JP2002069385A - Composition for floor polishing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for floor polishing capable of reducing maintenance operation of a coating film by improving hardness of the coating film for the floor polishing, improving abrasion resistance and scratch resistance, and further improving stain-proofness. SOLUTION: This composition for floor polishing, comprising a film-forming organic high-molecular material as an essential component is obtained by formulating scaly particles, preferably scaly silica secondary particles as a filler therewith.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor polish composition and a floor polish coating for the purpose of protecting the surface of a substrate, for example, a floor surface, preventing stains, imparting gloss, and the like.

[0002]

2. Description of the Related Art Conventionally, floor polish compositions have been
Plastic, wood, natural stone, hardened cement, metal,
It is widely used for the purpose of forming a floor polished film on the surface of a base material such as glass, ceramics, leather (natural or artificial), for example, a floor surface, for protecting the floor surface, imparting antifouling and imparting gloss. I have. Here, as the composition for floor polish, in addition to those derived from natural products such as conventional waxes commonly used as a polish for forming and polishing a floor polish film, those composed of synthetic organic polymers have recently been used in many cases. It is supposed to be.

[0003] In general, the physical properties required for a floor polish composition (or a floor polish coating formed therefrom (hereinafter sometimes simply referred to as a polish coating or coating)) include the following. That is,

[0004] The coating must have mechanical strength, durability and chemical durability to protect the floor and the like. The coating must be highly transparent (that is, do not obscure the original color or pattern on the floor or the like). The coating must have high gloss to enhance the appearance. Unlike paint, it is necessary to form a new film after the film is periodically peeled off and washed from the floor, etc., so that the film can be easily peeled off and washed. The composition and coating for floor polish have high safety to the human body.

However, in practice, it is not always easy to obtain a floor polish composition that satisfies all of the above required physical properties.

[0006] The problem will be specifically described below with reference to the use of the composition for floor polishing in office buildings, restaurants, department stores, supermarkets and other floors where the composition is commonly used.

[0007] Floor materials for forming these floors include:
Usually, plastic tiles are often used,
Above all, polyvinyl chloride tiles (so-called vinylites) are widely used because of their excellent physical properties and low price.

The floor polish composition is usually made of a transparent resin such as an acrylic resin, a urethane resin, a styrene resin, an epoxy resin, a silicone resin, a fluororesin, and a copolymer resin of at least two of these resins. Aqueous emulsion state floor polish composition (solid content is, for example, 10 to 3
0% by mass), which is applied to the floor surface, for example, the surface of a newly provided plastic tile (or, as described later, an aqueous release agent or neutral After the detergent is sprayed on the surface of the coating, the surface of the clean tile which has been peeled off and washed with a brush or the like and dried at room temperature is applied a plurality of times (usually within 15 times) using a mop or the like. . In addition, for convenience, the composition for floor polish is referred to as a “floor polish liquid” in the following description.
Or, it may be referred to as "polishing liquid".

Although the polishing liquid can be applied once, it is usually applied in a plurality of times to form a coating film having a laminated structure, so that the antifouling property, smoothness, and glossiness are improved. In general, because it can be a better coating film,
The composition for floor polish is applied in a plurality of times as described below.

That is, the coating amount per application is about 1 to 10 g / m ^{2 in} terms of solid content of an organic polymer substance, and dried at room temperature for about 1 hour for each application to form a layer of the coating. This coating / drying cycle is repeated a plurality of times.

However, the surface of a plastic tile generally has many fine holes having a hole diameter of several μm to about 100 μm. At the stage of about 1 to 2 times, the polishing liquid mainly penetrates the micropores, and the micropores are filled with the organic polymer substance. That is, the first or second application is intended to fill such micropores, and at this stage, the smoothness of the coating is not sufficient, and the gloss of the coating is insufficient. It is.

Next, when a polishing liquid is further applied on this in a similar manner 3 to 15 times, the smoothness of the coating is improved each time the coating is applied, and the final coating having the laminated structure is excellent. It has high glossiness.

[0013] The floor polish coating thus applied a plurality of times is a so-called curing, which is a phenomenon of stabilization of the coating layer due to the passage of days and the application of tread pressure by passing the surface. Is expressed,
Generally, an improvement in the film hardness and the like is observed from the initial stage of coating.

The freshly applied floor polish coating is a beautiful coating having glossiness, but when many people pass on it frequently, the floor polish coating is repeatedly trampled by the shoes, and is used in supermarkets and the like. In the case of, not only humans, but also heavy carts (carts) full of purchased daily necessities frequently move over the coating, and the coating supporting them rapidly wears and is damaged. And is contaminated by heel marks and the like. Furthermore, in the case of supermarkets,
The harshest environments in which the coating can be damaged by wear and abrasion are dedicated shelters where many carts are placed, where the damage to the polish coating is greatly accelerated.

[0015] Thus, when the floor polish coating becomes dirty and damaged and loses its luster (that is, when the floor surface becomes dirty), the entire sales floor is wrapped in a dirty atmosphere,
There is a big problem of giving a bad impression or disgust to the buyer. According to various studies, the beauty and cleanliness of a sales floor can be an important factor that has a very close relationship with sales, which appeals to the psychology of the customer and consequently greatly influences the increase or decrease in sales. It has been revealed, and this is now a common sense among sales managers.

For department store and supermarket department managers, periodic maintenance work is carried out on the worn and contaminated floor polished film as described below to constantly remove the dirt and restore the glossiness. It is imperative to keep the sales area as bright and clean as possible, and this is an extremely important task in sales area management.

Care work: This is an operation of washing the coating with a dilute aqueous solution of a neutral detergent, drying at room temperature, and then mechanically polishing (buff polishing (burnishing)), which is performed almost every day.

Further, in addition to the above-mentioned care work, the following restoring work and recoating work are performed at a required frequency. Restoration operation: After the coating surface is washed with a repair agent-containing liquid, it is dried at room temperature. Recoating work: about 1-2 layers (the most damaged and contaminated layers) on the surface of the polished film of the laminated structure,
After spraying and dissolving the chemical solution, it is washed with a dilute aqueous solution of a neutral detergent, one or two floor polish compositions are applied, dried at room temperature, and polished.

Basically, by repeating the maintenance work cycle (1) to (4), the quality of the floor coating on a daily basis is temporarily maintained.

However, even if these maintenance operations are carried out, after about 1.0 to 1.5 years, the coating is further stained and damaged, so that it is difficult to recover by the above maintenance. Therefore, it is necessary to perform the following work (hereinafter, referred to as “overall repair work”) in which the coating is completely peeled off and the coating is newly renewed. That is,

Stripping operation: First, a highly alkaline stripping chemical is sprayed on the surface of the coating to dissolve or decompose the coating to facilitate peeling, and then rubbed with a brush to peel the entire coating from the tile surface. Furthermore, after washing with a dilute aqueous solution of a neutral detergent, drying is performed at room temperature.

New coating operation: After the above-mentioned peeling operation,
The operation of applying the polishing liquid is performed a plurality of times (within 15 times) to form a new coating film on the floor tile surface (the maintenance operation is performed thereafter).

By the way, the above-mentioned restoration work, recoating work and full repair work cannot be performed during business hours when customers are crowded in department stores and supermarkets.
It is necessary to carry out the process during the night when the store is closed or to carry out the process quickly before opening the store in the early morning. In addition, the work is extremely difficult since the peeling, coating, and drying of the coating are repeated many times.

Under these circumstances, regarding the floor polished film, the characteristics of the film itself are improved by improving the hardness of the film, improving the abrasion resistance and abrasion resistance, and improving the stain resistance. It has been a much desired item to greatly reduce the maintenance work of the coating and to extend the period until the entire repair work of the coating as much as possible.

[0025]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a floor polish composition which greatly reduces the maintenance work of conventional floor polish coatings.

[0026]

Means for Solving the Problems The present inventors have conducted intensive studies in view of the importance of the above-mentioned problems, and as a result, have found that at least scaly particles have been added to a conventionally used floor polish composition comprising an organic polymer substance. By blending, preferably by blending scaly foliar silica secondary particles, the stain resistance, hardness, abrasion resistance and abrasion resistance of the floor polish coating, heel mark resistance and the like are greatly improved,
It has been found that the required maintenance work of the coating can be greatly reduced. The present invention has been made based on such findings.

That is, according to the present invention, there is provided a floor polish composition mainly containing a film-forming organic polymer substance, wherein the composition contains at least flaky particles. A polish composition is provided.

Further, according to the present invention, in a floor polish coating formed of a film-forming organic polymer substance provided on the surface of a substrate, it is considered that the coating contains scale-like particles. A featured floor polish coating is provided.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Composition for Floor Polishing Mainly Containing Film-Forming Organic Polymer) The composition for floor polishing in the present invention is mainly composed of a film-forming organic polymer. As such an organic polymer substance, at least one selected from the group consisting of acrylic resin, urethane resin, styrene resin, epoxy resin, silicone resin, fluororesin, vinyl chloride resin, and polyester resin (independently) Resin-based) and at least two or more of these copolymer resin systems, or a mixture or composite of two or more of these single resin systems and copolymer resin systems. Light refraction index is 1.3 ~
(Approximately 1.6).

These organic polymer substances are preferably used in the form of an aqueous emulsion dispersed in water as fine particles (solid content is, for example, about 10 to 30% by mass and pH is about 8.0 to 9.5). The aqueous emulsion,
By coating and drying the surface of the base material, the dispersed organic polymer substance particles approach and fuse with each other to form a coating.

In addition to a water-based solvent, a solvent other than water, such as a glycol ether-based solvent, can be used. However, an emulsion in the form of an aqueous emulsion is preferable because of easy handling.

The organic high-molecular substance is basically composed of the above-mentioned ones. Specifically, for example, a resin known for a floor polish composition as described below may be used.

(1) Aqueous resin having a carboxyl group (for example, selected from aqueous polyurethane resin containing carboxylic acid and / or carboxylate, acrylic resin, alkali-soluble resin, aqueous polyolefin resin and ionomer aqueous resin) And those containing a component in which an epoxy resin having an epoxy group is dispersed or cross-linked (Japanese Patent Application Laid-Open No. 2000-86977).

(2) Release of an alkali metal hydroxide and calcium ions into an aqueous emulsion or aqueous dispersion of a polymer selected from an α, β-unsaturated carboxylic acid polymer having a carboxyl group in the molecule and an aqueous urethane polymer. A compound obtained by adding a compound to crosslink the carboxyl group in the polymer with calcium (Japanese Patent Application Laid-Open No.
-102006).

(3) Those comprising an aromatic vinyl compound, a (meth) acrylic acid ester and an α, β-ethylenically unsaturated carboxylic acid (JP-A-9-95742).

(4) An aqueous dispersion of a polymer of an ethylenically unsaturated compound containing a polyvalent metal compound such as Zn (JP-A-8-60102).

(5) An acid value obtained by polymerizing a (meth) acrylic radical polymerizable monomer in the presence of an aqueous polyurethane having an acid value of 20 to 200 mgKOH / g (per resin solid content) is 4 to 150 mgKOH / g ( Containing one or more aqueous emulsion resins (per resin solid content) and a polyvalent metal complex (Japanese Patent Publication No. 8-19309)
).

(6) An oil-in-water emulsion of an organopolysiloxane and a mixture of an α, β-unsaturated carboxylic acid and a mixed monomer comprising an acrylic and / or methacrylic acid ester monomer are used as radical polymerization initiators. Obtained by emulsion polymerization in the presence of (Japanese Patent No. 2698447)
).

The floor polish composition of the present invention is preferably an emulsion mainly composed of an organic polymer substance in the form of an aqueous emulsion as described above, and the polish solution contains, as additives, a crosslinking agent and a film-forming agent. Agents, plasticizers, coalescing agents, surfactants, defoamers, leveling agents, slipperiness modifiers, detergents, delamination improvers, preservatives, bactericides, repellents (insect repellents), antistatic An auxiliary material such as an agent can be contained in an appropriate amount.

