JP2000239614A - Floor glazing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor grazing agent which is excellent in handleability and coating properties due to low viscosity and also in such properties as leveling properties, gloss, adhesion to flooring material, resistance to water, resistance to detergent, removability from floor surface, resistance to black heel mark and resistance to scuffing. SOLUTION: This agent has a structural unit (a) derived from a silicone macromonomer, a structural unit (b) derived from a styrene monomer and a structural unit (c) derived from other radical-polymerizable monomers, and is composed of an aqueous emulsion dispersion of a copolymer having 0.1-10 wt.% of the structural unit (a), 10-80 wt.% of the structural unit (b) and 10-89.9 wt.% of the structural unit (c) based on the total weight of all the structural units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a floor polish. More specifically, the present invention is a leveling property, gloss, adhesion to flooring, water resistance, detergent resistance, removability from the floor,
The present invention relates to a high-quality floor polish having excellent properties such as black heel mark resistance and scuff resistance, low viscosity, and excellent handleability and applicability.

[0002]

BACKGROUND OF THE INVENTION Floor polishes include oily floor polishes,
There are three types of polishes for emulsifying floors and polishes for aqueous floors, each of which is further roughly classified into polymer type or wax type. Among them, polymer type aqueous floor polishes have recently been used as floor polishes because they can be used commonly for various flooring materials and are excellent in durability and stain resistance. It has become mainstream.

[0003] Gloss is an important and basic performance in floor polishes, and higher gloss is desired for floors such as office buildings that require a high-grade appearance. Another important factor is that polishes for floors, which are used in office buildings that require regular maintenance, are durable and can maintain a long-lasting aesthetic appearance. I have. Various studies have hitherto been made to improve the gloss and durability of floor glazing agents. Polyurethane emulsions have been actively studied in recent years as techniques for improving durability and have been put to practical use. Is known as a floor polish. However, floor polishes containing a polyurethane emulsion are inferior in the removability when removing the floor polishes from the floor surface using an alkali release agent, etc.
There is a problem that it cannot be removed cleanly from the floor.

To improve the gloss and durability, floor polishes using polymers modified with silicone resins or silane compounds have been proposed. Specifically, (1) silane-containing monomers Polishing agent using acrylic polymer emulsion copolymerized with
No. 5-110170), and (2) a water-dispersible copolymer obtained by polymerizing an organosilicon unsaturated monomer having a Si-bond hydrolyzable group, a polymerizable unsaturated carboxylic acid, and another unsaturated monomer. Floor polishes containing a water-dispersible silicon-modified vinyl polymer which is a reaction product of a polymer and an organopolysiloxane having silicon-bonded hydrogen atoms (JP-A-62-161876), (3) radical polymerizable For floor polishes obtained by emulsion polymerization of a monomer mixture of an unsaturated monomer and (meth) acrylic acid or an ester thereof in an oil-in-water emulsion of an organopolysiloxane having a hydroxyl group or an SH group ( JP-A-3-86775 and JP-A-4-8675
No. 261454) and (4) Floor polishes containing an aminosilane-modified acetoacetate-functionalized polymer (JP-A-7-188617) are known.

However, the glossing agent for floors of the above (1) has insufficient gloss. In addition, the floor polisher of the above (2) is troublesome because the water-dispersible silicone-modified vinyl polymer is produced by two-stage polymerization, and the production rate of the polymer is low, and the productivity is low. Low. Further, in the above-mentioned floor polisher (3), the particle size of the polymer particles in the emulsion is large, and the gloss and the film-forming property are not sufficient. Further, the floor polish of the above (4) is insufficient in water resistance and detergent resistance. In addition, in any of the floor polishes (1) to (4), the black heel mark resistance (resistance to black rubber stains on the shoe sole adhered by walking) and the scuff resistance (produced by the shoe sole). Resistance to scratches) is not sufficient, and contamination and damage due to shoe soles are likely to occur.

[0006]

The object of the present invention is to provide gloss, leveling, adhesion to flooring, water resistance, detergent resistance, removability from floor, black heel mark resistance, scuff resistance. To provide floor polishes that have excellent properties such as excellent properties over a long period of time, low viscosity, excellent handleability and applicability, and that can be manufactured with low labor and high productivity. It is.

[0007]

Means for Solving the Problems As a result of repeated studies by the present inventor to achieve the above object, the structural units derived from the silicone-based macromonomer and the structural units derived from the styrene-based monomer have a specific ratio. Aqueous emulsified dispersion of the copolymer having a long-term gloss, leveling, adhesion to flooring, water resistance, detergent resistance, removal from floor, black heel mark resistance, scuff resistance, etc. It has been found that it is excellent in durability (hereinafter sometimes referred to as "durability"), has low viscosity, is excellent in handleability and applicability, and is suitable as a floor polish. Furthermore, the present inventor, among the aqueous emulsion dispersion of the copolymer described above,
A solution obtained by dissolving a silicone-based macromonomer and an oil-soluble radical polymerization initiator in a styrene-based monomer and other radically polymerizable monomers, and emulsifying and dispersing the solution in an aqueous medium to obtain a polymer. The aqueous emulsified dispersion of the copolymer is extremely small in particle size of the copolymer contained therein, so that when the aqueous emulsified dispersion is used as a polishing agent for floors, the gloss, durability, and properties of the emulsion are reduced. It was found that the film surname was extremely excellent. Further, the present inventors have found that when the acid value of the copolymer in the aqueous emulsified dispersion is 100 mgKOH / g or more, the black heel mark resistance and the scuff resistance are further improved when used as a floor polish. The inventors have found that the present invention is excellent, and completed the present invention based on those findings.

