JPS6048542B2 - floor gloss composition - Google Patents

Description

[Detailed description of the invention] FIELD OF THE INVENTION This invention relates to floor gloss compositions.

Specifically, the present invention relates to a floor gloss composition that exhibits high gloss and is used for protecting and polishing the surfaces of wood, concrete, rubber tiles, vinyl tiles, linoleum tiles, etc., and has excellent durability and removability. J. The floor gloss composition is
It exhibits good workability during application, and the film obtained after drying has a high level of gloss, and is durable as it is resistant to peel marks or scuff marks caused by shoes when walking, and has little adhesion of dirt such as dirt and dust. In addition, it needs to have detergent resistance so that it can maintain its luster even when cleaned with ordinary detergents, etc., and removability so that it can be easily removed with a remover if dirt or damage becomes severe. be done.

However, detergent resistance and removability are contradictory properties and are difficult to achieve simultaneously. In order to meet these conflicting demands, a method has been proposed in which an emulsion copolymer and a polyvalent metal ion or a polyvalent metal complex salt are used together. In this method, the so-called metal salt cross-linking increases the film strength and improves heel mark resistance, and the film can be removed by reversibly dissociating the metal salt cross-links with an ammonia-based removal agent. Although it is effective, it has the following problems.

That is, when polyvalent metal ions or polyvalent metal complex salts are used in combination with an emulsion copolymer as a floor gloss composition, the polyvalent metal ions tend to aggregate when added, and usually a large amount of nonionic salts is required to stabilize the composition. An emulsifier is required.

Furthermore, when polyvalent metal complex salts are used, although the stability upon addition is somewhat improved, complex salts with small stability constants tend to cause thickening and aggregation, whereas complex salts with large stability constants tend to cause thickening and aggregation. The amount of polyvalent metal ions liberated is small, resulting in substantially less crosslinking, resulting in problems such as slow drying and unsatisfactory film performance. moreover,
From the viewpoint of work efficiency, it is desired to increase the concentration of the dual active ingredients in the floor gloss composition so that the desired effect can be obtained by reducing the number of times of application. When the concentration is high, the viscosity tends to increase and workability tends to decrease. In addition, floor gloss compositions containing polyvalent metal ions or polyvalent metal complex salts have poor film-forming properties, especially low gloss compositions. It has the disadvantage that it does not form a continuous film when it is applied to floor surfaces during warm seasons, and so-called whitening phenomenon tends to occur.
Furthermore, it has poor adhesion to the surface of the floor base material, and in particular, it hardly adheres to floor materials with a dense surface such as vinyl tiles, vinyl sheets, or rubber tiles, which have been increasing in recent years. It tends to peel off from the flooring material due to the impact it receives, causing powdering. In addition, in order to stably coexist the emulsion copolymer with polyvalent metal ions or polyvalent metal complexes, ammonia or amine can be used to increase the 4r pH.
As a result, ammonia and amine odors are generated during coating work, worsening the working environment. In view of the current situation, the present inventors have conducted repeated research to solve various problems of conventional floor gloss compositions.
A floor gloss composition containing zinc oxide dispersed using a specific block copolymer and an aqueous dispersion of a specific acrylic copolymer has excellent performance, and has a variety of characteristics that conventional floor gloss compositions have. The present invention has been completed based on the discovery that the above problems can be solved.

Therefore, the object of the present invention is to have excellent durability, achieve both the contradictory properties of detergent resistance and removability, be odorless, have good workability even at high concentrations, and have excellent adhesion and dryness. The present invention provides an excellent floor gloss composition with improved properties and storage stability.

That is, the present invention provides an aqueous zinc oxide dispersion in which the following block copolymer (I) is used and dispersed at a ratio of 1 to 2 parts by mass per 1 part by weight of zinc oxide, and α as a monomer component.・An aqueous acrylic copolymer dispersion (■) derived using 5 to 15% by weight of β-monounsaturated carbonic acid, and a solid content of 1 weight % of the aqueous acrylic copolymer dispersion (Π) The present invention relates to a floor gloss composition characterized in that the solid content of zinc oxide is contained in a ratio of 1 to 2 parts by weight per part by weight.

