JPH0465472A - Glazing agent composition for floor and method for glazing floor - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing an aqueous polymer prepared by copolymerizing an alpha, beta-monoethylenic carboxylic acid monomer with a vinylic monomer and an aqueous polymer having masking properties. CONSTITUTION:The objective composition containing (A) an aqueous polymer obtained by copolymerizing an alpha, beta-monoethylenic carboxylic acid monomer [(meth)acrylic acid] with (B) a vinylic monomer (preferably methyl methacrylate, styrene, butyl acrylate, etc.) and (B) an aqueous polymer having masking properties.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a floor polish composition comprising a specific aqueous polymer and an aqueous polymer having hiding properties, and further relates to [Conventional technology and issues] Conventionally, raw materials for offices and hospitals, called vinyl asbestos tiles, homogeneous styles, cushion floor-1 coating materials, etc., include vinyl chloride, epoxy, urethane, acrylic lacquer, etc. Floor polishes have been applied to retain these resins and give them a shine. Special Publication No. 44-23429, Special Publication No. 44-2343
No. 0, Special Publication No. 47-15597, etc., as publicly known.
These polishing agents gave luster to the raw material and formed a thin film layer with less dust adhesion, thereby facilitating the maintenance and management of the raw material. However, due to long-term use, the dirt embedded in the floor coating layer becomes difficult to remove even with normal wiping with water and washing with detergents, so it is necessary to remove it with a special detergent containing a solvent such as calpitol called a stripping agent. This was used to wash away the dirt that had gotten into the floor along with the film layer. However, this peeling work...

This is extremely labor-intensive work, and in the current state of labor shortage in recent years, it has become increasingly difficult to carry out this work. Moreover, even if this removal work is continued for a long period of time, it is impossible to completely remove the dust, and due to the fact that dust has adhered to some areas and the polishing agent film has discolored due to aging, it is impossible to completely restore the beauty. It was becoming difficult to obtain.

[Means to solve the problem]

In view of the above problem, the present inventor conducted various studies and found that
An aqueous polymer obtained by copolymerizing an α,β-monoethylenic carboxylic acid monomer and a vinyl thread binder (hereinafter sometimes referred to as binder polymer J) and an aqueous polymer having hiding properties (hereinafter sometimes referred to as binder polymer J). We have devised a floor polish containing as the main ingredient ``concealing polymer''.
After applying this floor polish to the floor in a thin layer and drying it, the puffer was able to obtain a high gloss and hide the dirty floor surface, restoring the clean appearance of the floor.He completed the present invention. I ended up doing it.

The concealing polymer of the present invention is a polymer dispersion obtained with hollow pores, and is a patent application published in 1988-32513, a patent application published in 1982-185505, and a patent application published in 1982.
-69103. Patent application publication 1986-213509, patent application publication 1981-135409, patent application publication 1982
-223873, patent application published 1986-110208.
Patent application publication Hei-2140271. Patent application publication Hei-2
140272 etc. are publicly known. Examples of commercially available products include Lowpeke (also known as Primal or a-plex) OF-
42, Low Payk 0P-84J, Low Payk 0P-62
(manufactured by Rohm and Haas), etc. Boncourt (also known as Guerandole) PP-1000 and Boncourt PP-
10018, PP-2000, Boncourt PP-110
0 (manufactured by Dainippon Ink and Chemicals), etc. The components preferably include a methacrylic acid polymer or a methacrylic acid copolymer as a core component, and a methacrylic ester, an acrylic ester, styrene, etc. as a shell component. In addition, solvents (toluene,
It is a polymer consisting of a core that is soluble or swellable in octane (such as octane) and shell particles that are insoluble in solvents. The particle size is between 5 and 0.05 microns, preferably between 1 and 0.2 microns. Since the core is partially hollow, it has high hiding properties, and the particles are completely dispersed in water.

These hiding polymers have been considered as substitutes for titanium oxide, clay, and other inorganic pigments in matte paints, lightweight papers, heat insulating materials, etc., but their conventional use as brighteners involves heating the hiding polymer. This is a method in which the hollow layer is melted (transparent) or a portion thereof is melted using a press to obtain gloss, and as a result, the hiding property is reduced or lost. It has never been studied as a brightening agent other than for the special use mentioned above.