That is, the present invention relates to a structural unit (a) derived from a silicone-based macromonomer, a structural unit (b) derived from a styrene-based monomer, and a structural unit derived from another radical polymerizable monomer ( c), and based on the total weight of all the structural units, 0.1 to 10% by weight of the structural unit (a), 10 to 80% by weight of the structural unit (b) and 10 to 80% by weight of the structural unit (c). A floor polishing agent comprising an aqueous emulsified dispersion of a copolymer [hereinafter referred to as “copolymer (A)”] having a ratio of 10 to 89.9% by weight.

According to the present invention, the copolymer (A) in the aqueous emulsified dispersion is a structural unit derived from a radically polymerizable monomer having a carboxyl group as a part of the structural unit (c) [hereinafter referred to as “structure” Unit (d) "] and an acid value of 1
The above-mentioned floor polish which is a copolymer of 00 mgKOH / g or more is included as a preferred embodiment. The acid value in the present specification is obtained by calculation based on the content of the carboxyl group-containing monomer unit in the copolymer.

Further, the present invention provides a method of dissolving a silicone-based macromonomer and an oil-soluble radical polymerization initiator in a styrene-based monomer and other radically polymerizable monomers,
As a preferred embodiment, a floor polish comprising an aqueous emulsified dispersion of the copolymer (A) formed by emulsifying and dispersing the solution in an aqueous medium is included. Further, the present invention includes, as a preferred embodiment, any one of the above-mentioned floor polishes in which the average particle size of the copolymer (A) is 1 μm or less.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, in the present invention, “a floor glazing agent comprising an aqueous emulsified dispersion of a copolymer having a structural unit (a), a structural unit (b) and a structural unit (c)” refers to the floor polisher of the present invention. The polishes mean floor polishes based on the above-mentioned aqueous emulsified dispersion, and optionally blended with various components for floor polishes.

In the copolymer (A) in the aqueous emulsified dispersion used for the floor polish of the present invention, the structural unit (a)
Is a high-molecular-weight monomer having a silicone skeleton and having a radical polymerizable group at one end thereof. The number average molecular weight of the silicone-based macromonomer is preferably from 1,000 to 100,000, and more preferably from 2,000 to 50,000. If the number average molecular weight of the silicone-based macromonomer is less than 1,000, the length of the branch portion (silicone polymer portion) in the copolymer becomes short, and if the amount is not increased, the gloss and the durability of various physical properties are reduced. It becomes difficult to obtain an excellent floor polish. On the other hand, when the number average molecular weight of the silicone-based macromonomer exceeds 100,000, the copolymerizability with the styrene-based monomer and other radically polymerizable monomers decreases, and the silicone-based macromonomer in the copolymer decreases. The proportion of the structural unit (a) derived from the monomer is reduced, and gloss and durability are likely to be insufficient. Here, the “number average molecular weight” in the present specification refers to a number average molecular weight in terms of polystyrene measured by gel permeation chromatography.

The method for producing the silicone macromonomer used for producing the copolymer (A) is not particularly limited, and it can be produced by a conventionally known method. For example, (1) lithium trialkylsilanolate is used as a polymerization initiator A method for producing a living polymer by anionic polymerization of a cyclic siloxane such as a cyclic trisiloxane or a cyclic tetrasiloxane, and reacting the living polymer with γ-methacryloxypropyldimethylmonochlorosilane (JP-A-59-78236) ), (2) a method of subjecting a silicone having a terminal silanol group to a condensation reaction with an organosilicon compound (JP-A-58-167606, JP-A-60-1)
No. 23518). Further, a commercially available silicone-based macromonomer may be used as it is in the production of the copolymer (A).

The styrene monomer constituting the structural unit (b) in the copolymer (A) includes styrene, α-methylstyrene, p-methylstyrene and the like. ) May be formed from one of the above-mentioned styrene-based monomers, or may be formed from two or more thereof, and is preferably formed from styrene.