Block copolymer (I): General formula (wherein R represents hydrogen or a methyl group, x represents a methylene group or a carbonyl group, and n represents an integer from 1 to 100.

) and the general formula (wherein R2 represents hydrogen or a methyl group, and Y represents hydrogen or -COOZ.

Z and 4 each independently represent hydrogen, a monovalent metal, an ammonium group, or an organic amine group. A block copolymer consisting of a repeating structural unit (B) shown in ), in which the total weight ratio of the total weight of the block copolymer to the total weight of the block copolymer (B) is within the range of 5:95 to 60:40.

Conventionally, zinc oxide (solubility: 4.5% at 180°C), which does not substantially dissociate in water, has been used as a crosslinking agent in emulsion copolymers having acid groups.
2 x 10-', "Chemical Handbook Basics I" published by Maruzen Co., Ltd.) is known in the technical field of paints, but in low viscosity liquids such as floor gloss compositions, added zinc oxide It has not been put to practical use because of problems such as poor dispersion stability, most of it settling during storage, and causing thickening and aggregation of the emulsion copolymer.

The present inventors succeeded in dramatically improving the dispersion stability when zinc oxide is used in a floor gloss composition by using the block copolymer (I) for dispersing zinc oxide. We have now provided an excellent floor gloss composition.

The block copolymer (I) used in the present invention has, for example, the general formula (wherein R represents hydrogen or a methyl group,
X represents a methylene group or a carbonyl group, and n is 1 to 1
Represents an integer of 00.

) and a polyethylene glycol monomer (1) such as polyethylene glycol monoallyl ether or polyethylene glycol mono(meth)acrylate represented by the general formula (however, in the formula, R.

represents hydrogen or a methyl group, Y represents hydrogen or -COOZ
. Z and 4 each independently represent hydrogen, a monovalent metal, an ammonium group, or an organic amine group. ) The unsaturated carboxylic acid monomer (2), which is a (meth)acrylic acid monomer or a maleic acid monomer, is copolymerized using a polymerization initiator, and if necessary, an alkaline substance It can be obtained by neutralizing it with

The polyethylene glycol monomer (1) is polyethylene glycol monoallyl ether or polyethylene glycol mono(meth)acrylate, and has the general formula (i
), and the number n of added moles of ethylene oxide is 1 to 1.
00.

When the number of added moles n exceeds 100, copolymerization reactivity becomes low and a block copolymer that is effective in the present invention cannot be obtained. Preferably, those having an added mole number n of 5 to 50 are effectively used. Unsaturated carboxylic acid monomer (2)
is a (meth)acrylic acid monomer or a maleic acid monomer, and is represented by the general formula (Ii),
Specific examples include acrylic acid, methacrylic acid, maleic acid, and their monovalent metal salts, ammonium salts, and organic amine salts.

One or more of these can be used. In the block copolymer (I) used in the present invention, the total amount of repeating structural units (2) and the total amount of repeating structural units (B) are in a weight ratio of 5:95 to 60:40. is necessary.

If the ratio is outside this range, zinc oxide will not be stably dispersed in the floor gloss composition and will not exhibit excellent performance. In order to produce the block copolymer (I) used in the present invention from the polyethylene glycol monomer (1) and the unsaturated carboxylic acid monomer (2), copolymerization is performed using a polymerization initiator. Bye.

Copolymerization can be carried out by methods such as polymerization in a solvent or bulk polymerization. When producing the block copolymer (I), the charging ratio of the polyethylene glycol monomer (1) and the unsaturated carboxylic acid monomer (2), the amount of polymerization initiator used, the polymerization temperature, the solvent In the case of polymerization, the molecular weight of the resulting block copolymer (I) can be adjusted as appropriate by adjusting the type and amount of the solvent. The molecular weight of the block copolymer (I) used in the present invention is not particularly limited, but is 500 to 100,000, preferably 1,000 to 100,000.
A range of 20,000 is particularly effective. The block copolymer (I) thus obtained can be used as it is, but may be further neutralized with an alkaline substance if necessary. Preferred examples of such alkaline substances include monovalent metal hydroxides, chlorides, and carbonates; ammonia; and organic amines. Zinc oxide used in the present invention can be commercially available in powder form, and among them, pigment grade manufactured by a dry method known as the American method or French method, or a pigment grade manufactured by a wet method. Rubber grades are preferably used.