This is because these hiding polymers essentially have a matting effect at room temperature, and even when added in small amounts, the gloss is significantly reduced. The polishing agent of the present invention does not give much gloss after being applied and dried, but it is valuable as a polishing agent as it can give extremely high gloss just by polishing with a cloth or floor pad.
Effective in hiding dirt on the floor. Comb et al.'s hiding polymer is typically white in color. When the polishing agent of the present invention containing this is applied to a white floor surface, it has the effect of concealing dirt on the base, improving whiteness and restoring a clean, high-gloss floor. Furthermore, unlike the appearance of applying a white paint containing ordinary titanium oxide, clay, etc., a finish that retains the texture of the original raw material surface can be obtained. Hiding polymers having hollow particles are particularly effective. Hollow particles (also called small pore particles or microvoid particles).

) can be easily confirmed using a transmission electron microscope or a scanning electron microscope. On the other hand, even when the particles do not have a hollow structure, if the core and outer shell components of the particles have different structures, a concealing polymer can be obtained and is effective as a polishing agent component in the present invention. A component with a heterogeneous structure is, for example, a relatively hydrophilic polymer (such as methyl methacrylate or ethyl acrylate) in the core of the particle, and a hydrophobic polymer (such as styrene) in the outer shell of the particle. Something close to visible light wavelength (
(approximately 500 nanometers) has a large concealing effect. Such a concealing polymer can be easily obtained by an emulsion polymerization method, and the t1 polymerization method, emulsifier, polymerization initiator, monomers, etc. are common to the binder polymer described below, and are also known conventional methods.

Hiding polymers have a particle structure in which the core-shell is a heterogeneous component and the particle size.

It is 0.05 to 5 microns, preferably 0.2 to 1 micron. Binder polymer is usually 0.01~
The difference is that the particle size is 0.3 micron, preferably 0.05 to 0.1 micron, and a core-shell particle structure is not necessarily required. Furthermore, the hiding polymer does not form a continuous film at room temperature, is opaque at room temperature, and has no shine at room temperature unless polished.

The binder polymer of the present invention is disclosed in Japanese Patent Publication No. 47-14019.
It can be obtained by a known method. The monomer composition for obtaining the polymer consists of an α,β-monoethylenic carboxylic acid monomer and a vinyl monomer, which are copolymerized. Examples of α,β-monoethylenic carboxylic acid monomers include:

Methacrylic acid (abbreviated as Maa), acrylic acid (abbreviated as Aa), itaconic acid, maleic acid, crotonic acid, etc.
Preferred are Maa and Aa. 3-7 in weight ratio
0%, preferably 5 to 30%. Examples of vinyl monomers include Nisder (meth)acrylate (this expression refers to methacrylic esters and acrylic esters), styrene, vinyl acetate, butadiene, ethylene, vinyl chloride, vinylidene chloride, and (meth)acrylonitrile. , (meth)acrylamide, hydroxyalkyl (meth)acrylic ester, N-alkylaminoethyl (meth)acrylic ester, etc., preferably methyl methacrylate (hereinafter abbreviated as HMA) and styrene (hereinafter abbreviated as ST). ), butyl acrylate (hereinafter abbreviated as BA), acrylonitrile (hereinafter abbreviated as AN).

), 2 ethylhexyl acrylic acid ester (hereinafter 2E
(abbreviated as RA), etc. If necessary, a zinc complex liquid (ammine complex of zinc carbonate or zinc acetate, amino acid complex, etc.) may be added to the aqueous liquid of the binder polymer. As the binder polymer of the present invention, those already commercially available are also useful.

For example, Primal (also known as Lowplex) B-832,
or DP-1 etc. (commercially available from Rohm and Haas Co., Ltd., Nippon Acrylic Chemical), Boncourt 9438 or 9404 (
(commercially available from Dainippon Ink & Chemicals), JSR Acrylic Emulsion AE-116, AE-120, etc. (commercially available from Nippon Synthetic Rubber), Acryset FB-252, etc. (commercially available from Nippon Shokubai Kogyo).