As the crosslinking agent, for example, in the case of a crosslinking agent for an emulsion or dispersion of an α, β-unsaturated carboxylic acid-based polymer having a carboxyl group or a carbonyl group in the molecule or an aqueous urethane-based polymer, Compounds having two or more hydrazine groups or complexes or salts of divalent or higher polyvalent metals such as calcium, zinc, and aluminum can be used. Examples of the film-forming agent include alcohols and glycol ethers. ,
As the plasticizer, for example, adipates,
Examples thereof include dibutyl phthalate, dioctyl phthalate, 2-pyrrolidone, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, and adipates.

On the other hand, examples of the coalescing agent include diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, trimethylpentanediol.
Examples thereof include monoisobutylene, N-methyl-2-pyrrolidone, and texanol. Examples of the surfactant include an ethylene oxide adduct of polyoxyethylene nonylphenyl ether, an ethylene oxide adduct of sodium polyoxyethylene lauryl ether sulfate, and a fluorine-based interface. Activators and the like are exemplified, as a leveling agent,
For example, alkali-soluble resins and adipic esters are exemplified. Examples of the slip control agent include natural waxes such as plant-based, animal-based, mineral-based, and petroleum-based waxes, or synthetic hydrocarbons, polyethylene wax, and polypropylene wax. Modified wax and the like are exemplified, and as a repellent (insect repellent), for example, a pyrethroid-based insect repellent and the like are exemplified.

(Objects to be applied to the composition for floor polish) The composition for floor polish of the present invention is applicable to plastic, wood, natural or artificial stone, hardened cement, metal, glass, ceramics, leather ( Surface of a substrate such as natural or artificial), particularly a floor surface. In the present invention, “floor polish” is typically applied to a so-called narrow floor, but in some cases applied to a surface of a base material such as a wall surface, a ceiling surface, a staircase, or an outer surface of a car body. It is also possible.

As already mentioned, usually office buildings,
As flooring materials for restaurants, department stores, supermarkets, etc., plastic flooring materials are used, and polyvinyl chloride flooring tiles are widely used because they are particularly inexpensive.

Taking a general example of such a tile, there are various dimensions, for example, 304.8 mm ×
The surface (top surface) is 304.8 mm × 3.2 mm thick and has high smoothness and gloss on the tile surface. Generally, this surface has a wide variety of colors and beautiful patterns, patterns, patterns, etc. Is given. According to the atmosphere of the application place, such as a sales floor, the best fit pattern and color are carefully selected and constructed.

However, as described above, when the surface of a seemingly beautiful and smooth tile is observed with a microscope, it is quite common that a large number of micropores having a diameter of several μm to 100 μm are present. . Due to the presence of such micropores, when the floor polish liquid is applied, particularly in the first one or two layers, the polishing liquid permeates and fills the micropores. The above tiles are roughly classified into two types, a so-called composition tile and a homogenous style, depending on the layer configuration in the thickness direction of the board. However, the existence of micropores on the board surface is substantially the same, and the present invention The results of tests conducted by the authors have confirmed that both can be treated equally.

(Scaly Particles) The present invention is characterized in that scaly particles are blended in a floor polish composition mainly containing a film-forming organic polymer substance.

This is because scale-like particles having a large aspect ratio, which is the ratio of the length of the surface to the thickness of the particles, have a very large coverage due to the overlapping of particles per unit filling mass. It is based on the findings found by the present inventors that they can be blended to greatly improve the film properties.

That is, in the process of applying the floor polish solution to the floor surface and drying it to form a polish film, the flaky particles mixed with the polish solution are applied to the floor surface in the film. It is considered that the particles are oriented substantially parallel to each other, so that the particles exist in surface contact with each other in the coating. Therefore, it is considered that the strength of the coating is improved and the adhesion to the substrate surface is also increased.

There are no particular limitations on the particles having such a flaky morphology. For example, any of silica, mica, talc, glass, alumina, titanium oxide, zinc oxide, tin oxide and the like are preferably used. And silica, mica and talc can be more preferably used.

The average particle size of the flaky particles (measured by a Coulter counter, a laser diffraction / scattering type particle size distribution measuring device, a dynamic light scattering type particle size distribution measuring device, etc.)
Although not particularly limited, when it is used in the present invention, it is usually about 0.001 to 20 μm, and the ratio of the surface diameter to the particle thickness (aspect ratio) is 2 or more and 3 or more.
Those having a value of 00 or less are preferable.

The blending amount of the flaky particles is 1 to 80% by mass, preferably 1 to 70% by mass, more preferably 2 to 60% by mass in the composition for floor polish. This blending amount is appropriately selected depending on the environment of the floor surface to which the floor polish liquid is applied. For example, in a severe use environment such as the above-described cart place, the scale-like particles are 30% by mass.
More preferably, it is preferable to add 50% by mass or more.

In the past, it has been proposed to use colloidal silica as a filler in a floor polish composition (for example, see Japanese Patent Application Laid-Open No. 6-80933).
And JP-A-8-109353. The present inventors have found that colloidal silica has a minute spherical or irregular shape and has various problems. For example, when colloidal silica is blended with the floor polish solution, especially when blended by several tens% or more, the adhesion of the substrate surface is reduced, and in severe cases, the coating itself is easily peeled off. This is because the microspherical colloidal silica is only in point contact with each other in the coating, and at room temperature drying,
Since the film itself has no film forming effect, the effect of improving the film strength is not substantially large, and if particles having a slim shape are present on the surface of the substrate, the film-forming organic polymer substance and the surface of the substrate of the organic polymer substance may not be formed. It is considered that it hinders contact and lowers adhesion.

Further, according to the study of the present inventors, it has been found that a floor polish coating compounded and formed with colloidal silica as a main filler has a problem of poor heel mark resistance.

In the present invention, it is most preferred that the scaly particles are silica, which is generally called a layered polysilicic acid or a metal salt thereof. Here, the layered polysilicic acid refers to a polysilicic acid having a silicate layer structure whose basic structural unit is composed of only SiO ₄ tetrahedron. Accordingly, the layered polysilicic acid or a salt thereof is, for example, silica-X, silica-Y, Kenyaite, magadiite, macatite, islayite, kanemite, octosilicate, and the like. It is a general term for an H-type in which alkali metal or the like in a salt is ion-exchanged with hydrogen ions, or a salt type such as an alkali metal salt before the acid treatment. In the present invention, the layered polysilicic acid means both the H type and the salt type such as an alkali metal.

Of these, silica-X, later known as a type of layered polysilicic acid, was first described in detail by A. Heydemann (Beitr. Mineral. Petr.
Ogr., 10,242-259 (1964), followed by analogous crystals of silica-X and silica-Y, reported by BAMitsyuk (Geochem. Int. 13, 101-111 (1976)) and further silica-X
And silica-Y are also reported by S. Kitahara et al. (Proc. Inst. Symp. Hydrootherm. React., 1
s, 480-495t (1983).

On the other hand, other layered polysilicic acids and salts thereof include kanemite, macatite, magadiite,
Natural or synthetic layered polysilicic acids such as Kenyaite, ilite and octosilicate or salts thereof are known, and there are many research reports on this. For example, in Japan, representative and advanced papers include Katsunori Kosuge, Clay Science, 33 (4), 215-222, (1994). For Kenyaite, see K. Beneket et al., American Mineralog
ist, 68, 818-826, (1983). The naming of layered polysilicate or layered polysilicate is described in a review by Kuroda (Surface,
vol.27, No.2, 77-88 (1989)).

In particular, the scaly fine particles used in the polishing liquid are used to improve the hardness of the film, the transparency, the gloss, and the like.
The above-mentioned layered polysilicic acid is most suitable because a material having the most excellent stain resistance and adhesion to a substrate can be obtained.

The layered polysilicic acid used in the present invention is particularly preferably substantially composed of secondary particles of flaky silica formed by laminating primary particles of flaky silica in parallel with each other and forming a plurality of layers. Are flaky silica particles having a layered particle morphology that is present independently of each other. When such flaky silica particles are used, those having the most excellent properties such as improved hardness of the coating, transparency, glossiness, stain resistance, and adhesion to the substrate can be obtained.

The foliar silica secondary particles can be obtained by the methods proposed by the present inventors (JP-A-2000-72432, JP-A-11-351182, JP-A-2000-206264).
) Can be obtained industrially easily. Hereinafter, the foliar silica secondary particles that are particularly preferable to be used as a filler will be described in detail.

(Secondary Particles of Leaf-like Silica) The silica particles used as the filler in the present invention are most preferably basically composed of flake-like silica primary particles basically having parallel planes between planes. It is a leaf-like silica secondary particle formed by overlapping a plurality of sheets.

The silica secondary particles are formed by overlapping scale-like primary particles, but the primary particles cannot be identified by a scanning electron microscope (hereinafter abbreviated as SEM). This is because only the leaf-like secondary particles in which a plurality of sheets are overlapped with their planes oriented in parallel can be identified. When observed using a transmission electron microscope (hereinafter abbreviated as TEM), the electron beam is The primary particles, which are ultrathin flake particles that partially transmit, can be identified. The bonding between the layers of the primary particles is extremely strong, and it is difficult to separate and separate the flake-like primary particles, which are constituent units thereof, one by one from the leaf-like secondary particles.

The foliar silica secondary particles used in the present invention are:
It is obtained by crushing tertiary aggregate particles (tertiary particles) of silica.

The tertiary silica aggregate particles have a large number of gaps (voids or pockets) formed by the overlapping of the leaf-like secondary particles irregularly, as observed from the SEM photograph. It can take various forms such as cabbage, onion, petal, bud, snail, etc. depending on the state.

The tertiary silica particles can be produced preferably by the method proposed by the present inventors (JP-A-2000-72432).

That is, a method in which spherical or irregularly shaped silica hydrogel is used as a starting material and subjected to hydrothermal treatment in the presence of an alkali metal, wherein the silica tertiary aggregate particles silica-X, silica-Y, etc. of the present invention are used. With lower temperature and shorter time reaction without generating crystals such as quartz,
Moreover, it is a method that can be manufactured with high yield.

Here, the spherical silica hydrogel may be formed by solidifying a silica hydrosol in a petroleum or other medium into a spherical shape as has been known for a long time. As described in JP-B-48-13834, the silica / alkali molar ratio (SiO ₂
/ Ne ₂ O) 3.5 to 20 mol / mol, an aqueous solution of an alkali silicate having a silica concentration of about 2 to 20% by mass and an aqueous solution of a mineral acid are mixed to produce a silica sol having a pH of about 7 to 9 in a short time. It is produced by a method of releasing into a gaseous medium and gelling in a gas.

Using such a silica hydrogel as a starting material, a hydrothermal treatment is performed by heating in a heating pressure vessel such as an autoclave or the like to produce tertiary silica aggregate particles. In this case, the spherical silica hydrogel may be used as it is, but preferably, it is pulverized or coarsely pulverized to a particle size of 0.1.
A thickness of about 1 to 6 mm is desirable because stirring in the autoclave can be performed more effectively.

The hydrothermal treatment is performed at a temperature in the range of 150 to 220 ° C., preferably 160 to 200 ° C., in order to obtain a single phase such as silica-X or silica-Y in a short time.

The required time for the hydrothermal treatment may vary depending on the temperature of the hydrothermal treatment, the presence or absence of seed crystals, and the like, but is usually about 3 to 50 hours, preferably about 5 to 40 hours.

The silica 3 thus obtained in the form of a water slurry
By crushing and dispersing the secondary aggregate particles by the specific method proposed by the present inventors, a water slurry of foliar silica secondary particles having a solid content of 1 to 20% by mass can be obtained. No. 11-351182, Japanese Patent Application No. 2000-20626
No. 4).

That is, using a solid-liquid separation / water-washing device such as a belt filter or a filter cloth centrifuge, water-washing / solid-liquid separation is performed, and if necessary, repulping with water is further performed. Water slurry having a SiO ₂ concentration of 1 to 30% by mass, and supplying the water slurry to a wet grinding device (crushing device) such as a wet bead mill or a wet ball mill of a system of mechanically high-speed stirring using a grinding medium to produce scales. The silica tertiary aggregate particles are crushed. Here, in order to prevent the secondary particles of foliar silica from being pulverized and broken, the diameter of the secondary particles is 0.2 to 1.0 m.
Particularly preferred is a wet bead mill using medium beads such as alumina or zirconia.