In order to obtain a zinc oxide aqueous dispersion using the block copolymer (I) of the present invention, zinc oxide may be dispersed in water in the presence of the block copolymer (I). Book copolymer (
The amount of I) used is 1% per 100 parts by weight of zinc oxide.
~2 parts by weight, preferably 3 to 10 parts by weight. The amount of zinc oxide used is based on the acrylic copolymer aqueous dispersion (Π
) is 1 to 20 parts by weight per part by weight of solids,
Preferably it is 2 to W parts by weight.

If the amount used is less than 1 part by weight, the resulting coating will have little crosslinking and will not exhibit sufficient performance in terms of recoatability and durability.

Furthermore, if the amount exceeds 2 tumor areas, the transparency of the coating will decrease, which is not preferable. As a method for dispersing zinc oxide, for example, zinc oxide is added to an aqueous solution in which block copolymer (I) is dissolved, and the mixture is stirred using a commonly used stirring device such as a ribbon mixer, kneader, or high-speed disper. Here are some methods.

The zinc oxide aqueous dispersion may be prepared to have a solid content concentration of 20 to 70% by weight, which is suitable for use. 50-7%
It exhibits low viscosity even at such high concentrations and has excellent dispersion stability, making it extremely easy to handle. -5 to 15% by weight of α/β monounsaturated carboxylic acid as a monomer component
An aqueous dispersion of an acrylic copolymer derived using a method (previously, an aqueous dispersion obtained by emulsion copolymerization of monomer components or a solution copolymerization of monomer components and then an aqueous dispersion) is used.

Example of an aqueous acrylic copolymer dispersion (■) produced by emulsion copolymerization. 5 to 15% by weight of α/β monounsaturated carbonic acid (a) and methyl methacrylate (b) as monomer components.
) 35 to 95% by weight, acrylic acid alkyl ester having an alkyl group having 2 to 8 carbon atoms (c) 0 to 4% by weight
, α/β monounsaturated monomer copolymerizable with components (a) to (c) (d) O ~2% by weight (however, the total of components (a) to (d) is 100% by weight) %), produced by an emulsion polymerization method using a conventionally known emulsifier, polymerization initiator, etc. Further, as an example of solution copolymerization followed by an aqueous dispersion, the monomer mixture is solution copolymerized in a lower alcohol such as methanol or isopropyl alcohol, and then a portion of the carboxylic acid is neutralized, Examples include those that are dispersed in an aqueous medium to form an aqueous dispersion. The floor gloss composition of the present invention contains an aqueous zinc oxide dispersion dispersed using the block copolymer (I) and an aqueous acrylic copolymer dispersion (■), but of course it is Other known ingredients used in making gloss compositions may also be used.

Other commonly used known ingredients include paraffin,
Waxes such as montan and polyethylene wax; plasticizers such as dibutyl phthalate and tributoxyethyl phosphate; diethylene glycol monoethyl ether,
Examples include film-forming aids such as butyl cellosolve; alkali-soluble resins such as rosin-modified maleic acid resins and styrene-maleic acid resins; and leveling agents mainly containing fluorine-based surfactants. When obtaining the floor gloss composition of the present invention, the zinc oxide aqueous dispersion and the acrylic copolymer aqueous dispersion (■) may be mixed together and then mixed with other components, or the acrylic copolymer aqueous dispersion (■) may be mixed with other components. The zinc oxide aqueous dispersion may be mixed after the aqueous dispersion (■) and other components are mixed.