The other radically polymerizable monomer constituting the structural unit (c) in the copolymer (A) includes a radically polymerizable monomer copolymerizable with a silicone-based macromonomer and a styrene-based monomer. Any of the monomers can be used. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and (meth)
Isobutyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate Mono (meth) of hydroxybutyl (meth) acrylate and polyethylene glycol
Acrylic acid ester, mono (meth) acrylic acid ester of polypropylene glycol, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate,
(Meth) acrylic esters such as perfluoroalkyl (meth) acrylate; fluorine-containing (meth) acrylates such as polyfluoroalkyl (meth) acrylate and perfluoroalkyl (meth) acrylate; acrylic Acid, methacrylic acid, crotonic acid,
Radical polymerizable monomers having a carboxyl group such as maleic acid, fumaric acid, itaconic acid, citraconic acid, maleic anhydride; (meth) acrylonitrile, vinyl acetate, vinyl propionate, N-methylol (meth) acrylamide, vinyl chloride , Vinyl fluoride, vinylidene chloride, vinylidene fluoride, trichloroethylene, vinylpyridine, N-vinylpyrrolidone, and the like.
The structural unit (c) may be composed of only one type of these monomers, or may be composed of two or more types. Among them, the majority of the structural unit (c) is composed of one or more (meth) acrylic acid esters, and as a part of the structural unit (c), a carboxyl group such as methacrylic acid or acrylic acid is used. It is preferable to have a structural unit derived from one or two or more radical polymerizable monomers having a group, in which case the removal of the polishing agent from the floor surface is performed smoothly, In addition, black heel mark resistance and scuff resistance are improved.

In the copolymer (A), 0.1 to 10% by weight of the structural unit (a) derived from the silicone-based macromonomer is derived from the styrene-based monomer based on the total weight of all the structural units. 10 to 80% by weight of the structural unit (b) and a structural unit (c) derived from another radical polymerizable monomer
At a rate of 10 to 89.9% by weight, the structural unit (a) is 1 to 10% by weight, the structural unit (b) is 30 to 75% by weight, and the structural unit (c). 15
Preferably, it has a proportion of about 69% by weight.

In the copolymer (A), the ratio of the structural unit (a) derived from the silicone-based macromonomer is 0.1%.
If the amount is less than 10% by weight, the gloss and durability of the floor glazing agent decrease, while if the amount exceeds 10% by weight, a stable aqueous emulsified dispersion cannot be obtained. This leads to an increase in the cost of the polishing agent.

In the copolymer (A), when the proportion of the structural unit (b) derived from the styrene monomer is less than 10% by weight, the gloss of the floor glazing agent becomes insufficient, and the aqueous emulsion dispersion When various additives for floor polishes are incorporated into the body, the viscosity is remarkably increased, and the handleability, applicability, leveling property and the like are deteriorated. On the other hand, when the ratio of the structural unit (b) exceeds 80% by weight, the glass transition temperature of the copolymer is too high, and the film-forming property is poor.

The proportion of the structural unit (c) derived from the other radical polymerizable monomer in the copolymer (A) is calculated based on the total weight (100% by weight) of all the structural units, ) And the total weight of the structural units (b) are subtracted. If the proportion of the structural unit (c) is less than 10% by weight, the proportion of the structural unit (a) and / or the structural unit (b) becomes too large, so that the dispersion stability of the aqueous emulsified dispersion described above decreases. On the other hand, when the proportion of the structural unit (c) exceeds 89.9% by weight, the gloss and durability of the floor glazing agent are reduced, the viscosity is increased, the coating property and the leveling property are reduced.

In the polishing agent for floors of the present invention, when the acid value of the copolymer (A) in the aqueous emulsion dispersion is 100 mgKOH / g or more, the black heel mark resistance and the scuff resistance are further improved. From 100 to 1
More preferably, it is 50 mgKOH / g. Therefore, the copolymer (A) has a structural unit (d) derived from a radically polymerizable monomer having a carboxyl group (for example, methacrylic acid, acrylic acid, etc.) as a part of the structural unit (c). Is preferred. Copolymer (A)
Has an acid value of 100 mgKOH / g or more, especially 100 to 15
The ratio of the structural unit (d) necessary to make 0 mgKOH / g depends on the acidity of the carboxyl group-containing radical polymerizable monomer constituting the structural unit (d) and the carboxyl group-containing radical polymerizable monomer. When methacrylic acid is used as the radically polymerizable monomer having a carboxyl group, for example, methacrylic acid is usually contained in the copolymer (A). Is preferably 15% by weight or more, particularly 15 to 23% by weight, based on the weight of all the structural units.

The copolymer (A) in the aqueous emulsified dispersion preferably has a glass transition temperature of 5 to 80 ° C.,
More preferably, it is 10 to 70 ° C. When the glass transition temperature of the copolymer (A) is less than 5 ° C., sticking is likely to occur when a polishing agent is applied to the floor, while
If the temperature is higher than ℃, film formation on the floor at room temperature tends to be difficult. In addition, the glass transition temperature of the copolymer in the present specification refers to a glass transition temperature calculated by using a glass transition temperature of a homopolymer of each monomer constituting the copolymer.

The average particle size of the copolymer (A) is preferably 1 μm or less from the viewpoint of improving the leveling property, film formability and durability, and more preferably 0.5 μm or less. .

[0023] Polishing agent for floor of the present invention (aqueous emulsified dispersion)
Is the copolymer (A) based on the total weight of the floor polish
15 to 60% by weight, more preferably 25 to 50% by weight
It is good to contain in the ratio of, if the above content,
The viscosity of the floor polisher is appropriate, improving the handling properties, the applicability to the floor surface, and the leveling property, as well as the gloss, the adhesion to the floor material, the water resistance, the detergent resistance, and the floor surface. , Good black heel mark resistance, good scuff resistance, etc. The preferred viscosity of the floor polish of the present invention,
The dispersion after adding various additives such as a crosslinking agent, a plasticizer, and a film-forming auxiliary described below has a density of 10 centipoise or less.