Thus, a plurality of flake primary particles substantially free of tertiary particles, which are oriented parallel to each other and overlap each other, have an average particle diameter of 0.001 to 10 μm. Obtained as a slurry.

The basic physical properties of the foliated silica secondary particles used in the present invention are as follows. The SiO ₂ purity of the silica in the silica secondary particles is 99.0% by mass or more. The pH is 6.0-8.0, and the spectrum of X-ray diffraction is ASTM (American Society f
or Testing and Materials) (hereinafter simply referred to as an ASTM card) No. 16-03
2θ = 4.9 °, 26.0 °, and 2 corresponding to 80
2θ = Silica-X characterized by a main peak at 8.3 ° and / or ASTM card number 31-1233
Silica consisting of silica Y characterized by main peaks at 5.6 °, 25.8 ° and 28.3 °. As peaks other than the above, peaks such as ASTM card numbers 31-1234 and 37-0386 are observed for silica-X, and ASTM card numbers 35-63 and 25-1332 are observed for silica-Y. is there.

The oil absorption (JIS K5101) is 100
１５０150 ml / 100 g. The average particle diameter of the foliar silica secondary particles is in the same range as the other scaly particles already described, and is not particularly limited, but is usually 0.001 to 20 μm, preferably 0.01 to 10 μm.
m, more preferably about 0.1 to 10 μm.

The average particle diameter can be measured by a laser diffraction / scattering type particle size distribution analyzer (for example, model LA-920 manufactured by Horiba, Ltd.) or a dynamic light scattering type particle size distribution measuring device (for example, Horiba (LB-500 type, manufactured by Seisakusho)
Alternatively, it is measured by using a Coulter counter (e.g., Coulter Electronics Co., Ltd., MA-II type) as appropriate according to the range of the particle diameter.

When observed by SEM, the foliar silica secondary particles have a thickness of 0.001 to 0.5 μm, and the ratio of the longest length of the foliar silica secondary particles (plate) to the thickness (aspect ratio). Is at least 5 or more, and the ratio (aspect ratio) of the minimum length of the leaf-like silica secondary particles (plates) to the thickness is 2 or more. The upper limit of the ratio of the longest length to the thickness of the foliar silica secondary particles and the upper limit of the minimum length are not particularly defined, but the former is 30%.
0 or less, and the latter is preferably 150 or less.

When the pore distribution of the silica secondary particles was measured by a BET method (Bellsoap-28, trade name, manufactured by Nippon Bell Co., Ltd.), the pore volume was 0.05 to 0.15 ml / g.
The specific surface area is 30~80m ² / g.

As the optical properties, the silica secondary particles have a light refractive index of 1.48 to 1.52.

The infrared absorption spectrum (FT-IR) of the silica (SiO _{2 at} room temperature without heat treatment)
Is 3600-3700 cm ^-1 , 3400-3500c
Silica having silanol groups each having one absorption band at m ^-1 . Further, the amount of silanol groups per specific surface area by the BET method has a large value of 50 to 70 μmol / m ² (several times that of silica gel).

The saturated solubility of the silica in an aqueous acid solution and aqueous alkali solution at 20 ° C. is low. That is, the dissolved SiO ₂ concentration is 0.008% by mass for a 10% by mass aqueous HCl solution, and 0.1% for ion-exchanged water.
For a 006 mass%, 5 mass% NaOH aqueous solution,
It is 0.79% by mass with respect to 0.55% by mass and 10% by mass of NaOH aqueous solution, indicating that it has small solubility in both acids and alkalis and has acid resistance and alkali resistance. In particular, it has a very small solubility in an aqueous alkali solution as compared to silica gel or colloidal silica, and indicates that it has alkali resistance.

As described above, the layered polysilicic acid such as secondary particles of foliated silica used as a filler of the composition for floor polish in the present invention is preferably silica 3
It is obtained by crushing the secondary aggregate particles (tertiary particles) by a specific mechanical method discovered by the present inventors.

On the other hand, heretofore, proposals have been made to chemically disintegrate and disperse the tertiary aggregated particles by treating them with an aqueous alkali solution such as lithium hydroxide, potassium hydroxide or ammonium hydroxide. (For example, Katsunori Kosuge et al., Journal of the CeramicSociety of Japan, 100 (6),
872-875 (1992), Katsunori Kosuge et al., Zeolite, 13 (3), 89-96
(1996), JP-B-6-104565, etc.) (hereinafter referred to as "chemical disintegration method").

However, the inventors of the present invention have studied the above-mentioned chemical disintegration method in detail, using sodium-type kenyaite as an example, according to the method of the known example. It was confirmed that particles having a form substantially corresponding to the secondary particles of the foliar silica used in the above were not obtained. That is, when the particles after the treatment by the chemical disintegration method are observed with a SEM, the particles are apparently observed to be disintegrated. (For example, a Coulter counter, a laser diffraction / scattering type particle size distribution measuring device, a dynamic light scattering type particle size distribution measuring device, and the like), the particle size distribution does not significantly change before and after the treatment, No significant decrease in the average particle diameter, which should be recognized by the particle dispersion, was observed. Further, particles obtained by these chemical disintegration methods basically do not have a strong film-forming ability.

On the other hand, in the mechanical disintegration / dispersion method proposed by the present inventors, the average particle diameter after the disintegration treatment is smaller than the basic particle shape of the secondary silica secondary particles. It is recognized that the particles are substantially smaller than before the treatment without substantial destruction, and that the secondary particles of foliar silica are present independently of each other in the observation of the dispersed particles by SEM. It is clearly known (Japanese Patent Application No. 11-3)
No. 51182, Japanese Patent Application No. 2000-206264). Further, the leaf-like silica secondary particles have a film forming ability by themselves, and are characterized in that a strong film can be formed even at room temperature drying conditions without adding a binder or the like.

Thus, the foliar silica secondary particles are:
A water slurry of layered polysilicic acid or layered polysilicate, which is a method of dispersing constituent particles of tertiary aggregated particles as applied in the present invention, is a method of mechanically high-speed stirring using a pulverizing medium, that is, a wet bead mill, It has been confirmed that a method using a wet crushing device (crushing device) such as a wet ball mill is most suitable.

(Method for Preparing Composition for Floor Polishing of the Present Invention) The above-mentioned scaly particles such as the secondary particles of leaf-like silica (hereinafter referred to as “secondary particles of leaf-like silica”) are used for the polish composition. In the case of using it in a water slurry, it is suitable because it is easy to handle. When the water slurry such as the foliar silica secondary particles is used for a polishing liquid, the solid content in the water slurry such as the foliar silica secondary particles is 5 to 20% by mass.
Is preferred.

In particular, when the water slurry in the case of using the foliar silica secondary particles is used by being mixed with a polish solution comprising an organic polymer substance in an aqueous emulsion state, the water of the foliar silica secondary particles is used in advance. Pretreatment adjustment of the slurry is required. The polish solution generally has a pH of 8.0 to 8.0.
It is a liquid in an alkaline aqueous emulsion state of 9.5. Since the stability of the aqueous emulsion depends on the pH, by mixing the foliar silica secondary particles with the water slurry,
After the pH value of the polish solution and the pH value of the water slurry of the foliar silica secondary particles are substantially matched so that the pH of the blended solution does not greatly fluctuate and destroy the emulsion state of the polish solution, It is preferable to mix both solutions.
The pH adjustment of the aqueous slurry of the foliar silica secondary particles is performed by N
An alkali such as an aOH aqueous solution may be used. In addition,
The pH adjustment operation may be performed before or after mechanical pulverization using a wet bead mill or the like.

It is of course possible to use general layered polysilicic acid as a filler. In this case, a salt type such as an alkali metal salt type has a high pH in a state of a water slurry, which may cause the above problem. It is extremely easy and more preferable to adjust the pH of the polish solution to a pH range that forms a suitable aqueous emulsion state. In this case, when the slurry has a silica concentration of 1 to 30% by mass and has a pH of 4.0 to 9.5, preferably about pH 6.0 to 9.5, the slurry is most suitable. I have.

The method for preparing the polish composition is generally carried out as follows. That is, the solid content concentration and the pH value of a polishing liquid composed of an organic polymer substance in an aqueous emulsion state, which has been conventionally used as a polishing liquid, are measured in advance. Next, the p of a polish liquid composed of an organic polymer substance in an aqueous emulsion state to be blended
The pH of the aqueous slurry of the foliar silica secondary particles and the like is adjusted to substantially match H, and the pH value and the solid content concentration are measured. Finally, the polishing liquid and a water slurry such as foliar silica secondary particles are mixed. The p of the polishing liquid containing the secondary particles of foliar silica thus obtained
Naturally, H is adjusted to have the same pH of about 8.0 to 9.5 as that of a generally used polish liquid.

In the present invention, the method for preparing the polish composition is not particularly limited, and the two liquids described above may be charged and mixed at room temperature in a mixing container at a predetermined ratio. The mixing device is not particularly limited,
A stirring device having stirring blades, a wet disperser using dispersed beads, and the like can be applied.

After mixing the two liquids, it is preferable to measure the solid content concentration and the pH value in the liquids for confirmation.
When the liquid has foaming, the stirring is stopped and the solution is allowed to stand until the foaming disappears, and then used as a polishing composition.

(Composition ratio in polish composition and polish coating) The composition for floor polish in the present invention comprises an organic polymer substance in the form of an aqueous emulsion, foliar silica secondary particles and the like, and a low-volatile liquid (water or organic). solvent)
It consists of As the low volatile liquid, water is desirable from the viewpoint of handling. The concentration of the total solid content (organic polymer substance + foliar silica secondary particles and the like) in the composition is preferably 5 to 30% by mass, more preferably 10 to 25% by mass. If the amount is less than 5% by mass, the drying time after application becomes extremely long. If the amount exceeds 30% by mass, the viscosity of the composition increases and it becomes difficult to apply the composition uniformly.

[0093] In the present invention, the most preferable one to be used as a filler is secondary particles of foliar silica. When secondary particles of foliar silica are used, this is in addition to other layered polysilicic acid or mica. Scale-like particles such as talc may be mixed and used. In addition, if it is 30 mass% or less of the whole filler consisting of flaky particles, it can be replaced with colloidal silica and used.

Further, the foliated silica 2 relative to the total solid content (organic polymer substance + foliated silica secondary particles, etc.) in the composition was used.
The ratio of the secondary particles and the like is preferably from 1 to 90% by mass, and more preferably from 2 to 80% by mass, since a tough film having excellent stain resistance can be obtained. If the amount is less than 1% by mass, the above-mentioned effect due to the addition of the secondary particles of foliar silica is substantially reduced. If the amount exceeds 90% by mass, the coating becomes opaque and the color and pattern of the underlying tile become difficult to see.
The flexibility of the coating is also greatly reduced.

The surface of the coating containing the foliar silica secondary particles and the like in the above preferred range is subjected to a low-temperature oxygen plasma incineration treatment to remove organic polymer substances by incineration and to remove the foliar silica secondary particles and the like. When the state is observed by SEM, the state in which the foliar silica secondary particles and the like are oriented substantially parallel to the tile surface and stacked, and the overlap of the foliar silica secondary particles and the like covers the tile surface, Observable clearly.

In the floor polish coating of the present invention, the coating contains scaly particles, for example, lamellar polysilicic acid, and particularly preferably secondary foliar silica particles made of flaky silica flakes. Due to this, the coating of the present invention is characterized by being less susceptible to breakage and contamination than conventional polished coatings, even when a large number of people pass over it and the pressure on the shoes is constantly applied. Having. This is presumably because such an overlapping coating of the foliar silica secondary particles and the like extremely effectively blocks the invasion of dirt into the coating.