"To obtain a polishing agent layer as an acid, film-forming aids, plasticizers, leveling aids, alkali-soluble resins, wax, water necessary for solid content adjustment, coloring agents, etc. are blended as necessary. Film-forming The auxiliary agent is a type of solvent necessary to form a continuous film with the binder polymer, and includes ethyl carpitol,
Methyl calpitol, ethylene glycol, and texanol (trade name manufactured by Eastman Kodak Company). The plasticizer has the effect of imparting a plasticizing effect to the binder polymer, and includes, for example, tributoxyethyl phosphate and dibutyl phthalate. The leveling aid is a fluorine-based surfactant that has the effect of preventing repellency due to oil on the floor surface and providing a uniform coating surface, such as Florado FC-149 (commercially available from Jujutsu 3M) or Megafac F. -120 (commercially available from Dainippon Ink and Chemicals).

Alkali-soluble resins are low-volume resins that have a large amount of carboxyl groups, such as styrene maleic acid resins, rosin-modified maleic acid resins, and (meth)acrylic acid ester (meth)acrylic acid resins, which are used in an ammonia-dissolved state. Examples include 5MA2625A (commercially available from Arco), Sumilite Resin PR19788 (commercially available from Jurette), Acrisol 644 (commercially available from Rohm and Haas), and the like. Wax is effective in preventing scratch marks and dust adhesion on the soles of shoes when walking on the floor, and includes polyethylene wax, carnauba wax, etc., and is usually used in an aqueous emulsion state, such as Hytic E-4B (manufactured by Toho Chemical Industry Co., Ltd.). commercially available). The solid content is 5-50%, preferably 10-30%, usually adjusted with water, and the viscosity is 100e.
ps or less, preferably 10 cps or less, which facilitates application with a mop. If the floor is white, no special coloring agent is required, but if the floor is green or red, for example, an aqueous dispersion of water-based dye and colored pigment (organic or inorganic pigment) depending on the color is mixed. For example, in the case of green color, it is preferable to use Luconyl Grun 93
60 (BAS) and EM GREEN B (Toyo Ink Manufacturing).

The following blending ratios are usually preferred. Per 100 parts of binder polymer: a) Concealing polymer 5-500 (b) Binder polymer 100 (standard value) (c) Film-forming aid
O~200 (d) Plasticizer O~50 (e) Leveling aid 0~10 (f) Alkali-soluble resin O~200 (g) Wax 0~200 (h) Water Total solids content 5~50% (i) Coloring agent is blended in an amount of 0 to 100.

When the polishing agent of the present invention is applied to a floor, it is applied uniformly with a mop, a rag, a spray, etc. By drying at room temperature, a film thickness of about 0.1 to 5 microns can be obtained with one coating. It may be applied again and overcoated. In this way, depending on the blending ratio of the concealing polymer, a matte or low-gloss film with a thickness of about 1 to 10 microns is usually formed by three coats.

Next, extremely high gloss can be obtained by light polishing or high-speed polishing, either manually using a piece of cloth or a polishing pad, or by applying a puff or using an electric polisher. Conventional polishes give a high gloss surface, but it is impossible to restore the original clean appearance of the floor surface unless dirt embedded in the floor surface and old yellowed film layers are removed. . -With the invention of strength wood,
The glossy film obtained is a thin film that has concealing properties, exhibits high gloss, and has a beautiful appearance that takes advantage of the original texture of the raw material. It also hides the layers, reproducing a floor surface with an extremely ideal appearance.

The present invention will be explained below with reference to Examples, but the invention is not limited in any way by the Examples.

Example 1. Synthesis of concealing polymer (particles with hollow pore structure) (i) Preparation of core A 500+ml separable flask reactor with a cover was equipped with a thermometer, stirrer, reflux condenser, water bath, dropping funnel, and nitrogen seal. Equipped with an entrance.

Add 475 ml of deionized water to the reactor. Cataloid 5I-40
(Colloidal silica, 40% solids, Catalyst Chemical Industry
1 item) 7.5g was charged, the atmosphere was replaced with nitrogen, and the mixture was heated to 85°C. Sodium persulfate (NFS) 10% aqueous solution 4g
was added, and a mixture of 6 g of Kaa and 9 g of HMA was continuously added dropwise using a dropping funnel at 85±1° C. over 20 minutes, and the temperature was maintained at 85° C.±1° C. for an additional 45 minutes. The mixture was cooled to below 30°C and filtered through a 300 mesh nylon cloth.