The block copolymer (I) used for dispersing zinc oxide may be used in its entirety when preparing the zinc oxide aqueous dispersion, but a portion may be added to the acrylic copolymer aqueous dispersion (■) in advance. It may be added in advance.

PH of the floor gloss composition of the present invention thus prepared
is preferably in the range of 6 to 8. If the pH is less than 6, the leveling properties of the floor gloss composition will tend to decrease when applied, and if the pH exceeds 8, storage stability and drying properties will tend to decrease, both of which are unfavorable. P
When ammonia or organic amines are used for H adjustment, they must be used in an amount that does not dissolve zinc oxide. In the present invention, zinc oxide is dispersed by the block copolymer (I), but the dispersibility of sodium naphthalene sulfonic acid formalin condensate, which is normally used as a dispersant for zinc oxide, is low, resulting in a high concentration dispersion. cannot be replaced. In addition, sodium polyacrylate, which has a structure similar to the anion block of the block copolymer (I) used in the present invention and is usually used as a dispersant for inorganic pigments, has relatively low dispersibility in zinc oxide. However, when an aqueous zinc oxide dispersion dispersed using a polyacrylic acid sorter is added to an aqueous acrylic copolymer dispersion, storage stability is poor and formation of aggregates is observed. However, in the present invention, zinc oxide is mixed with an aqueous acrylic copolymer dispersion (■) and other components as an aqueous dispersion using the block copolymer (I), and therefore zinc oxide is mixed with an aqueous acrylic copolymer dispersion (■) and other components. The formation of aggregates seen when added to dispersions does not occur. Moreover, the zinc oxide aqueous dispersion using this book copolymer (I) is added to an aqueous copolymer dispersion containing no emulsifier (for example, the one disclosed in JP-A-55-142044). It is surprising that it shows stable dispersibility even when Furthermore, in conventional methods using polyvalent metal ions and polyvalent metal complexes, the amount used was limited because thickening and aggregation occur when used in large amounts, but in the present invention, zinc oxide can be used within the above range. You can choose the amount as you like.

Moreover, the floor gloss composition of the present invention has superior adhesion to the substrate compared to conventional floor gloss compositions using polyvalent metal ions or polyvalent metal complexes, and the coating does not become powdery. It has the characteristic of being difficult to use. The reason why the floor gloss composition of the present invention exhibits such excellent features is not yet clear, but it is thought to be as follows.

That is, in the present invention, since zinc oxide is not substantially dissociated in water, the copolymer dispersion liquid is not agglomerated; The nonionic block part consisting of ethylene oxide adsorbs and helps in dispersion, which improves stability; Since the emulsion copolymer is ionically cross-linked at a relatively early stage when it begins to volatilize, the emulsion copolymer tends to have poor affinity with the floor substrate and its adhesion decreases. The combined (I) and dispersed zinc oxide particles are emulsified.
Since the crosslinking reaction occurs for the first time when it comes into contact with the copolymer particles, it is thought that the emulsion copolymer retains its affinity to the floor base material and exhibits good adhesion during the coating formation stage. However, the present invention is not limited in any way solely by these reasons. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

However, the present invention is of course not limited to these examples. In addition, unless otherwise specified, "part" in the examples means parts by weight, and "%" means weight %. Reference Example 1 334 parts of polyethylene glycol monoallyl ether (containing an average of 2 ethylene oxide units per molecule) and 10 parts of water were placed in a glass reaction vessel equipped with a thermometer, stirrer, dropping load, gas introduction tube, and reflux condenser. The inside of the reaction vessel was replaced with nitrogen while stirring, and the mixture was heated for 90 minutes in a nitrogen atmosphere.
Heated to 5°C.