(Method of Coating and Drying Polishing Composition) The method of applying and drying the polishing composition of the present invention containing the secondary particles of foliar silica to the surface of a plastic tile is not particularly limited. Instead, a method of applying the polish liquid manually by using a mop for applying a polish liquid and drying at room temperature is adopted as usual.

In a laboratory, as a method of applying a polishing composition to a small plastic tile test piece, a method of applying the composition using a bar coater or a brush and drying at room temperature may be employed.

The coating method in the present invention is carried out a plurality of times (usually one
It is preferable to divide and apply them within 5 times.

[0100] The amount of application per application is 1 to 10 as solid content (organic polymer substance + foliar silica secondary particles, etc.).
g / m ² and dried at room temperature to form a film. An operation of forming a coating film on the dried coating film and drying the coating film is repeated. The number of operations is not particularly limited, but is generally repeated within about 15 times as described above.

The film of the polishing liquid composed of the organic polymer substance and the foliar silica secondary particles and the like forms a filler such as foliar silica secondary particles and the like with respect to the total solid content (organic polymer substance + foliar silica secondary particles and the like). The greater the ratio of the film, the higher the hardness of the coating (pencil hardness test in the paint test method according to JIS K5400) and the better the adhesion of the coating film to the substrate (cross-cut peel test in the paint test method according to JIS K5400). It is preferable to show a high level. However, when the ratio of the secondary particles of the leaf-like silica is large, the transparency and glossiness of the coating tend to decrease, and a problem arises that the aesthetic appearance is impaired.

The above problem can be solved very effectively by the following method proposed by the present inventors.
The first method is to coat and dry the organic polymer substance and the foliar silica secondary particles etc. formed in a plurality of times to increase the transparency and glossiness of the coating to a desired level. Then, a liquid containing an organic polymer in the form of an aqueous emulsion of the same or different type as the organic polymer in the film containing the secondary particles of foliar silica is applied and dried to form an overcoat. As a result, the transparency and glossiness of the coating film, which are the above-mentioned disadvantages, are greatly improved (Japanese Patent Application No. 2000-139659).

In this method, a transparent overcoat layer substantially made of an organic polymer substance is provided on a floor polish coating containing flaky silica or the like, so that the floor polish coating has enhanced transparency. Things. Here, “substantially” means that a crosslinking agent, a plasticizer, a surfactant, an antifoaming agent, a leveling agent, and the like are contained in a range that does not impair the transparency of the film, for example, even if the content is less than about 5 mass%. Means good.

The second method is to prepare a polish composition in which an aqueous polymer containing an organic polymer substance in an aqueous emulsion state and secondary particles such as foliar silica having an average particle diameter of less than 1 μm are blended. It is. in this case,
The coating composed of an organic polymer substance and foliar silica secondary particles formed by being applied and dried, as in the first method,
It is characterized in that a film having high transparency and gloss can be obtained without overcoating an organic polymer substance in an aqueous emulsion state (Japanese Patent Application No. 2000-206264).

The mechanism by which these two methods greatly improve the transparency and glossiness of the film is unknown, but it is supposed that the fineness in the film composed of the foliar silica secondary particles or the like and a transparent organic polymer substance is probably unknown. It is presumed that the transparency is greatly improved by the two effects of the effect of reducing the volume of the pores and / or the reduction of light scattering due to the reduction of the unevenness on the surface of the film, and that a film having glossiness can be obtained.

(Necessary time until stabilization after application of the polish coating) For example, a conventional polish liquid (that is, an organic powder containing no scaly particles) is applied to a tile such as a polyvinyl chloride resin commonly used for floor tiles. As described above, in the case of a coating film formed by applying a plurality of coatings of an aqueous emulsion of a molecular substance (an aqueous emulsion), at first, the heel mark resistance (ease of soiling when pressed with a shoe). About 10 days is required for the period called curing until stain resistance such as heel mark resistance is improved and stabilized over time as the number of stain resistances is not sufficient. Met. For this reason, the heel mark is particularly likely to be formed during that time, and it is necessary to particularly carefully maintain the coating on the floor surface, which is extremely difficult.

On the other hand, in the polishing composition to which the secondary particles of foliar silica and the like of the present invention are blended, the secondary particles of foliar silica and the like are laminated in the coating so as to be oriented parallel to the floor surface. The presence of the filler forms a tough film. Therefore, it is virtually unnecessary to wait for the number of days for the coating layer to stabilize, and a stable coating can be obtained immediately after coating and drying, so that maintenance of the coating is easy from the beginning. It has been found that there are significant features.

(About the effect of preventing and permeating the polish composition into the underlying tile and the film quality of the polished film of the present invention) As described above, in the case of a tile made of polyvinyl chloride resin and the like generally used for floor tiles, The surface of the tile is porous and generally has many micropores. When a polish solution consisting only of a conventional aqueous emulsion of an organic polymer substance is applied to the tile surface, the aqueous emulsion permeates from the tile surface into the tile. The present inventors set the SE of the vertical section of the tile.
According to examination by M, it was found that the permeation thickness is usually about several tens of μm. The polish liquid that has penetrated into the tile as it permeated cannot perform its original function and is not only wasted, but also reduces the surface smoothness of the coating layer close to the tile surface. There was a problem.

On the other hand, in the polishing composition containing the foliar silica secondary particles of the present invention, the penetration of the polishing liquid into the tile, which is inevitable with the conventional polishing liquid, is substantially reduced. This is foliated silica 2
In the case of a coating containing foliar silica secondary particles, etc., the foliar secondary particles, etc., should be in contact with the floor surface and be aligned and overlap with each other, as compared with the case of a simple coating containing no secondary particles. And, and the coating containing the particles formed between the surface of the tile having a large number of fine irregularities on the surface, because it can significantly improve the adhesion and covering properties to the fine irregular surface, It is presumed that the penetration of the polish liquid into the tiles is greatly reduced. That is, when the polishing composition of the present invention is applied, the polishing liquid is substantially less penetrated into the tile interior, and the surface smoothness of the coating layer close to the tile surface is also good. , SEM observation of the fracture surface and the coating film surface.

It is extremely remarkable that the polished film of the present invention containing the secondary particles of foliar silica is usually formed with a polished film on the underlayer and the cross section of the polished film is observed by SEM, as will be described in detail in Examples described later. In the case where the coating containing the secondary particles such as foliar silica on the surface of the tile as the base is different from the conventional coating,
That is, it cannot be clearly distinguished from the underlayer. That is,
In other words, the resin compound forming the tile and the resin compound forming the coating are formed into a completely integrated and homogenized coating such that the boundaries thereof cannot be apparently recognized. And, the higher the content of secondary particles such as foliar silica, the more remarkable the tendency of integration. in this way,
The floor polished film blended with the secondary particles of foliar silica of the present invention is a tough film in which the film quality is integrated with the base, so that the abrasion resistance, scratch resistance, heel mark resistance, etc. are significantly improved. It is considered something.

Incidentally, in the case of the film containing no filler and the film containing colloidal silica or the like as the filler in the comparative examples described later, both of them can be seen on the tile underlayer by SEM observation. In general, a film different from that of the present invention is formed, and it is recognized that the film of the present invention has a remarkable contrast in film quality. It is naturally expected that such a conventional coating has low adhesion to the base and low abrasion resistance and the like.

Further, in the case where the concrete surface of the base of the floor tile is moist, for example, when the conventional polish is applied, the coating portion above the slight gap between the tiles may be damaged. In many cases, the phenomenon of discoloration occurs due to an increase in moisture and dirt from the surface. In the polishing liquid of the present invention, even in such a case, the foliar silica secondary particles and the like mixed in the liquid are used. It also has a significant feature that it has a significant sealing effect on small gaps between tiles and can effectively prevent the discoloration of the coating film on the small gap between tiles. found.

[0113]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments. (Method of Evaluating Stain Resistance and Scratch Resistance of Floor Polished Film) In general, as a method for evaluating a floor polished film, a floor polish test method specified in JIS K3920 can be applied as a basic physical property test method.

In the present invention, not only the above-mentioned basic physical property test but also an evaluation test in a more realistic environment were performed.
In other words, after applying and drying a polish composition on a polyvinyl chloride floor tile in an actual supermarket store to form a cured product, supermarket customers frequently pass over the coating, Field tests were conducted under daily traffic conditions. In the meantime, during the time period after the store is closed, only the daily care work (cleaning of the coating surface with a dilute aqueous solution of a neutral detergent and work of drying at room temperature) in the above-mentioned maintenance work is performed, and the floor surface after three months is performed. The evaluation method of visually observing the situation and measuring the glossiness with a gloss meter was applied, and the stain resistance and scratch resistance of the coating film were evaluated.

For comparison, the case of using a conventional polishing liquid containing an organic polymer substance in the form of an aqueous emulsion containing no foliar silica secondary particles was compared with the condition of maintenance work, and the daily care work was performed. In addition, a test for performing only the above was also performed. First, in Synthesis Examples 1 to 5, foliar silica secondary particles to be blended were produced.

[Synthesis Example 1] (Production of tertiary aggregated silica particles using hydrogel as starting material) A silica hydrogel as a starting material was prepared as follows using sodium silicate as an alkali source. SiO ₂ / N
a ₂ O = 3.0 (molar ratio), 2,000 ml / min of an aqueous solution of sodium silicate having an SiO ₂ concentration of 21.0% by mass
And a sulfuric acid aqueous solution having a sulfuric acid concentration of 20.0% by mass are introduced into a container provided with a discharge port through separate inlets, and are mixed instantaneously and uniformly. Was adjusted to 7.5 to 8.0, and the silica sol solution uniformly mixed was continuously discharged into the air from the discharge port. The released liquid became spherical droplets in the air, and gelled in the air while flying in a parabola for about 1 second. At the drop point, leave an aging tank filled with water,
Dropped here and aged.

After aging, the pH was adjusted to 6, and the mixture was sufficiently washed with water to obtain a silica hydrogel. The obtained silica hydrogel particles have a spherical particle shape and an average particle diameter of 6
mm. SiO ₂ in the silica hydrogel particles
The mass ratio of water to mass is 4.55 times, and the residual sodium in the silica hydrogel particles is 110 ppm.
Met.

The above silica hydrogel particles were roughly pulverized to an average particle diameter of 2.5 mm using a double roll crusher and used in the next hydrothermal treatment step.

In a 50,000 ml autoclave (electrically heated, with an anchor-type stirring blade), the total Si in the system was
The silica hydrogel having a particle diameter of 2.5 mm (SiO ₂ 18% by mass) so that the O ₂ / Na ₂ O molar ratio is 12.0.
23.7 kg and sodium silicate aqueous solution (SiO ₂ 2
8.75% by mass, 9.3% by mass of Na ₂ O, SiO ₂ / N
5.5 kg of a ₂ O = 3.17 (molar ratio) was added, and 10.7 kg of ion-exchanged water was added thereto, and a hydrothermal treatment was performed at 185 ° C. for 8 hours while stirring at 50 rpm. The total silica concentration in the system was 15% by mass as SiO ₂ .

The slurry after the hydrothermal treatment was subjected to filtration water washing using a filter cloth type vertical centrifugal separator (manufactured by Toko Kikai Co., Ltd., TU-18 type), and the solid water content was 69.7% by mass (solid content concentration). 3
0.3% by mass) of a silica wet cake.

Water is added to the above wet cake and repulped.
A slurry of silica having a SiO ₂ concentration of 7.0% by mass was obtained.
The pH of this slurry was 6.4, and the concentration of sodium in the silica slurry was 50 ppm. Next, this silica slurry was heated at a hot air temperature of 300 ° C. by using a medium fluidized bed dryer (SFD-MINI type manufactured by Okawara Seisakusho).
To obtain 5.6 kg of a dry fine powder.

The product phase of the resulting fine powder was identified by powder X-ray diffraction spectrum. As a result, the X-ray diffraction spectrum of 2θ = 4.9 ° and 26.0 ° corresponding to ASTM card No. 16-0380 was obtained. In addition to the main peak of silica-X, which is characterized by the main peak, peaks corresponding to ASTM card numbers 31-1234 and 37-0386 were observed.