The aqueous medium in the aqueous emulsified dispersion constituting the floor polish of the present invention may be water alone or water and a water-soluble organic solvent (alcohol, ether, ketone, DMS).
O, DMF, etc.). Among them, water alone is preferred from the viewpoints of safety, harmlessness to human bodies, and the like.

The type of the emulsifier used in the aqueous emulsified dispersion constituting the glazing agent for floors of the present invention is not particularly limited, and the emulsifier used in the production of the aqueous emulsified dispersion [at the time of polymerization of the copolymer (A)]. Can be contained as it is. In some cases, an emulsifier different from the emulsifier used for the polymerization may be further added. Examples of the emulsifier that can be preferably used in the present invention include, for example, an alkali metal salt-based anionic surfactant of sulfosuccinic acid, a sulfonated alkali metal salt-based anionic surfactant, a sulfate ester alkali metal salt-based anionic surfactant, and a nonionic surfactant. Surfactants and the like. The less the content of the emulsifier in the floor polisher, the lower the water resistance of the floor polisher is improved, but if the amount is too small, the emulsion stability is impaired. Therefore, it is preferably about 0.3 to 3% by weight.

In the polishing agent for floors of the present invention, when the copolymer (A) in the aqueous emulsified dispersion has a carboxyl group in the molecule, it is desirable to add a crosslinking agent reactive with the carboxyl group. By the reaction of the carboxyl group in the copolymer (A) with the crosslinking agent, a glossing agent film having excellent gloss, adhesion, durability, water resistance, detergent resistance, black heel mark resistance and scuff resistance is obtained. It can be formed on the floor. As the crosslinking agent in this case, a material obtained by solubilizing an oxide of a polyvalent metal such as zinc or calcium with an alkali (for example, aqueous ammonia, ammonium bicarbonate, or ammonium carbonate) is preferably used. The amount of the crosslinking agent is preferably set so that the ion equivalent of the polyvalent metal is 10 to 90% based on the carboxyl group in the copolymer (A). When the ion equivalent of the polyvalent metal is less than 10%, it becomes difficult to obtain a balance between the removability and durability of the polishing agent film applied to the floor surface, while when it exceeds 90%, the polishing agent for flooring is used. Tends to have low storage stability.

The floor glazing agent of the present invention may optionally contain
Waxes such as paraffin and montan; alkali-soluble resins such as rosin-modified maleic acid resin and styrene-maleic acid resin; plasticizers such as dibutyl phthalate and triethyl phosphate; and components such as diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether. It may contain one or more of auxiliary components such as a film assistant; a leveling agent for tributoxyethyl phosphate nad; a fluorosurfactant; a pigment; The content of these subcomponents may be the same as that of a generally known aqueous floor polish. When these subcomponents do not cause a gelling reaction with the copolymer in the aqueous emulsified dispersion, they can be added to the aqueous emulsified dispersion in advance, and also cause a gelling reaction. If it is easy, it is desirable to add it when applying it to the floor.

The method for producing the aqueous emulsion dispersion used for the floor polish of the present invention is not particularly limited, and any method can be employed as long as it can produce a stable aqueous emulsion dispersion of the copolymer (A). . Among them, in producing the aqueous emulsified dispersion used for the floor glazing agent of the present invention, an oil-soluble radical polymerization initiator is used as a polymerization initiator, and this radical polymerization initiator and a silicone-based macromonomer are used as a silicone-based macromonomer. A monomer to be copolymerized with a monomer, that is, a monomer solution is prepared by dissolving in a mixture of a styrene monomer and another radical polymerizable monomer, and the monomer solution is placed in an aqueous medium. A method in which emulsion polymerization is carried out by emulsification and dispersion (hereinafter, this method is sometimes referred to as “microsuspension polymerization method”) is preferably employed. In the case of this microsuspension polymerization method, the particle size of the copolymer (A) contained in the aqueous emulsion dispersion is very small, 1 μm or less, and often 0.5 μm or less. When used as a dispensing agent, it is extremely excellent in gloss, durability, film forming property and the like.

In producing the aqueous emulsified dispersion used for the floor polish of the present invention by microsuspension polymerization, any of oil-soluble radical polymerization initiators can be used, and specific examples thereof include 2,2 ′ -Azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4, 4 ' Azo polymerization initiators such as azobis-4-cyanovaleric acid; lauryl peroxide, benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, di-n-propylperoxydicarbonate, t-butylperoxypivalate And the like. These oil-soluble radical polymerization initiators may be used alone or in combination of two or more.
The amount of the oil-soluble radical polymerization initiator to be used is 0.1 to the total weight of the silicone macromonomer and the comonomer.
It is preferably from 1 to 10% by weight, more preferably from 0.5 to 5% by weight.