Thereafter, 12 portions of an aqueous solution prepared by dissolving 239.3 parts of maleic acid and 141 parts of ammonium persulfate in 225 parts of water were added. After the addition was completed, 141 parts of a 20% ammonium persulfate aqueous solution was added in two powders. After completing the addition, 10 ginma 9
The temperature inside the reaction vessel was maintained at 5°C to complete the polymerization reaction, and a block copolymer (1) was obtained. This copolymer (1)
The pH of the 55% aqueous solution of was 1.1 and the viscosity was 136 Cps. The polymerization rate was 97.8%. Moreover, the molecular weight of this copolymer (1) was 1,800, and the acid value was 285. Next, a 40% aqueous sodium hydroxide solution was added to neutralize the mixture to obtain an aqueous sodium salt solution of copolymer (1). PH of 45% aqueous solution of sodium salt of this copolymer (1)
was 8.2, and the viscosity was 203 cps. Reference Example 2 In the same reaction vessel as in Reference Example 1, a monomer mixture aqueous solution consisting of polyethylene glycol monomethacrylate (containing an average of 9 ethylene oxide units per molecule) 3 and 18.4% sodium acrylate aqueous solution 92 was added. 20% of this and 20% of 40 parts of a 5% ammonium persulfate aqueous solution were respectively charged, and while stirring, the inside of the reaction vessel was purged with nitrogen and heated to 95°C.

Thereafter, the remainder of the above monomer mixture aqueous solution and the remainder of the ammonium persulfate aqueous solution were each added 12 times a day.
After the addition was complete, 8 parts of 5% ammonium persulfate aqueous solution was further added over 20 minutes. After completing the addition of the monomer mixture aqueous solution,
The temperature was maintained at 95°C for 12 minutes to complete the polymerization reaction.
An aqueous solution of block copolymer (2) was obtained. The molecular weight of this copolymer (2) is 4600, and the pH of a 40% aqueous solution is
was 7.4, and the viscosity was 428 CpS. Reference Example 3 Sodium salt of the block copolymer (1) obtained in Reference Example 1, block copolymer (2) obtained in Reference Example 2,
The amounts of low molecular weight sodium polyacrylate and sodium naphthalene sulfonic acid formalin condensate shown in Table 1 were placed in stainless steel beakers, and water was added to obtain an aqueous dispersant solution.

All aqueous dispersant solutions were uniform and transparent. This aqueous dispersant solution: *Glass beads (manufactured by Toshiba, '゛GB-5)
After adding 300 parts of 03M''), one powder of zinc oxide shown in Table 1 was added while stirring with a Lab Disper (manufactured by Tokushu Kika Kogyo Co., Ltd., ``MR-L type''). After the addition was completed, the mixture was further stirred for 3 minutes and the zinc oxide aqueous dispersion (1) to (
4) was obtained. Obtained zinc oxide aqueous dispersions (1) to (4)
The properties are shown in Table 1. Reference Example 4 Neoperex F-60 (
5.33 parts of anionic surfactant (manufactured by Kao Atlas Co., Ltd.), 0.8 parts of potassium persulfate, and 24 g of water were charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and then heated in a hot water bath.

After the liquid temperature reached 75°C, methyl methacrylate 84
．． 8 parts, butyl acrylate 40.0 parts, styrene 16"
part and methacrylic acid 19. A monomer mixture consisting of three components was added dropwise over 12 times to perform emulsion copolymerization. After the monomer mixture was added dropwise, the temperature was raised to 80'C, and the same temperature was maintained during the printing period, followed by cooling to room temperature. The pH was then adjusted to 7 using aqueous ammonia to obtain an acrylic copolymer (1) having a solid content of 40.1% and a viscosity of 23 CpS. Reference Example 5 In a reaction vessel similar to Reference Example 1, 12 parts of acrylic acid and 91 parts of ethyl acrylate were added. 3. Methyl methacrylate 136.
8 parts of a monomer mixture solution consisting of 8 parts of azobisisobutyronitrile, 2.4 parts of azobisisobutyronitrile, and 16 parts of isopropyl alcohol were charged, and after purging the system with nitrogen, it was heated in a hot water bath.

After starting the flux at 81°C and continuing the three-powder reaction, the remaining 322.4 parts of the monomer mixture solution was added dropwise over 2 hours at the same temperature.