Further, the oil absorption of this fine powder (JIS K5
When 101) was measured, it was 110 ml / 100 g. Observation of the morphology of the formed particles by TEM showed that the scale-shaped flake primary particles were oriented parallel to each other in planes, and a plurality of sheets were overlapped to form leaf-like silica secondary particles.

On the other hand, when the morphology of the formed particles was observed by SEM, the primary particles could not be identified, and were observed as if the secondary particles of foliar silica were primary particles. The shape of the leaf-like particles was scaly, and it was observed that the tertiary silica aggregate particles having a large number of gaps (voids or pockets) were irregularly overlapped and formed. This is the silica tertiary aggregate particle in the present invention.

The average particle diameter of this fine powder (silica tertiary aggregate particles) was measured using a Coulter Counter (manufactured by Coulter Electronics, MAII type, aperture tube diameter 50).
It was 6.1 μm when measured using μm (same in the following Synthesis Examples 2 to 4).

[Synthesis Example 2] (Production of tertiary aggregated silica particles using hydrogel as starting material) A silica hydrogel as a starting material was prepared as follows using NaOH as an alkali source. SiO ₂ / Na ₂ O =
A sodium silicate aqueous solution having a concentration of 3.0 (molar ratio) and an SiO ₂ concentration of 21.0 mass% and a sulfuric acid aqueous solution having a sulfuric acid concentration of 20.0 mass% were separately placed in a container provided with a discharge port. The liquid introduced from the inlet is instantaneously mixed uniformly, and the pH of the liquid discharged into the air from the outlet is 7.5 to 7.5.
The flow rate ratio of the two liquids was adjusted so as to be 8.0, and the uniformly mixed silica sol liquid was continuously discharged into the air from the discharge port. The released liquid became spherical droplets in the air, and gelled in the air while flying in a parabola for about 1 second. An aging tank filled with water was placed at the dropping point, and the ripening tank was dropped and ripened.

After aging, the pH was adjusted to 6, and the mixture was sufficiently washed with water to obtain a silica hydrogel. The obtained silica hydrogel particles have a spherical particle shape and an average particle diameter of 6
mm. SiO ₂ in the silica hydrogel particles
The mass ratio of water to mass is 4.38 times, and the residual sodium in the silica hydrogel particles is 112 ppm.
Met.

The silica hydrogel particles were coarsely pulverized to an average particle diameter of 2.5 mm using a double roll crusher and used in the next hydrothermal treatment step.

In a 5000 ml autoclave (electrically heated, with anchor type stirring blades), the total SiO 2 in the system was added.
2688 g of the above silica hydrogel having a particle diameter of 2.5 mm (18.6% by mass of SiO ₂ ) and an aqueous solution of sodium hydroxide (NaOH) so that the molar ratio of ₂ / Na ₂ O is 11.0.
126 g of 48.5 mass%), 1186 g of ion-exchanged water was added thereto, and 0.5 g of a seed crystal was added thereto.
Hydrothermal treatment was performed at 180 ° C. for 12 hours while stirring at rpm. The total silica concentration in the system was 12.5 as SiO _2.
% By mass.

The slurry after the hydrothermal treatment was subjected to filtration water washing using a filter cloth type vertical centrifugal separator (manufactured by Toko Kikai Co., Ltd., TU-18 type) to give a solid water content of 66.7% by mass (solid content concentration). 3
(3.3% by mass) of silica was obtained.

[0131] Water is added to the wet cake and repulped.
A slurry of silica having a SiO ₂ concentration of 7.0% by mass was obtained.
The pH of this slurry was 6.4, and the sodium concentration in this silica slurry was 80 ppm. Next, the silica slurry was heated to a hot air temperature of 30 using a medium fluidized bed dryer (Okawara Seisakusho, SFD-MINI type).
Drying at 0 ° C. yielded 408 g of dry fine powder.

The generated fine powder was identified by a powder X-ray diffraction spectrum to identify the generated phase.
ASTM card number 31-
In addition to the main peak of silica-Y characterized by main peaks of 2θ = 5.6 ° and 25.8 ° corresponding to 1233, AST
Peaks corresponding to M card numbers 35-63 and 25-1332 were observed.

The oil absorption of this fine powder (JIS K5
When 101) was measured, it was 100 ml / 100 g. Observation of the morphology of the formed particles by TEM showed that the scale-shaped flake primary particles were oriented parallel to each other in planes, and a plurality of sheets were overlapped to form leaf-like silica secondary particles.

On the other hand, when the morphology of the formed particles was observed by SEM, the primary particles could not be identified, and were observed as if the secondary particles of foliar silica were primary particles. The shape of the leaf-like particles was scaly, and it was observed that the tertiary silica aggregate particles having a large number of gaps (voids or pockets) were irregularly overlapped and formed.

The average particle size of the fine powder was determined by using a Coulter counter (manufactured by Coulter Electronics, MA
It was 6.5 μm when measured using Type II).

[Synthesis Example 3] (Production of slurry-like leaf-like silica secondary particles from wet cake of Synthesis Example 1) 1000 g of wet cake after filtration and washing with a centrifuge shown in Synthesis Example 1 (solid content: 30.3% by mass)
020 g was added and repulped to prepare a silica slurry having a solid content of 15% by mass. In this slurry state, the average particle size measured by a Coulter counter is 7.2 μm,
The viscosity measured by a B-type viscometer was 0.010 Pa · s. The pH of this slurry was 6.4.

Next, the pH of this slurry was adjusted to the pH of the polish solution comprising an organic polymer substance in an aqueous emulsion state.
After adjusting the pH of the slurry to 8.5 by adding a trace amount of sodium hydroxide aqueous solution so as to match the above, the slurry was subjected to a medium stirring bead mill (Dynomill KDL-PILOT A type, manufactured by Shinmaru Enterprises Co., Ltd.).
(Vessel capacity 1.4L, 0.5mm diameter zirconia beads 80% filling)), shaft rotation speed 3400rpm,
The mixture was passed once at a flow rate of 30 L / h to crush and disperse the silica tertiary aggregate particles.

The average particle size of the fine particles in the slurry after crushing and dispersing was 1.6 μm as measured by a Coulter counter. The solid concentration of this slurry is 15% by mass.
The viscosity of the slurry was measured with a B-type viscometer and found to be 0.45 Pa · s, and the pH was 8.5. This slurry was used in Example 3 described later.

Next, in order to investigate the physical properties of the dried leaf-like silica secondary particles close to the state of the fine particles in the slurry,
A dry powder was obtained by the following method.

Since the slurry has a peculiar property that it is extremely easily coagulated by drying, in order to obtain a monodispersed dry powder, a water slurry having a very low concentration is dried while preventing coagulation. There is a need.

That is, the slurry (solid content concentration 15
), Water was added thereto to dilute the slurry, and the slurry concentration was adjusted to a solid concentration of 0.3% by mass.

Using a small spray dryer (GA32 type, manufactured by Yamato Scientific Co., Ltd.), the slurry was supplied at a slurry supply rate of 1.7 ml / min and a spray pressure of 0.3 MPa.
(G), spray drying was performed at a hot air temperature of 130 ° C. to obtain a dry fine powder. The average particle size of the obtained dry fine powder measured by a Coulter counter was 1.9 μm.

When this fine powder was observed by SEM, substantially no silica tertiary aggregate particles were observed.
It turned out that it consists essentially of the foliar silica secondary particles of the present invention which are present independently of each other. Also, SE
The average value of the aspect ratio of the secondary particles by M observation is
It was about 50.

The product phase was identified by the powder X-ray diffraction spectrum in consideration of this fine powder. As the X-ray diffraction spectrum, 2θ = 4.9 ° and 26.0 corresponding to ASTM card No. 16-0380. In addition to the main peak of silica-X, which is characterized by the main peak of 該当, peaks corresponding to ASTM card numbers 31-1234 and 37-0386 were recognized, and it was confirmed that the peaks were the same before disintegration.

When the morphology of the formed particles was observed by TEM, the flaky primary flake particles were oriented parallel to each other, and a plurality of flaky silica secondary particles according to the present invention were present independently of each other. Was formed.

Further, this fine powder was embedded in an epoxy resin, and an ultra-thin section was prepared with an ultramicrotome.
When observed at M, the thickness of the primary particles was 1 to 10 nm.
It turned out to be extremely thin.

The fine powder had a pore volume of 0.12 ml / g and a specific surface area of 65 m ² / g by a BET method pore distribution measuring apparatus (Bellsoap 28, manufactured by Nippon Bell Co., Ltd.).
In the pore distribution curve, a sharp large peak in the mesopore region was observed around 3.6 nm.

In the measurement of the infrared absorption spectrum (FT-IR510, manufactured by Nicolet Japan) of the fine powder, 3600 to 3700 cm ^-1 and 3400 to 3500 c
A silanol group having one absorption band was observed at m ^-1 .

In addition, the amount of the silanol group (SiOH)
From the difference between the loss on drying at 120 ° C. for 2 hours and the loss on heating at 1200 ° C. for 3 hours (W mass%), silanol groups per unit mass of silica (SiOH) = W × 111.
According to a calculation formula of 1.1 (μmol / g), 36
It was 50 μmol / g, which was a large value of 56.2 μmol / m ² per specific surface area according to the BET method.

The heat resistance was measured under air atmosphere at 500
At 〜1000 ° C., no particular change was observed by SEM observation.

20 for acid aqueous solution and alkali aqueous solution
For saturated solubility at 0 ° C., the dissolved SiO ₂ concentration is 1
0% by mass, 0.008% by mass for HCl aqueous solution, 0.006% by mass for ion exchanged water, 0.55% by mass for 5% by mass NaOH aqueous solution, 10% by mass
It was 0.79% by mass with respect to the mass% NaOH aqueous solution. Particularly with respect to alkali resistance, for example, the solubility was very small as compared with silica gel (in the case of silica gel, the solubility was also high even in a 3% by mass NaOH aqueous solution,
6.5% by mass).

[Synthesis Example 4] (Production of slurry-like leaf-like silica secondary particles from wet cake of Synthesis Example 2) Synthesis Example 3 using wet cake after filtration and washing with a centrifuge shown in Synthesis Example 2 In the same manner as described above, a medium stirring bead mill (manufactured by Shinmaru Enterprises Co., Ltd., Dynomill KD)
L-PILOT A type (vessel capacity: 1.4 L, diameter: 0.5 mm, filled with 80% zirconia beads: 80%)) is passed once at a shaft rotation speed of 3,400 rpm at a flow rate of 30 L / h to crush and disperse silica tertiary aggregate particles. And a water slurry of foliar silica secondary particles having a solid content of 15% by mass was obtained. The pH of this slurry was 6.4.

A small amount of aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 8.5 so that the pH of the slurry coincided with the pH of the polish solution comprising an organic polymer substance in an aqueous emulsion state. did. The average particle size of the fine particles in the slurry measured by a Coulter counter was 1.7 μm. The solid concentration of this slurry is 15% by mass. Also, the viscosity of this slurry is
When measured with a B-type viscometer, it was 0.40 Pa · s. The slurry adjusted to pH 8.5 was used in Example 4.

[Synthesis Example 5] (Production of slurry-like foliar silica secondary particles from wet cake of Synthesis Example 1) Water was added to the wet cake after filtration and washing with a centrifuge shown in Synthesis Example 1 Using a silica tertiary aggregate water slurry adjusted to a solid concentration of 14% by mass, a medium stirring bead mill (Dyno Mill K, manufactured by Shinmaru Enterprises Co., Ltd.)
DL-PILOT A type (vessel capacity 1.4 L, diameter 0.5 mm, filled with 70% zirconia beads 70%)), 3 passes at a shaft rotation speed of 3400 rpm and a flow rate of 10 L / h, and disintegration and dispersion of silica tertiary aggregate particles And a water slurry of foliar silica secondary particles having a solid content of 14% by mass was obtained. The pH of this slurry was 6.4.