As an emulsifier used in microsuspension polymerization, a solution in which a silicone-based macromonomer and an oil-soluble radical polymerization initiator are dissolved in a mixture of a styrene-based monomer and another radical-polymerizable monomer is used in an aqueous medium. Any emulsifier that can be stably emulsified and dispersed can be used, and among them, the above-described alkali metal salt-based anionic surfactants of sulfosuccinic acid, alkali metal sulfonic acid-based anionic surfactants, and alkali metal sulfates Anionic surfactants, nonionic surfactants and the like are preferably used. Specific examples of the alkali metal salt-based anionic surfactant of sulfosuccinic acid include di-2
-Ethylhexyl sodium sulfosuccinate, sodium polycyclic phenylpolyethoxysulfosuccinate, sodium monoester of polyoxyethylene alkyl allyl ether sulfosuccinate, sodium polyoxyethylene lauryl ether sulfosuccinate and the like. Specific examples of the alkali metal sulfonic acid salt-based anionic surfactant include alkali metal salts of alkyl benzene sulfonic acid such as sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, and formalin naphthalene sulfonate. Alkali metal salts of the product. Specific examples of the sulfated alkali metal salt-based anionic surfactant include alkali metal salts of alkyl sulfates such as sodium lauryl sulfate and sodium stearyl sulfate, sodium polyoxyethylene lauryl ether sulfate, and sodium polyoxyethylene octyl phenyl ether sulfate. And sodium polyoxyethylene alkylene ether sulfate. Specific examples of the nonionic surfactant include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene sorbitan monoalkylate, polyethylene glycol distearate, and polyoxyethylene cetyl ether. it can. In the microsuspension polymerization, one or more of the above-mentioned surfactants can be used.

A monomer solution obtained by dissolving a silicone-based macromonomer and an oil-soluble radical polymerization initiator in a styrene-based monomer and another radical-polymerizable monomer is mixed with 100 parts by weight of the monomer solution. On the other hand, the above-mentioned emulsifier (surfactant) is used in an amount of 3 to 5 parts by weight, and
In 100 parts by weight, a homomixer, a homogenizer, an ultrasonic stirrer or the like is used to emulsify and disperse in a micelle form of preferably 1 μm or less, more preferably 0.5 μm or less, and generally polymerize at a temperature of 50 to 90 ° C. As a result, an aqueous emulsified dispersion of the copolymer (A) which is preferably used as a floor polish of the present invention is obtained. The copolymer (A) contained in the aqueous emulsified dispersion has an extremely fine average particle size of 1 μm or less, and often 0.5 μm or less.

The floor polishes of the present invention include vinyl tiles such as homogeneous vinyl floor tiles and composition vinyl floor tiles, rubber tiles such as single-layer rubber tiles, rubber or plastic flooring materials such as asphalt, flooring and cork tiles. For various flooring materials such as wood flooring materials, stone materials, terrazzo, porcelain flooring, etc.
It can be effectively used for the purpose of cosmeticization and protection. The application of the floor polish of the present invention to a floor can be performed in the same manner as in the case of the conventional floor polish.

[0033]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited thereto. In the following examples, preparation of test pieces, leveling properties of floor polishes, gloss, adhesion, water resistance, detergent resistance, removability, black heel mark resistance and evaluation or measurement of water resistance are described below. Was done in the manner described.

(1) Specimen: A black standard tile (vinyl asbestos tile) for JFPA standard test was used in Minnesota
Using a “51 line red buffer pad” manufactured by Mining Co., Ltd., washing was performed according to the method described in JIS K3920 to prepare a test piece. This cleaning is a very mild cleaning condition compared to the cleaning process actually used when applying a polishing agent to a building floor or the like.

(2) Leveling property: The test piece prepared in the above (1) was prepared by adding each floor polishing agent of the following Examples or Comparative Examples to a level of about 10 g per 1 m ^2.
Immediately after application (in an undried state), the surface was marked with an X mark using gauze and dried. The surface condition after drying was visually observed, and evaluated on a 5-point scale according to the following criteria.

[Evaluation Criteria of Leveling Property] 5: No X mark is observed. 4: The outline of the X mark is slightly seen as a difference in gloss. 3: The outline of the X mark is clearly seen as a gloss difference. 2: X mark is partially ridge-shaped. 1: The X mark has a ridge shape as a whole and is uneven.

(3) Gloss: The test piece prepared in the above (1) was coated with the respective floor polishes of the following Examples or Comparative Examples in an amount of about 10 g per 1 m ² and then at room temperature. For 1 hour, and this operation was repeated four times (four coatings). For the surface of each test piece obtained thereby,
Gloss was measured at 60 degrees according to JIS Z8741 and measured three times to obtain an average value.

(4) Adhesion: After applying the glazing agent for each floor of the following Examples or Comparative Examples to the test specimen prepared in the above (1) in an amount of about 10 g per 1 m ^2, After drying at room temperature for 1 hour, this operation was repeated 4 times (4
Times). The surface of each test piece obtained thereby was subjected to a tape peeling test in accordance with JIS K5400 to measure the residual film area ratio (%), and measured five times to obtain an average value.