After the dropwise addition was completed, the reaction solution was kept at the flux temperature for 3 hours.
After the polymerization reaction, m parts of 28% aqueous ammonia and 450 m of water were added.
The mixture was heated again to distill off a total of 259 parts of the isopropyl alcohol used as a solvent and a portion of the water, resulting in a solid content of 40% and a viscosity of 31 CpS. ) An aqueous acrylic copolymer dispersion (2) having a pH of 7.5 was obtained. Reference Example 6 The aqueous acrylic copolymer dispersions (1) and (2) obtained in Reference Examples 4 and 5 are listed in Chapter 20, respectively, and the zinc oxide aqueous dispersions (1) to (3) obtained in Reference Example 3 are ) and the zinc compounds shown in Table 2 were added, respectively, to obtain zinc-added acrylic copolymers (1) to (9).

Obtained zinc-added acrylic copolymer aqueous dispersion (1)
The properties of (9) are shown in Table 2. Manufacturing Examples 1 and 2 of Floor Gloss Compositions Using the aqueous zinc-added acrylic copolymer dispersions (1) and (7) obtained in Reference Example 5, floor gloss compositions were prepared according to the following formulations, respectively. Prepared.

Zinc-added acrylic polymer aqueous dispersion (adjusted to 25% solids)
(Note 1) 'AC-392' (solid content 25%)
(Note 2) Ethyl carbitol tributoxyethyl phosphate ''FC-128'' (Adjusted to 1% solids) (Note 3) Water (Note 4) January 1st 8 parts 2 parts 1. 5 parts variable (Note 1) Manufactured by Sumitomo Duretz Co., Ltd., alkali-soluble resin (Note 2) Manufactured by Allied Chemical Co., Ltd., polyethylene wax (
Note 3) Fluorine surfactant manufactured by Sumitomo 3M Co., Ltd. (Note 4) Amount required to obtain a solid content concentration of 16% Properties, storage stability, and commercially available vinyl of each floor gloss composition prepared in this manner We measured various performances of Yang Ga applied to asbes tiles.

The results are shown in Table 3. Note that the performance test method is as shown in k. Viscosity: Measured at 25°C and 60 rpm using a Bismethron viscometer manufactured by Seiki Kogyo Research Institute.

Storage stability: Determined from viscosity change and phase separation after storage in a constant temperature bath at 50'C for 20 days. S Odor; Frontage 4.5771 with vinyl asbestos tiles laid on the floor.
In a room with a depth of 4.57 TL) and a height of 2.4 rr1, apply the floor gloss composition in a sealed state, and remove the odor immediately after application.
Judgment based on human smell evaluation. i Workability: Judged by the difficulty of work when applying the floor gloss composition on vinyl asbestos tiles with a mop.

) Leveling property: Determined from the surface condition when the floor gloss composition is applied with a mop onto vinyl asbestos.

5 Recoatability: Evaluate the surface condition when recoating is performed at intervals of 3 coats.

l Gloss: Two coats of floor gloss composition, 20°C, 65%
The 60° specular reflection gloss after being left for 2 $f under RH conditions was measured using a gloss meter (``GM-dou'' manufactured by Murakami Color Giken).

8 Adhesion: Cut the surface coated with the floor gloss composition at 1-1 intervals to create 10-wide squares per 1 cm square, and adhere cellophane tape (manufactured by Nichiban) over the squares.
Judgment was made from the number of squares remaining without peeling off the coating when the force was applied at an angle of 0'C.

9 Removability: Determined by precision method using a washability tester specified by the Japan Floor Polish Industry Association.

10 Water resistance: Determined by the method of Japan Floor Polish Industry Association standards.

11 Heel mark resistance; The surface of the white vinyl asbestos tile coated with the floor gloss composition was 3.
Judgment is based on the amount of dirt and scratches that occur when struck for 1 minute at rotational speeds of 00, 400, and 600 rpm, respectively.

Comparative Examples 1 to 3 In Example 1, the aqueous acrylic copolymer dispersion (1) obtained in Reference Examples 4 and 5 was used instead of the zinc-added acrylic copolymer dispersion (1) or (7). A floor gloss composition was prepared using the same formulation as in Example 1 using (2) and the zinc-added acrylic copolymer aqueous dispersion (4) obtained in Reference Example 6, respectively.