Next, the pH of this slurry was adjusted to the pH of the polish solution comprising an organic polymer substance in an aqueous emulsion state.
Was added to adjust the pH of the slurry to 8.5. The average particle diameter of the fine particles in the slurry measured by a laser diffraction / scattering type particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.) was 0.54 μm. The solid concentration of this slurry is 14% by mass. When the viscosity of this slurry was measured with a B-type viscometer, it was 0.15 Pa · s.
Met. The slurry adjusted to pH 8.5 was used in Examples 1, 2, and 5, and 6.

Next, in order to examine the physical properties of the dried foliated silica secondary particles close to the state of the fine particles in the slurry,
A dry powder was obtained by the following method. The average particle size of the obtained dry powder measured by a laser diffraction / scattering type particle size distribution analyzer was 0.8 μm.

As described above, the slurry has a unique property that it is extremely easily aggregated by drying. Therefore, in order to obtain a monodispersed dry powder, a water slurry having an extremely low concentration is used to prevent aggregation. It is necessary to dry while drying.

Water was added to the slurry (solid content concentration: 14% by mass) to adjust the slurry concentration to 0.1% by mass. The slurry was supplied using a small spray dryer (GA32 type, manufactured by Yamato Scientific Co., Ltd.) at a slurry supply rate of 1.7 ml / min and a spray pressure of 0.3 MPa.
(G), spray drying was performed at a hot air temperature of 130 ° C. to obtain a dry fine powder.

Observation of this fine powder with a SEM revealed that substantially no tertiary aggregated silica particles were observed.
It turned out that it consists essentially of the foliar silica secondary particles of the present invention which are present independently of each other. Also, SE
The average value of the aspect ratio of the foliar silica secondary particles observed in M was about 40.

Example 1 (1) A slurry of secondary particles of foliar silica having a solid content of 14% by mass, which was treated with a medium stirring bead mill and obtained by repeating the method described in Synthesis Example 5, having a pH of 8. 5. The average particle diameter measured by a laser diffraction / scattering particle size distribution analyzer is
0.54 μm) 2.76 kg, and a floor polish liquid in an aqueous emulsion state containing an acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component (trade name: COMFORT, manufactured by JSP Corporation)
UHS, pH 8.5, solid content concentration 17.4 mass%) 2
0.0 Kg was placed in a container equipped with a stirrer, and sufficiently stirred and mixed to prepare a floor polish composition in which leaf-like silica secondary particles were blended. The mass ratio of this composition in terms of solid content is resin: silica content = 90: 10, and pH is 8.
It was 5.

(2) An application test was performed on the floor of a food counter aisle in a large supermarket store. That is, a polyvinyl chloride floor tile (composition vinyl floor tile, manufactured by Achilles Co., Ltd., trade name: Benes 50-311)
(White gray pattern) 304.8 mm x 3
After peeling, washing and drying the conventional polish liquid on the floor where tiles of 44.8 mm x 3.2 mm were spread,
The polish liquid containing the above-mentioned foliar silica was manually applied to the floor tile in four times using a mop dedicated to application of the polish liquid to the floor tile. Each time you apply
A room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content.

After coating and drying, the coating was subjected to a mechanical polishing operation (buff polishing (burnishing)). The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(3) The hardness of the coating is as follows.
In the state of the coating applied on the vinyl chloride tile, the pencil hardness of the coating is accurately determined by the pencil hardness test method (JIS K5400) because the tile as the base material is soft and there are irregularities on the tile surface. Measurement is virtually impossible. Therefore, the following measuring method was applied as a method for accurately measuring the hardness of the coating itself in a laboratory.

A glass plate (soda-lime glass, 70 mm × 150 mm × 2 mm thick) was prepared as a base material, and was coated with # 80 by a bar coater coating method (JIS K5400).
The polish solution was applied on a glass plate using a bar coater (manufactured by Eto Kikai Co., Ltd.) in an amount of 20 g / m ^{2 in} terms of solid content, and then dried at room temperature for 24 hours to obtain a test piece.

Using this test piece, the hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross cut test described in the paint test method of JIS K5400 (the following Examples). In the comparative example, the same measurement method was applied). The pencil hardness was B, and the evaluation score in the crosscut peel test was 10 points.

[0166] Also, the tile having the coating formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating consisting of the organic polymer substance and the foliar silica secondary particles does not permeate into the tile, and a uniform coating with good adhesion at the interface between the coating and the fine irregularities on the tile surface is remarkable. It was confirmed that a significant sealing effect was exhibited.

The characteristic feature is that the SE of the fractured surface is
According to M observation, the portion where the coating containing the leaf-like silica secondary particles on the surface of the tile as the base is not clearly distinguishable from the base. In other words, the resin compound forming the tile and the resin compound forming the coating are completely integrated so that their boundaries cannot be recognized apparently, and a uniform coating which is difficult to distinguish from the underlayer is formed. As described above, the floor polished film containing the foliar silica secondary particles and the like of the present invention is a tough film integrated with a base material whose film quality is substantially different from the conventional one, and therefore has abrasion resistance and abrasion resistance. It is thought that it greatly improves.

Further, the surface of the coating formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, and to determine the presence of secondary foliar silica particles. Observed by SEM, foliated silica 2
It was clearly observed that the secondary particles were stacked and the secondary particles of the foliated silica covered the tile surface.

(4) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor every day for 11 hours, and carts constantly came and went. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

[0170] The coating was applied from the first point after application and drying.
Stain resistance, such as heel mark resistance, was stably exhibited, and stains attached to the film could be easily removed with a mop in daily care work. No accumulation of dirt with the passage of days was observed at all.

[0171] Evaluation points of visual observation of the coating on the floor surface after 3 months and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.)
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 2 (1) A 14% by mass solid content slurry (pH 8.5, laser diffraction / scattering particle size distribution measurement) treated with a medium stirring bead mill obtained by repeating the method described in Synthesis Example 5 The average particle size of the apparatus is 0.54 μm) 3.65 Kg
And an aqueous emulsion containing a acrylic (methacrylate) resin component and a styrene resin component, a floor polish solution (manufactured by JSP Corporation, trade name: PRIMOD)
UAL, pH 8.46, solid content concentration 23.0% by mass) 2
0.0 Kg was placed in a container equipped with a stirrer, and sufficiently stirred and mixed to prepare a floor polish composition in which leaf-like silica secondary particles were blended. The mass ratio of this composition in terms of solid content is resin: silica content = 90: 10, and the pH is
8.5.

(2) An application test was performed on the floor of the toy counter aisle in the same supermarket store as in Example 1. That is, a polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles, trade name: Benes 50)
-311 (white background gray pattern))
After the conventional polishing liquid is peeled off, washed and dried on the floor on which tiles of mm × 304.8 mm × 3.2 mm are spread, the polishing liquid containing the secondary particles of foliar silica is applied to the floor tile. Was manually applied to the floor tile in four times using a mop dedicated to the application of the above. With each application, a room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content.

After application and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was H. The evaluation score in the eye peel test is
10 points.

[0176] Further, the tile having the coating formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating composed of the organic polymer substance and the foliated silica secondary particles did not penetrate into the tile as in Example 1,
The adhesion at the interface between the fine irregularities on the tile surface and the coating was good, and a uniform coating was formed with the base, and it was confirmed that a remarkable sealing effect was exhibited.

According to the SEM observation of the fractured surface, as in the case of the coating of Example 1, the portion where the coating containing the leaf-like silica secondary particles on the tile surface as the base was formed was clearly seen as the base. Could not be identified. That is, also in this case, it was confirmed that the underlying tile and the coating were completely integrated so that their boundaries could be hardly recognized, and a uniform coating that was difficult to distinguish from the underlying layer was confirmed.

Further, the surface of the film formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, and to determine the state of secondary particles of foliar silica. Observed by SEM, foliated silica 2
It was clearly observed that the secondary particles were stacked and the secondary particles of the foliated silica covered the tile surface.

(4) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts were constantly coming and going. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

From the first time point after coating and drying,
Stain resistance, such as heel mark resistance, was stably exhibited, and stains attached to the film could be easily removed with a mop in daily care work. No accumulation of dirt with the passage of days was observed at all.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 3 (1) A 15% by mass solids slurry (pH 8.5, average particle diameter measured by a Coulter counter) treated with a medium stirring bead mill obtained by repeating the method described in Synthesis Example 3 1.6 μm) 23.2 Kg, an aqueous emulsion containing a acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component, a floor polish liquid (manufactured by JSP Co., trade name: COMFORT)
UHS, solid content concentration 17.4 mass%) and 20.0 kg were put into a vessel equipped with a stirrer, and sufficiently stirred and mixed to prepare a composition for floor polish containing secondary particles of leaf-like silica. The mass ratio of this composition in terms of solid content is as follows:
Silica content = 50: 50 and pH was 8.5.

(2) An application test was performed on the floor between the registers having a row of registers in the same supermarket store as in Example 1. That is, a tile having dimensions of 304.8 mm × 304.8 mm × 3.2 mm, which is a polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles Corporation, trade name: Benes 50-311 (white background gray color pattern)) is used. After peeling, washing, and drying the conventional polish on the floor, the polish containing foliar silica is manually applied to the floor tile using a mop dedicated to applying the polish to the floor tile. The coating was performed four times. With each application, a room temperature drying time of about 1 hour was provided. The amount of application each time is 2 to 3 g / m in terms of solid content.
^{Was 2} .

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was F. The evaluation score in the eye peel test is
10 points.

(4) Since the glossiness and transparency of the coating film are insufficient with the coating film containing the secondary particles of foliar silica alone, a polish containing no foliar silica is further added on the coating film. Floor polish liquid in the form of an aqueous emulsion containing an acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component, which is a liquid (manufactured by JSP Co., trade name: COMFORT UHS, solid content concentration 17.4% by mass) Was applied in two separate applications. A room temperature drying time of about one hour was provided for each application. The application amount of each application was ² to 3 g / m ² in terms of solid content.

Further, after coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation is
The coating film was high in glossiness, and the coating film was a transparent coating film in which the color and pattern of the tile were clearly visible.

[0187] Also, the tile having the coating formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating consisting of the organic polymer substance and the foliar silica secondary particles did not penetrate into the tile almost in the same manner as in Example 1, and it was found that the unevenness on the tile surface and the good adhesion at the interface between the coating and the base were uniform. Thus, it was confirmed that a remarkable sealing effect was developed.

According to the SEM observation of the fractured surface, similarly to the film of Example 1, the underlying tile and the film are completely integrated so that their boundaries can be hardly recognized, and it is difficult to distinguish them from the underlying layer. It was confirmed that a homogeneous coating was formed.

Further, the surface of the coating film formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, thereby confirming the state of existence of the foliar silica secondary particles. When observed by SEM, the foliated silica secondary particles are stacked, and the foliated silica secondary particles overlap,
The state of covering the tile surface was clearly observed.

(5) The floor on which the coating was applied may be used by many customers in supermarkets for 11 hours a day,
The cart was exposed to constant traffic. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

The coating has been stably developed from the first time after application and drying, such as heel mark resistance, and the dirt adhering to the coating during daily care work is removed by a mop. And was easily removed. No accumulation of dirt with the passage of days was observed at all.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 4 (1) A 15% by mass solids slurry (pH 8.5, average particle size measured by a Coulter counter) treated with a medium-stirred bead mill obtained by repeating the method described in Synthesis Example 4 1.7 μm) 23.2 Kg, a floor polish liquid in an aqueous emulsion state containing an acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component (trade name: COMFORT, manufactured by JSP Corporation)
UHS, solid content concentration 17.4% by mass) was placed in a vessel equipped with a stirrer, and sufficiently stirred and mixed to obtain a composition for floor polish containing secondary particles of leaf-like silica. The mass ratio in terms of solid content of this composition was resin: silica content = 50: 50, and pH was 8.5.