(5) Water resistance: The test piece prepared in the above (1) was coated once with the glazing agent for each floor of the following Examples or Comparative Examples in an amount of about 10 g per 1 m ^2. After drying at room temperature for 1 hour, each test piece was allowed to stand at room temperature at a relative humidity of 80% or less for 24 hours, and then 0.2 ml of distilled water was dropped on the coated surface. After standing for 1 hour in that state, the water droplets were wiped off. After 30 minutes, the degree of whitening of the coating film surface was visually observed, and evaluated according to the following criteria on a 5-point scale.

[Evaluation Criteria for Water Resistance] 5: No whitening / damage. 4: The outline of whitening is slightly seen. 3: Although whitening is partially observed. No blistering. 2: Whitening was observed on the entire surface, and no blister was generated. 1: Full whitening accompanied by blisters was observed.

(6) Detergent resistance: After applying each of the test pieces prepared in the above (1) with the glazing agent for floors of the following Examples or Comparative Examples in an amount of about 10 g per 1 m ^2, The operation of drying at room temperature for one hour was repeated four times (four coatings). Next, each test piece was allowed to stand at room temperature at a relative humidity of 80% or less for 24 hours, and then the coated surface was subjected to JIS K392.
The tip of the gauze moistened with the standard washing solution described in
A rubbing test of 300 reciprocations was performed with a load of g.
The surface condition of the coating film after rubbing was visually observed, and evaluated on a 5-point scale according to the following criteria.

[Evaluation Criteria for Detergent Resistance] 5: No peeling or damage. 4: A change in gloss is partially observed. No damage. 3: Fine streak-like damage is observed. 2: Peeling is partially observed. 1: The entire surface is peeled.

(7) Removability: The test piece prepared in the above (1) was coated with the floor polish of each of the following Examples or Comparative Examples in an amount of about 10 g per 1 m ² , and then cooled to room temperature. The operation of drying for 1 hour was repeated twice (coating twice). Next, each test piece was allowed to stand at room temperature at a relative humidity of 80% or less for 24 hours, and then the coated surface was subjected to JIS K392.
The tip of the gauze moistened with the standard washing solution described in
A rubbing test of 75 reciprocations was performed with a load of g. The surface condition of the coating film after rubbing was visually observed, and evaluated on a 5-point scale according to the following criteria.

[Evaluation Criteria of Removability] 5: The entire surface is peeled off cleanly, and the tile surface is completely exposed. 4: The tile surface is exposed, but the undercoat layer partially remains. 3: The undercoat layer remains on the entire surface. 2: The overcoat layer partially remains. 1: Only abrasion scratches or no damage (polishing agent remains as it is).

(8) Black heel mark resistance: Each of the test pieces prepared in the above (1) was coated with the floor polish of each of the following Examples or Comparative Examples in an amount of about 10 g per 1 m ^2. After that, the operation of drying at room temperature for 1 hour was repeated three times (three coatings). Then each test piece was subjected to a relative humidity of 8
After standing overnight at room temperature of 0% or less, JIS K39
The test was performed according to No. 20. That is, a test piece was set on a heel mark tester described in the standard, and 50
Six standard square rubber blocks of mm square are put in, and both sides are rotated at a rotation speed of 50 rpm for two and a half minutes, respectively, and a black heel mark (black scumming stain) on the coating film surface is obtained.
Was visually observed, and a relative five-point evaluation was performed in comparison with a five-point control sample relating to black heel mark resistance described in JIS K3920.

(9) Scuff resistance: After the black heel mark resistance test of (8) above was performed, the amount of scuff marks (scratching scratches) on the surface of the test piece was visually observed. , Relative to a 5-point control sample relating to scuff resistance described in JIS K3920.

Example 1 (1) Silicone-based macromonomer (“X-22-174DX” manufactured by Shin-Etsu Chemical Co., Ltd. (glass transition temperature−
130 ° C.) 1 part by weight and 4,2 parts by weight of 2,2′-azobis (2-methylpropionate) were added to 54 parts by weight of styrene, 25 parts by weight of butyl acrylate and 2 parts by weight of methacrylic acid.
Dissolved in a monomer mixture consisting of 0 parts by weight at 25 ° C.
A monomer solution was prepared. (2) An aqueous emulsion was prepared by emulsifying the monomer solution obtained in the above (1) in 43 parts by weight of ion-exchanged water using 1 part by weight of sodium lauryl sulfate as an emulsifier using a Moho mixer. . (3) 80 parts by weight of ion-exchanged water and 0.5 parts by weight of the aqueous emulsion obtained in the above (2) are placed in a polymerization vessel, and the internal temperature is kept at 80 ° C. while bubbling nitrogen, followed by stirring. While the rest of the aqueous emulsion obtained in (2) above was added to 4
After gradually dropping over time, the polymerization reaction is further continued at the same temperature for 2 hours to obtain a silicone-based macromonomer unit,
An aqueous emulsified dispersion of a copolymer having styrene units, butyl acrylate units and methacrylic acid units (copolymer content 38% by weight) was produced. (4) The acid value of the copolymer in the aqueous emulsified dispersion obtained in (3) was 130 mgKOH / g. In addition, the glass transition temperature of the copolymer is defined as the glass transition temperature of a homopolymer of styrene (100 ° C.), the glass transition temperature of a homopolymer of butyl acrylate (−54 ° C.), and the glass transition temperature of a homopolymer of methacrylic acid. (185 ° C.) and the glass transition point (−130) of the silicone macromonomer.
° C) was 48 ° C.

