc ammonia carbonate (contains 8.03% as zinc) 2. Carbon a zirconium ammonia (contains 9.63% as zirconium) 3. Zinc acetate ammonia (contains 5.36% as zinc) 4゜ Zinc acrylate ammonia ( 5,62 as zinc
%) 5. Aminoacetic acid zinc ammonia (8.03% as zinc)
6. Zinc malate ammonia (containing 8.03% as zinc) Among these, the following complexes are exemplified as representative examples in the examples.

0 Zinc carbonate ammonia 0 Zirconium carbonate ammonia ○ Aminoacetic acid ammonia (Note-1) Water-based polyurethane A in Table 1 (Note-2) Acrylic resin emulsion monomer composition (10% methacrylic acid, 30% butyl acrylate, 60% methyl methacrylate) %], a polyacrylic resin emulsion with an acid value of 65 and an active ingredient of 40%, obtained by a conventional emulsion polymerization method using sodium lauryl sulfate.

(Note-3) Acrylic-styrene resin emulsion monomer composition [3% methacrylic acid, 40% ethyl acrylate, 37% methyl methacrylate, 20% styrene] and a commonly used emulsion polymerization method using sodium laurylbenzenesulfonate. A polyacrylic resin emulsion with an acid value of 20 and an active ingredient of 40%.

(Note-4) Oxidized type polyethylene wax emulsion Manufactured by Allied Chemical Co., USA, oxidized type polyethylene wax, trade name AC-392, acid value 40, softening point 138°C, penetration 0.5 or less (ASTM D 5), non-toxic. A polyethylene wax emulsion containing 40% active ingredients emulsified using an ionic surfactant.

(Note-5) Styrene-maleic acid copolymer aqueous solution manufactured by Alco Chemical Company, USA, trade name 5MA2625A, acid value 2
20. An aqueous solution of 17% active ingredient dissolved in ammonia using a styrene-maleic acid copolymer resin having a molecular weight of 1900.

(Note-6) Rosin-maleic acid copolymer aqueous solution manufactured by Ziegler Chemical & Minerals Co., USA, product name 2 ecolac 802, acid value 200
, a rosin-maleic acid copolymer with a softening point of 175°C, an aqueous solution containing 17% of the active ingredient dissolved using ammonia.

(Note-7) Acrylic alkali-soluble resin Acrylic alkali-soluble resin manufactured by Rohm and Haas, USA, trade name Brimal B-644, solid content 42%, minimum film forming temperature 15°C.

(Note-8) Slip agent manufactured by Dow Corning Co., Ltd., silicone-based wear resistance imparting, flattening improver, trade name, Hay 79-/) FSXB 2725° Examples 1 to 10 and Comparative Examples 1 to 14 Table 3 Compositions of the present invention and compositions other than the present invention were prepared using the formulations shown in Table 4, and the performance of each composition was evaluated. The results are shown in Table 4.

[Performance test method and comparative performance evaluation]

1. Approximately 100 samples are placed in a vertical cylindrical, uncolored bottle with a storage stability of approximately 120 days and sealed. After storing in a thermostat at a temperature of 45±2° C. for 24 hours, the presence or absence of layer separation is examined.

2. Apply the sample to a standard tile (vinyl asbestos tile) for glossiness JFPA standard test - 10±2rnl per square meter. After drying for 30 minutes at room temperature, the gloss is measured. Using the same method, apply two coats and three coats, and measure the glossiness of each coat. Glossiness measuring device is JIS
- Z8741 is dominant, and the angle of incidence is 60°.

3. A test piece coated according to the water resistance gloss measurement method is left overnight at room temperature with a relative humidity of 80% or less.

The test piece was placed on a horizontal fixed table at 23 ± 10°C, and
．． Distilled water from item 1 was added dropwise, covered with a cover glass, and allowed to stand for 60 minutes.The water was then absorbed and left for one hour, and the state of whitening was visually measured.

4. A test piece coated according to the removability gloss measurement method was 38±2
After being left in a thermostat at 38±2°C for 6 hours and immersed in distilled water at room temperature for 1 hour, the test piece was taken out and left in a thermostat at 38±2°C for 18 hours.

The release plate contains 3.97 g of potassium hydroxide (KO885%
) and 17.7 g of oleic acid dissolved in 1000-ml distilled water containing 5 ml of aqueous ammonia (NH40828%).
After soaking the washability tester's boar bristle brush in the stripping solution for 2 minutes, pour 10±2 ml onto the test piece and immediately start the test. After 25 cycles, rinse the test piece with clean water and remove completely. Determine whether it has been done. For washability tester, ASTM-D-17
92-66.

5. A test piece made with φ cloth according to the detergent resistance gloss measurement method was 38±2
Place in an incubator at 18:00 with the neck open. Cleaning liquid is 0.1g
Sodium dodecylbenzenesulfonate and 0.2 g
200 mjl of sodium tripolyphosphate! Using a cleaning solution (pH 9.0 ± 0.2) dissolved in distilled water, soak the boar bristle brush of the Guard Donor Straightline Washability Tester in the stripping solution for 2 minutes, and then
Pour mj7 onto the specimen and begin the test immediately. 10
After reciprocating 0 times, the test piece is rinsed with clean water, air-dried, and evaluated. The leveling state of the coated test piece is visually evaluated according to the related standard ASTM-D 3207-6, leveling property, recoatability gloss measurement method. The reapplicability test is evaluated by visually observing whether the base is re-emulsified during the second application.

7. Black heel mark resistance A test piece was coated on a standard white tile (vinyl asbestos tile) for JFPA standard testing according to the gloss measurement method, and after drying at room temperature for 24 hours, a 30 x 30 mm square rubber 6
The test piece was screwed onto the mounting surface of a Schnell-type dirt capsule containing
Rotate in both directions for 5 minutes each. Visually compare and evaluate the amount of black heel marks attached to the tiles.

8. Abrasion resistance A test piece coated five times using the same method as the gloss measurement method was left to dry at room temperature for 168 hours, and the degree of abrasion was measured using a taper tester (wearing wheel C3-17, load 10,100O). Measure and evaluate.

9. Durability Evaluate the overall performance from the performance of water resistance, abrasion resistance, black heel mark resistance, etc.

10.Adhesion Black heel mark resistance
Apply cellophane tape to the top surface of the substrate with a 0-frame bias, and after adhering sufficiently, peel off the cellophane tape at once at a 45° angle to the substrate, measure the number of remaining coatings, and show it in quantity. (Based on JISK5400).

11. Film-forming properties Each of Examples 1 to 10 (compositions of the present invention) and Comparative Examples 1 to 4 listed in Table 3 was placed in a flat chalet with a diameter of IQ mm,
Five grams of the film was collected in each flat chalet, dried at a temperature of 20° C. and a humidity of 60%, and the transparency of the film was visually observed and evaluated.

〔Effect of the invention〕

The floor coating agent composition of the present invention forms a hard coating without reducing adhesion or film-forming properties, has excellent durability such as abrasion resistance and black heel mark resistance, and has excellent detergent resistance. It has an improved balance of removability and reapplicability.

Claims (1)

[Claims] A floor coating composition containing an aqueous emulsion resin having a carboxyl group and/or a salt thereof obtained by polymerizing a radically polymerizable monomer in the presence of an aqueous polyurethane, a wax, and a polyvalent metal complex.