(2) A coating test was performed on the floor between the registers in the same manner as in Example 3. That is, PVC floor tiles (Achilles composition vinyl floor tiles,
Product name: Benes 50-311 (white background gray color pattern)) 304.8 mm × 304.8 mm × 3.2 mm
After the conventional polish solution is peeled, washed and dried on the floor covered with tiles, the polish solution containing leaf-like silica is manually applied to the floor tiles using a mop exclusively for applying the polish solution to the floor. The coating was performed on the tile in four times. With each application, a room temperature drying time of about 1 hour was provided. The amount of application each time is 2 to 3 g / m in terms of solid content.
^{Was 2} .

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was F. The evaluation score in the eye peel test is
10 points.

(4) Since the glossiness and transparency of the coating film are insufficient with the coating film containing the secondary particles of foliar silica alone, a polish containing no foliar silica is further added on the coating film. Floor polish liquid in the form of an aqueous emulsion containing an acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component, which is a liquid (manufactured by JSP Co., trade name: COMFORT UHS, solid content concentration 17.4% by mass) Was applied in two separate applications. A room temperature drying time of about one hour was provided for each application. The application amount of each application was ² to 3 g / m ² in terms of solid content.

Further, after coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation is
The coating film was high in glossiness, and the coating film was a transparent coating film in which the color and pattern of the tile were clearly visible.

[0198] Further, a tile having a film formed on its surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating composed of the organic polymer substance and the foliated silica secondary particles did not penetrate into the tile almost in the same manner as in Example 1, and the tile surface had good adhesion at the interface between the fine irregularities on the tile surface and the coating. It was confirmed that a uniform coating was formed on the base and that a remarkable sealing effect was exhibited.

According to the SEM observation of the fractured surface, similarly to the film of Example 1, the underlying tile and the film are completely integrated so that their boundaries can hardly be recognized, and it is difficult to distinguish them from the underlying layer. It was confirmed that a homogeneous coating was formed.

Further, the surface of the coating film formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, and to determine the presence of secondary foliar silica particles. When observed by SEM, the foliated silica secondary particles are stacked, and the foliated silica secondary particles overlap,
The state of covering the tile surface was clearly observed.

(5) The floor on which the coating was applied may be used by many supermarket customers every day for 11 hours.
The cart was exposed to constant traffic. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

The coating has been stably developed from the initial point of application and drying, such as heel mark resistance, and the dirt adhering to the coating during daily care work is removed by a mop. And was easily removed. No accumulation of dirt with the passage of days was observed at all.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 5 (1) A 14% by mass solids slurry (pH 8.5, laser diffraction / scattering particle size distribution measurement) treated with a medium stirring bead mill and obtained by repeating the method described in Synthesis Example 5 The average particle size by the apparatus is 0.54 μm) 37.7 Kg
And a floor polish liquid in the form of an aqueous emulsion containing an acrylic (methacrylate) resin component and a styrene resin component (trade name: ACHIEV, manufactured by JSP Corporation)
E, pH 8.45, solid content concentration 17.6% by mass) 20.
0 kg was placed in a container equipped with a stirrer, and sufficiently stirred and mixed to obtain a floor polish composition (hereinafter referred to as solution A) in which leaf-like silica secondary particles were blended. The mass ratio of this composition in terms of solid content was resin: silica content = 40: 60, and pH was 8.5.

Next, a slurry having a solid content of 14% by mass treated with a medium stirring bead mill described in Synthesis Example 5 (the average particle diameter by a laser diffraction / scattering type particle size distribution analyzer was:
0.54 μm) 2.79 Kg, an aqueous emulsion-containing floor polish liquid containing an acrylic (methacrylate) resin component and a styrene resin component (Achieve, manufactured by JSP Co., solid content concentration 17.6% by mass) 2
0.0 Kg was placed in a container equipped with a stirrer, and sufficiently stirred and mixed to prepare a floor polish composition (hereinafter referred to as solution B) in which leaf-like silica secondary particles were blended. The mass ratio of this composition in terms of solid content is as follows: resin: silica content = 9
0:10.

(2) An application test was performed on the floor of a cart storage in the same supermarket store as in Example 1. That is,
Dimension 304.8 mm × 304. Polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles, trade name: Benes 50-311 (white background gray color pattern)).
After the conventional polish solution is peeled, washed and dried on the floor on which tiles of 8 mm × 3.2 mm are spread, the above-mentioned solution A, which is the polish solution containing the above-mentioned foliar silica secondary particles, is polished to the floor tile. Using a mop dedicated to the application of the liquid, the liquid was manually applied to the floor tile in two separate applications. With each application, a room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content.

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 5H. The evaluation score in the eye peel test was 10.

(4) Next, a liquid B as a floor polish containing foliar silica secondary particles was applied onto the coating made of the liquid A using a mop dedicated to applying the polish to the floor tile. It was manually applied to the floor tile in two separate applications. With each application, a room temperature drying time of about 1 hour was provided. The amount of application each time is 2 to 3 g / m in terms of solid content.
^{Was 2} .

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation was glossy, and the coating was a coating in which the color and pattern of the tile were visible.

(5) The hardness of the coating film surface and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peel test in the same manner as in Example 1, and the pencil hardness was H. The evaluation score in the crosscut peel test is
10 points.

[0211] Also, the tile having the coating formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating consisting of the organic polymer substance and the foliar silica secondary particles did not penetrate into the tile almost in the same manner as in Example 1, and it was found that the unevenness on the tile surface and the good adhesion at the interface between the coating and the base were uniform. Thus, it was confirmed that a remarkable sealing effect was developed.

According to the SEM observation of the fractured surface, similarly to the coating of Example 1, the tile and the coating of the base were completely integrated so that their boundaries could be hardly recognized, and it was difficult to distinguish them from the base layer. It was confirmed that a homogeneous coating was formed.

Further, the surface of the coating formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, and to check the existence state of the foliar silica secondary particles. Observed by SEM, foliated silica 2
It was clearly observed that the secondary particles were stacked and the secondary particles of the foliated silica covered the tile surface.

(6) The floor on which the coating was applied was exposed to the environment of a yard where a large number of customers in a supermarket put carts in and out every day for 11 hours. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) is carried out,
Three months later, the condition of the floor surface was visually observed and the gloss was measured with a gloss meter.

[0215] From the first time point after coating and drying, the coating exhibited stable stain resistance, and the dirt adhering to the coating could be easily removed with a mop in daily care work. . Although the coating was slightly scratched, the number was significantly smaller than that of Comparative Example 5 described below.

After three months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 6 (1) A 14% by mass solid content slurry (pH 8.5, laser diffraction / scattering particle size distribution measurement) treated with a medium stirring bead mill obtained by repeating the method described in Synthesis Example 5 The average particle diameter by the apparatus is 0.54 μm) 1.31 Kg
And a floor polish liquid in the form of an aqueous emulsion containing an acrylic (methacrylate) resin component, a urethane resin component and a styrene resin component (trade name: COMFORT UHS, solid content concentration 17.4% by mass, manufactured by JSP Co.) 20 0.0Kg was placed in a container equipped with a stirrer, and sufficiently stirred and mixed to obtain a floor polish composition. The mass ratio of this composition in terms of solid content is as follows: resin: silica content = 9
5: 5 and the pH was 8.5.

(2) An application test was performed on the floor of the food aisle aisle in the same supermarket store as in Example 1. That is, a polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles, trade name: Benes 50-311)
(White gray pattern) 304.8 mm x 3
On a floor with tiles of 44.8 mm x 3.2 mm,
After peeling, washing and drying the conventional polish, the polish containing the foliar silica secondary particles is manually applied onto the floor tile six times using a mop dedicated to application of the floor tile polish. It was applied separately. With each application, a room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content. Coating ・
After drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation shows high gloss, and the coating is
It was a transparent coating film in which the color and pattern of the tile could be seen well.

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

[0220] Further, the tile having the film formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. The coating consisting of the organic polymer substance and the foliar silica secondary particles did not penetrate into the tile almost in the same manner as in Example 1, and it was found that the unevenness on the tile surface and the good adhesion at the interface between the coating and the base were uniform. Thus, it was confirmed that a remarkable sealing effect was developed.

According to the SEM observation of the fractured surface, similarly to the coating of Example 1, the underlying tile and the coating are completely integrated so that their boundaries can be hardly recognized, and it is difficult to distinguish them from the underlying layer. It was confirmed that a homogeneous coating was formed.

Further, the surface of the coating formed on the tile surface was subjected to low-temperature oxygen plasma incineration at 100 W for 10 minutes to remove organic polymer substances by incineration, and to determine the existence state of the foliar silica secondary particles. Observed by SEM, foliated silica 2
It was clearly observed that the secondary particles were stacked and the secondary particles of the foliated silica covered the tile surface.

(4) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts constantly came and went. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

[0224] From the first time point after application and drying, this film has been stably developed with stain resistance such as heel mark resistance. And was easily removed. No accumulation of dirt with the passage of days was observed at all.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 7 (1) Fine particles of mica (synthetic mica manufactured by Topy Industries, Ltd.)
Trade name: PDM-9WA, average particle diameter by Coulter counter: 6.31 μm, aspect ratio: about 30)
18 Kg of a floor polish in an aqueous emulsion state containing an acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component (manufactured by JSP Co., trade name: COMFORT UHS, solid content concentration 1)
(7.4% by mass) in a vessel equipped with a stirrer, and sufficiently stirred and mixed to obtain a composition for floor polish. The mass ratio of this composition in terms of solid content is resin: mica = 95: 5.

(2) An application test was performed on the floor of a food counter aisle in the same supermarket store as in Example 1. That is, a polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles, trade name: Benes 50-311)
(White gray pattern) 304.8 mm x 3
On a floor with tiles of 44.8 mm x 3.2 mm,
After stripping, washing and drying the conventional polish solution, the above-mentioned mica-containing polish solution was manually applied to the floor tile in six separate steps using a mop dedicated to application of the floor tile polish solution. . With each application, a room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content. After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

(4) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts constantly came and went. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

Example 8 (1) Fine particles of talc (trade name: T-M70Y, manufactured by Fukuoka Talc Kogyo KK, average particle diameter by Coulter counter: 5.60 μm, aspect ratio: about 20) 0.183
Kg and an aqueous emulsion containing a acrylic (methacrylate) resin component, a urethane resin component, and a styrene resin component in a floor polish solution (manufactured by JSP Co., Ltd.
Product name: COMFORT UHS, solid content concentration 17.4
20.0 Kg) in a vessel equipped with a stirrer, and sufficiently stirred and mixed to obtain a floor polish composition. The mass ratio of this composition in terms of solid content is as follows: resin: talc = 9
5: 5.

(2) An application test was performed on the floor of the food section aisle in the same supermarket store as in Example 1. That is, a polyvinyl chloride floor tile (composition vinyl floor tile manufactured by Achilles, trade name: Benes 50-311)
(White gray pattern) 304.8 mm x 3
On a floor with tiles of 44.8 mm x 3.2 mm,
After the conventional polish solution was peeled off, washed and dried, the polish solution containing the above talc was manually applied on the floor tile in six times using a mop dedicated to application of the polish solution of the floor tile. . With each application, a room temperature drying time of about 1 hour was provided. The application amount of each application was ² to 3 g / m ² in terms of solid content. After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(3) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

(4) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts constantly came and went. As maintenance work after closing the store, only care work (cleaning of the coating surface with a dilute aqueous solution of a neutral detergent, drying at room temperature) is carried out every day. It was measured with a gloss meter.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 shows the measured values (measuring angle: 60 degrees).

[Comparative Example 1] (1) Foliate silica 2 was placed on the floor of the same food section passage as in Example 1.
Aqueous emulsion state floor polish liquid containing acrylic (methacrylate) resin component, urethane resin component, and styrene resin component which is a polish liquid containing no secondary particles (manufactured by JSP Co., trade name: COMFORT)
UHS, solid content concentration 17.4% by mass) was applied in four separate applications. A room temperature drying time of about one hour was provided for each application. The amount of application each time was ² to 3 g / m ² in terms of solid content as in Example 1.

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(2) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

[0239] Also, the tile having the coating formed on the surface is
It was cooled with liquid nitrogen and cut, and the cut surface was observed by SEM. Organic polymer substance is tens of μ
m, and no fusion / integration at the interface between the fine irregularities on the tile surface and the coating film was observed, and it was confirmed that the sealing effect was not substantially obtained.