(5) Zinc oxide solubilized with ammonium bicarbonate and aqueous ammonia is added to the aqueous emulsion dispersion of the copolymer obtained in the above (3) with respect to the carboxyl group in the copolymer. It was added in such an amount that the molar ion equivalent of zinc became 20%. The wetting agent, the defoaming agent, the film-forming auxiliary, and the leveling were adjusted so that the content of each component in the finally obtained floor glazing agent became the amount (% by weight) shown in Table 1 below. Additives, plasticizers, alkali-soluble resins and waxes were added to produce floor polishes with a copolymer content of 37.5% by weight. The viscosity of this floor polish was 6 centipoise (25 ° C.). (6) Using the floor polish obtained in (5) above,
Leveling, gloss, adhesion, water resistance,
Tests for detergent resistance, removal properties, black heel mark resistance, and water resistance were performed, and the results were as shown in Table 2 below.

<< Examples 2 to 4 >> (1) In the same manner as in (1) to (3) of Example 1, except that monomers of the type shown in Table 2 below were used in the proportions shown in Table 2. In this way, an aqueous emulsion dispersion of the copolymer was produced. The acid value and glass transition temperature of the copolymer in this aqueous emulsified dispersion were as shown in Table 2. (2) To the aqueous emulsion dispersion of the copolymer obtained in (1) above, solubilized zinc oxide was added in the same manner as in (5) of Example 1, and various components are shown in Table 1. The copolymer content was 37.5% by weight.
Was produced. The viscosities of the resulting floor polish at 25 ° C. were 6 centipoise (Example 2), 8 centipoise (Example 3), and 6 centipoise (Example 4), respectively. (3) Using the floor polish obtained in the above (2),
Leveling, gloss, adhesion, water resistance,
Tests for detergent resistance, removal properties, black heel mark resistance, and water resistance were performed, and the results were as shown in Table 2 below.

<< Comparative Examples 1 and 2 >> (1) In the same manner as in (1) to (3) of Example 1, except that monomers of the type shown in Table 2 below were used in the proportions shown in Table 2. In this way, an aqueous emulsion dispersion of the copolymer was produced. The acid value and glass transition temperature of the copolymer in this aqueous emulsified dispersion were as shown in Table 2. (2) To the aqueous emulsion dispersion of the copolymer obtained in (1) above, solubilized zinc oxide was added in the same manner as in (5) of Example 1, and various components are shown in Table 1. The copolymer content was 37.5% by weight.
Was produced. The viscosity of the resulting floor polish was 7 centipoise (25 ° C.) and 3
It was 0 centipoise (25 ° C.). (3) Using the floor polish obtained in the above (2),
Leveling, gloss, adhesion, water resistance,
Tests for detergent resistance, removal properties, black heel mark resistance, and water resistance were performed, and the results were as shown in Table 2 below.

<< Comparative Example 3 >> (1) The same procedures as in (1) to (3) of Example 1 were carried out, except that monomers of the type shown in Table 2 below were used in the proportions shown in Table 2. To produce an aqueous emulsion dispersion of the copolymer. The acid value and glass transition temperature of the copolymer in this aqueous emulsified dispersion were as shown in Table 2. (2) To the aqueous emulsion dispersion of the copolymer obtained in (1) above, solubilized zinc oxide was added in the same manner as in (5) of Example 1, and various components are shown in Table 1. The copolymer content was 37.5% by weight.
Was produced. The viscosity of the resulting floor polish was 220 centipoise (25 ° C.). Since this floor polisher had too high a viscosity to be applied to the test specimen, it had leveling properties, gloss, adhesion, water resistance, detergent resistance, removal properties, black heel mark resistance and water resistance. Sex tests could not be performed.

Comparative Example 4 (1) Monomers of the type shown in Table 2 below were mixed at the ratio shown in Table 2 to prepare a monomer mixture containing no polymerization initiator. (2) In a polymerization vessel, 43 parts by weight of ion-exchanged water, 1 part by weight of sodium lauryl sulfate and 2,2′-azobis (2
-Methyl propionate), and the monomer mixture prepared in the above (1) was cooled to an internal temperature of 80 mL.
The emulsion polymerization was carried out in the usual manner by supplying over 4 hours while maintaining the temperature at 0 ° C., and the polymerization reaction was further continued at the same temperature for 2 hours to obtain a silicone macromonomer unit, a styrene unit,
An aqueous emulsion dispersion of a copolymer having butyl acrylate units and methacrylic acid units (copolymer content 38% by weight) was produced. (3) The acid value and glass transition temperature of the copolymer in the aqueous emulsified dispersion obtained in (3) were as shown in Table 2 below. (4) Solubilized zinc oxide was added to the aqueous emulsified dispersion of the copolymer obtained in (3) in the same manner as in (5) of Example 1, and various components are shown in Table 1. The copolymer content was 37.5% by weight.
Was produced. (5) Using the floor polish obtained in (4) above,
Leveling, gloss, adhesion, water resistance,
Tests for detergent resistance, removal properties, black heel mark resistance, and water resistance were performed, and the results were as shown in Table 2 below.