The properties, storage stability, and various performances when applied to commercially available vinyl asbestos tiles of each of the floor gloss compositions thus prepared were compared. The results are shown in Table 3. Example 3 Floor light containing no zinc oxide obtained in Comparative Example 1. 10 sides of sawa composition (using acrylic copolymer dispersion (1))
1 part of the zinc oxide aqueous dispersion (1) obtained in Reference Example 3 was added to prepare a floor gloss composition containing zinc oxide.

No formation of aggregates was observed during addition, and a floor gloss composition was obtained that exhibited the same performance as the floor gloss composition obtained in Example 1 (zinc-added acrylic co; polymer (1) was used). . Comparative Example 4 In Example 1, the zinc-added acrylic copolymer dispersion (5) obtained in Reference Example 6 was used instead of the zinc-added acrylic copolymer aqueous dispersion (1) or (7). An attempt was made to prepare a floor gloss composition using the same formulation as in Example 1, but a large amount of aggregates formed during mixing, and a coatable floor gloss composition could not be obtained.

Comparative Example 5 0.5 part of zinc oxide powder was added to one concave portion of the zinc oxide-free floor gloss composition obtained in Comparative Example 1 (using acrylic copolymer aqueous dispersion (1)).

No aggregate formation was observed at the time of addition, but a large amount of zinc oxide was observed to settle after being left for one day. When this was stirred and applied to vinyl asbestos tiles, the surface smoothness was low and satisfactory performance could not be obtained. Comparative Example 6 When 0.5 part of zinc acetate was added to 1 concave part of the zinc oxide-free floor gloss composition obtained in Comparative Example 1 (using acrylic copolymer aqueous dispersion (1)), aggregates were formed. A large amount of was produced, and a coatable floor gloss composition could not be obtained.

Example 4 Using the zinc-added acrylic copolymer aqueous dispersion (1) obtained in Reference Example 6, a floor gloss composition with a solid content concentration of 25% was prepared according to the following formulation.

Zinc-added acrylic copolymer aqueous dispersion (solid content 40%)
Marked part: Durets 19788'' (prepared to 25% solid content) 5 parts ``AC-392'' (solid content 30%) Ethyl carbitol tributoxyethyl phosphate ``FC-128'' (solid content 1%) water (Note 1)
15 parts 8 parts 2 parts 1.5 parts Quantity (Note 1) Amount necessary to obtain a solid content concentration of 25% Properties, storage stability, and application to commercially available vinyl asbestos tiles of the floor gloss composition thus prepared Various performances were measured when L.

The results are shown in Table 4. Comparative Example 7 In Example 4, the zinc-added acrylic copolymer aqueous dispersion (4) obtained in Reference Example 6 was used instead of the zinc-added acrylic copolymer aqueous dispersion (1). A floor gloss composition of the same formulation was prepared.

Claims (1)

[Claims] 1. A zinc oxide aqueous dispersion prepared by dispersing the following block copolymer (I) at a ratio of 1 to 20 parts by weight per 100 parts by weight of zinc oxide, and α as a monomer component.・An aqueous acrylic copolymer dispersion (II) derived using 5 to 15% by weight of β-unsaturated carboxylic acid, and a solid content of 100 parts by weight of the aqueous acrylic copolymer dispersion (II). A floor gloss composition characterized in that the solid content of zinc oxide is contained in a ratio of 1 to 20 parts by weight. Block copolymer (I): General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_1 represents hydrogen or a methyl group, X represents a methylene group or a carbonyl group, and n is 1 to 100
represents an integer. ) and the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (However, in the formula, R_2 represents hydrogen or a methyl group, Y represents hydrogen or a -COOZ_2 group, and Z_1 and Z_
2 each independently represents hydrogen, a monovalent metal, an ammonium group, or an organic amine group. ) and the repeating structural unit (B) shown in (A
) and (B) in a weight ratio of 5:95 to 60:
A block copolymer within the range of 40.