In the case of such a film containing no filler, a different film that can be clearly distinguished from the underlayer is formed on the tile underlayer in SEM observation without adhering to the interface and not being fused and integrated. It is naturally expected that such a coating has low adhesion to the base and low abrasion resistance and scratch resistance. In the case of a film containing colloidal silica as a filler, it was only recognized that a heterogeneous film was formed which could be similarly distinguished from the underlayer.

(3) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor every day for 11 hours, and carts constantly came and went. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

[0242] Immediately after coating and drying, this coating has insufficient stain resistance such as heel mark resistance.
Although it improved with the passage of days, it took about two weeks to be sufficiently stabilized.

In the daily care work, it was clearly observed that the dirt adhering to the film, which cannot be easily removed with a mop, accumulates with the passage of days. In addition, scratches on the surface of the coating were also noticeable.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 also shows the measured values (measuring angle 60 °) according to the mold.

[Comparative Example 2] (1) An aqueous emulsion containing an acrylic (methacrylate) resin component and a styrene resin component, which is a polish liquid containing no secondary particles of leaf-like silica, on the floor of the same toy counter aisle as in Example 2. Floor polish liquid (Jay
SP Corporation, PURIMODUAL, solid content concentration 2
(3.0% by mass) was applied four times. A room temperature drying time of about one hour was provided for each application. The amount of application each time was 2 to 3 g / m ^{2 in} terms of solid content in the same manner as in Example ^2.
Met.

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(2) The hardness of the coating film and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was B. The evaluation score in the eye peel test is
10 points.

(3) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts constantly came and went. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

[0249] This coating film had insufficient stain resistance such as heel mark resistance immediately after application and drying.
Although it improved with the passage of days, it took about two weeks to be sufficiently stabilized.

In the daily care work, it was clearly observed that dirt attached to the film, which could not be easily removed with a mop, accumulated with the passage of days. In addition, scratches on the surface of the coating were also noticeable. .

After three months, the evaluation value of the visual observation of the coating on the floor surface and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.)
Table 1 also shows the measured values (measuring angle 60 °) according to the mold.

[Comparative Example 3] (1) An acrylic (methacrylate) resin component which is a polishing liquid containing no foliated silica secondary particles on the same floor between registers having adjacent register rows as in Example 3, An aqueous emulsion containing a urethane resin component and a styrene resin component in the form of an aqueous emulsion (manufactured by JSP Co., trade name: COMFORTUHS, solid content concentration 17.4% by mass) was applied in six coats. A room temperature drying time of about one hour was provided for each application. The amount of each application was 2 to 3 g in terms of solid content in the same manner as in Example 3.
/ M ² .

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tiles were clearly visible.

(2) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

(3) The floor on which the coating was applied can be used by many supermarket customers every day for 11 hours.
The cart was exposed to constant traffic. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

This coating film had insufficient stain resistance such as heel mark resistance immediately after application and drying.
It took about two weeks to improve and stabilize over time.

Further, in the daily care work, it was clearly observed that the dirt adhering to the film, which cannot be easily removed by the mop, accumulates with the passage of days. Table 1 also shows the visual observation evaluation points of the coating on the floor surface after three months, and the measurement values (measuring angle 60 °) by a portable gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., PG-1M type).

Comparative Example 4 (1) Acrylic (methacrylate) resin component, urethane, which is a polishing liquid containing no foliated silica secondary particles on the same floor between registers having adjacent register rows as in Example 4 An aqueous emulsion containing a resin component and a styrene resin component in the form of an aqueous emulsion (manufactured by JSP Corporation, trade name: COMFORT UHS, solid content concentration 17.4% by mass) was applied in six coats. A room temperature drying time of about one hour was provided for each application. The amount of application each time was 2 to 3 g in terms of solid content as in Example 4.
/ M ² .

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(2) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

(3) The floor on which the coating was applied can be used by many supermarket customers every day for 11 hours,
The cart was exposed to constant traffic. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

The coating film had insufficient stain resistance such as heel mark resistance immediately after application and drying, and improved with the lapse of days, but it took about 2 weeks to stabilize. .

In the daily care work, it was clearly observed that dirt adhering to the film, which cannot be easily removed with a mop, accumulates with the passage of days. 3
Table 1 also shows the visual observation evaluation points of the coating on the floor surface after a lapse of months and the measurement values (measurement angle of 60 degrees) by a portable gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., PG-1M type).

[Comparative Example 5] (1) Foliar silica 2 was placed on the floor of a cart storage similar to that in Example 5.
An aqueous emulsion containing an acrylic (methacrylate) resin component and a styrene resin component, which is a polishing liquid containing no secondary particles (JS.
ACHIEVE, manufactured by P. Co., Ltd., solid content concentration: 17.6% by mass) was applied four times. A room temperature drying time of about one hour was provided for each application. The application amount of each application was ² to 3 g / m ² in terms of solid content as in Example 5.

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(2) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was HB. The evaluation score in the eye peel test was 10.

(2) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket constantly put carts on and off the floor for 11 hours every day. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of a neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after one month was visually observed and the glossiness was checked. It was measured with a gloss meter.

[0268] Immediately after the coating was dried, the coating exhibited insufficient stain resistance such as heel mark resistance, and improved with the lapse of days. However, it took about 2 weeks to be sufficiently stabilized. did.

In the daily care work, it was observed that the dirt adhering to the film, which cannot be easily removed by the mop, remarkably accumulated with the passage of days. In addition, the number of scratches on the film was remarkably increased, and peeling of the film was clearly observed.

After three months, the evaluation of the coating on the floor surface by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.)
Table 1 also shows the measured values (measuring angle 60 °) according to the mold.

[Comparative Example 6] (1) Foliate silica 2 was placed on the floor of the same food section aisle as in Example 6.
Aqueous emulsion state floor polish liquid containing acrylic (methacrylate) resin component, urethane resin component, and styrene resin component which is a polish liquid containing no secondary particles (manufactured by JSP Co., trade name: COMFORT)
UHS, solid content concentration 17.4% by mass) was applied in six coats. A room temperature drying time of about one hour was provided for each application. The amount of application each time was ² to 3 g / m ² in terms of solid content, as in Example 6.

After coating and drying, the film was subjected to a mechanical polishing operation. The initial appearance of the coating after the polishing operation showed high gloss, and the coating was a transparent coating in which the color and pattern of the tile were clearly visible.

(2) The hardness of the coating and the adhesion to the substrate were measured by a pencil hardness test and a cross-cut peeling test in the same manner as in Example 1, and the pencil hardness was 2B. The evaluation score in the eye peel test was 10.

(3) The floor on which the coating was applied was exposed to an environment in which a large number of customers in a supermarket passed on the floor for 11 hours every day, and carts were constantly coming and going. As maintenance work after closing the store, only daily care work (cleaning of the coating surface with a dilute aqueous solution of neutral detergent, drying at room temperature) was carried out, and the condition of the floor surface after three months was visually observed and the gloss was checked. It was measured with a gloss meter.

[0275] This coating film exhibited insufficient stain resistance such as heel mark resistance immediately after application and drying, and improved with the passage of days. However, it took about 2 weeks to be sufficiently stabilized. Cost.

[0276] In the daily care work, it was clearly observed that dirt adhering to the film, which cannot be easily removed with a mop, accumulates with the passage of days. In addition, scratches on the surface of the coating were also noticeable.

After 3 months, the floor coating was evaluated by visual observation and a portable gloss meter (PG-1M, manufactured by Nippon Denshoku Industries Co., Ltd.).
Table 1 also shows the measured values (measuring angle 60 °) according to the mold.

[0278]

[Table 1]

(Note :) The evaluation of the coating on the floor surface by visual observation after the lapse of three months in the table was evaluated according to the following criteria in four grades. 1: The glossiness of the coating film was very high, and scars on the coating film were hardly observed. Also, no darkening due to stains on the coating film is observed at all. 2: Although the glossiness of the coating film is high, scratches on the coating film are slightly observed. Further, darkening due to stains on the coating film is slightly recognized. 3: The glossiness of the coating film is low, and scratches on the coating film are observed. Further, blackening due to stains on the coating film is observed. 4: The coating film is not glossy, and the coating film is markedly scratched.
Also, darkening due to stains on the coating film is remarkably observed.

Based on the results of the above three months, based on the numerous field data and technical knowledge accumulated over many years from daily maintenance to full repair of the applicants who have long experience in the field of floor polish, Analyzes and investigations have shown that the use of the floor polish composition of the present invention is expected to significantly extend the period up to full repair.

[0281]

When the surface of a base material such as a floor surface is treated with the floor polish composition of the present invention, the floor polish coating has significantly improved hardness, abrasion resistance, abrasion resistance, stain resistance and the like. However, as a result of the improvement of the characteristics of the coating film itself, maintenance work of the coating film is greatly reduced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 201/00 C09D 201/00 C09G 1/04 C09G 1/04 1/16 1/16 1/72 (72) Inventor Kunihiko Terase 13-1, Kitaminato-machi, Wakamatsu-ku, Kitakyushu-city, Fukuoka Prefecture Inside the Dokai Chemical Industry Co., Ltd. (72) Inventor Maki Inoue 13-1, Kitaminato-machi, Wakamatsu-ku, Wakamatsu-ku, Fukuoka Prefecture (72) Inventor Atsushi Fujii 13-1 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-city, Fukuoka Prefecture (72) Inventor Eiichi Ono 131-1 Kitaminato-cho, Wakamatsu-ku, Fukuoka Prefecture Dokai Chemical Industry Co., Ltd. (72) Inventor Takayoshi Sasaki 13-1 Kitaminato-cho, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Dokai Chemical Co., Ltd.F-term (reference) 4D075 AE03 CA02 CA34 CB04 CB06 DA06 DB01 DB12 DB13 DB14 DB16 D B21 DB38 DC02 EA06 EA13 EB14 EB15 EB16 EB22 EB33 EB35 EB38 EB42 EC03 EC23 4J038 CC021 CD021 CD091 CG141 DB001 DD001 DG001 DL031 HA156 HA446 KA08 KA20 MA08 MA10 NA01 NA05 NA11 PB05

Claims (10)

[Claims] 1. A floor polish composition comprising a film-forming organic polymer substance as a main component, wherein the composition contains at least flaky particles. 2. The floor polish composition according to claim 1, wherein the flaky particles are silica corresponding to layered polysilicic acid. 3. The lamellar polysilicic acid is substantially composed of flaky silica secondary particles formed by laminating flaky silica primary particles in parallel with each other and forming a plurality of flake primary silica particles.
The floor polish composition according to claim 2, wherein the composition is a flaky silica particle having a particle form of a layered structure that exists independently of each other. 4. The foliar silica secondary particles constituting the flaky silica have a main peak in a X-ray diffraction analysis of silica-X.
And / or silica corresponding to silica-Y.
Or the floor polish composition according to 3. 5. The floor polish composition according to claim 1, wherein the organic polymer substance in the floor polish composition is an organic polymer substance in an aqueous emulsion state. 6. A floor polish coating provided on a surface of a base material and comprising a film-forming organic polymer substance, wherein the coating contains scale-like particles. . 7. The floor polish coating according to claim 6, wherein the flaky particles are silica corresponding to layered polysilicic acid. 8. The layered polysilicic acid is substantially composed of flaky silica secondary particles formed by stacking a plurality of flake primary particles of flaky silica with their planes oriented parallel to each other,
The floor polish coating according to claim 7, which is a flaky silica particle having a layered particle form that exists independently of each other. 9. The foliar silica secondary particles constituting the flaky silica in the coating are silica whose main peak in X-ray diffraction analysis corresponds to silica-X and / or silica-Y. Or a floor polish coating according to 8. 10. An overcoat layer substantially composed of an organic polymer substance is provided on a floor polished film containing flaky silica according to any one of claims 6 to 9, and the floor polished film is transparent. Floor polished film with enhanced properties.