[0053]

[Table 1]

[0054]

[Table 2]

From the results of Examples 1 to 4 in Table 2 above, it was found that the structural unit (a) derived from the silicone macromonomer was present in an amount within the range of 0.1 to 10% by weight, and It has the structural unit (b) derived from the body in an amount within the range of 10 to 80% by weight, and the structural unit (c) derived from another radical polymerizable monomer has an amount of 10 to 89.9% by weight. Example 1 consisting of an aqueous emulsified dispersion of a copolymer having an amount in the range
The floor polishes of Nos. 1 to 4 have low viscosity, are excellent in handleability and applicability, and have leveling, gloss, adhesion,
Excellent water resistance and detergent resistance, and Examples 1 to
Among 4, the acid value of the copolymer in the aqueous emulsified dispersion was 10
It can be seen that the floor polishes of Examples 1 to 3 having 0 mgKOH / g or more are more excellent in the removability, the black heel mark resistance and the scuff resistance in addition to the above-mentioned properties.

On the other hand, from the results of Comparative Examples 1 and 4 shown in Table 2, the copolymer having no structural unit (a) but having only structural unit (b) and structural unit (c) was obtained. It can be seen that the floor polishes of Comparative Examples 1 and 4 comprising the aqueous emulsified dispersion of the above were poor in gloss, black heel mark resistance and scuff resistance. Also,
From the results of Comparative Example 2 in Table 2 above, even a floor polisher comprising an aqueous emulsified dispersion of a copolymer having the structural units (a), (b) and (c), It can be seen that the floor polish of Comparative Example 2, in which the content of the structural unit (a) in the copolymer exceeds 10% by weight, is too high in viscosity and inferior in leveling properties. Furthermore, from the results of Comparative Example 3 in Table 2 above, it has only the structural unit (a) and the structural unit (c), and does not have the structural unit (b) (a structural unit derived from a styrene monomer). It can be seen that the floor polish of Comparative Example 3, which is composed of an aqueous emulsified dispersion of the copolymer, has too high a viscosity to be applied to the floor and cannot be used as a floor polish.

Reference Example 1 An aqueous emulsion dispersion was prepared using the same monomer composition as in Example 2 by the usual emulsion polymerization method in the same manner as in Comparative Example 4. It became a gel inside, an aqueous emulsified dispersion was not obtained, and the floor polish of the present invention could not be prepared.

[0058]

EFFECT OF THE INVENTION The floor polisher of the present invention has a low viscosity and is excellent in handleability and applicability, and furthermore has a leveling property, gloss, adhesion to flooring, water resistance, detergent resistance and floor surface. It is excellent in various properties such as removability, black heel mark resistance, scuff resistance, and long-lasting properties. Therefore, the floor glazing agent of the present invention takes advantage of the above-mentioned excellent properties, and uses homogeneous vinyl floor tiles, vinyl tiles such as composition vinyl floor tiles, rubber tiles such as single-layer rubber tiles, and rubber or plastics such as asphalt. Various flooring materials, such as wood flooring materials, flooring, cork tiles, and other flooring materials made of stone, terrazzo, porcelain, etc., are effectively used in common for the purpose of cosmetic and protection. can do.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J038 CC021 CC051 CC061 CC071 CD011 CD09 CF021 CG021 CG031 CG061 CG141 CG161 CH031 CH041 CH051 CH071 CH081 CH171 CH201 CH251 CJ031 CK03 CK04 GA03 GA06 GA07 GA08 GA09 MA10 MA14 MA15 NA01 NA03 NA04 NA11 NA12 NA24 PB02 PB05

Claims (4)

[Claims] 1. It has a structural unit (a) derived from a silicone-based macromonomer, a structural unit (b) derived from a styrene-based monomer, and a structural unit (c) derived from another radically polymerizable monomer. And based on the total weight of all the structural units, 0.1 to 10% by weight of the structural unit (a);
A floor polish comprising a water-based emulsified dispersion of a copolymer having a structural unit (b) content of 10 to 80% by weight and a structural unit (c) content of 10 to 89.9% by weight. 2. The copolymer in the aqueous emulsified dispersion has a structural unit derived from a radically polymerizable monomer having a carboxyl group as a part of the structural unit (c), and has an acid value of 100 mgKOH / The floor polisher according to claim 1, which is a copolymer of at least g. 3. The aqueous emulsion disperses a silicone-based macromonomer and an oil-soluble radical polymerization initiator in a styrene-based monomer and other radical-polymerizable monomers, and converts the solution into an aqueous medium. The polisher for floors according to claim 1 or 2, which is an aqueous emulsion dispersion of a copolymer formed by emulsion-dispersion and polymerization. 4. The floor polishing agent according to claim 1, wherein the copolymer has an average particle size of 1 μm or less.