There is no aggregate of filter cloth residue, and the residual upper limit is 125p.
An emulsion polymer having a milky white appearance and a pH of 3.5 was obtained. Below, unless otherwise specified, the unit is grams (g).

(ii) Creation of polymer particles with a shell (outer shell) surrounding a core (meth)acrylic acid ester Emulsion polymer liquid 486 obtained in (i) above
．． 5 was placed in a 10100O reaction tank and heated to 80℃, NFS (22% aqueous solution) 38.5 was added, and Maa2
．． 8, MMA 106°5 and BA25.8 mixed upper Zimmer's solution was continuously dropped into the reaction tank over 30 minutes,
During this time, the temperature was maintained at 80±2°C. 80 minutes for another 35 minutes
It was maintained at ±2°C and aged. Ammonia water (25%)8.
5 was added and heated to 90°C over 15 minutes. 30℃
The mixture was cooled down and filtered using a 100 mesh nylon cloth. Aggregates of filter cloth residue 0.1, aggregates attached to blades 0
．． 2. Residue on top - 350pp11. An emulsion polymer with a milky appearance of pH 7.9 was obtained.

(iii) Creation of polymer particles further encapsulated with ST to form a shell (outer shell) double layer Emulsion polymer liquid 67 obtained in the above (it)
0 and ammonia water (25%) 1.5 to about 10o.

ml of the reaction vessel and heated to 85°C. NFS (22
% aqueous solution) 10%, deionized water 70% and sodium dodecylbenzenesulfonate (>99% purity) 0
．． A monomer emulsion consisting of ST 15 and ST 250 was continuously added dropwise over a period of about 90 minutes using a dropping funnel.
During this time, the reaction temperature was maintained at 85°C. After finishing dropping, 8
It was held at 5°C for about 15 minutes and cooled to below 30°C. 100
It was filtered using mesh nylon cloth. Approximately 0.5゜ aggregate of filter cloth residue/7-420ppm, PH9,
5. An emulsion polymer having a milky white appearance with a viscosity of 240 cps (centiboise), an average particle diameter of 0.9 micrometers, and a non-volatile content of 40.2% was obtained.

Example 2. Synthesis of concealing polymer (particles with non-hollow structure) (i) Creation of core The following procedures were carried out in accordance with (i) of Example 1 using the following components.

Deionized water 475 Cataloid 5r-407,5 NFS (10%) 4 MMA 15 Aggregates of filter cloth residue 0.05 g, residual monomer 1° Op.
An emulsion polymer having a milky appearance with pH 6.5 and below pa+ was obtained.

(n) Creation of polymer particles surrounded by a double shell around the core Emulsion 545 obtained in (i) of Example 2 above
was charged into a reaction vessel at about 10,100O and heated to 70°C. NFS (22% aqueous solution) was added and Maa
A mixed monomer solution of 2.8, MMA 106.5, and BA25.8 was continuously added dropwise over about 50 minutes, and the reaction temperature was maintained at 70 C during this time, and the mixture was aged for 10 minutes.

Aqueous ammonia (25%) 8 was added and heated to 85°C. Then, a monomer emulsion consisting of deionized water 80 and sodium dodecylbenzenesulfonate 0115 and ST 250 was continuously added dropwise over a period of 90 minutes, during which time the reaction temperature was maintained at 85° C. and incubated for 15 minutes. 30℃
It was then cooled and filtered using a 100 mesh nylon cloth. Filter cloth residue 0.5. Residual monomer 150pp
An emulsion polymer with a milky white appearance was obtained, having a pH of 9.4, a viscosity of 9 cps, an average particle size of 0.8 micrometers, and a non-volatile content of 39.8%.

Example 3. Synthesis of Binder Polymer 360° deionized water and 2 parts sodium dodecylbenzenesulfonate were added to a 1000+1 reaction vessel and heated to 80°C. N.F.
S (5% solution) 24 was added, and 7-summer emulsion (deionized water 100, sodium dodecylbenzenesulfonate 0
．． 8, Maa32, ST 60, BA 100, M
An emulsion consisting of MA 208) was continuously added dropwise over a period of 3 hours, during which time the temperature was maintained at 80±1°C. It was heated to about 90°C and held for 30 minutes. The mixture was cooled to 30° C. or lower, and an aqueous solution of zinc carbonate ammine complex (also known as ammonium complex) 135 containing 4% zinc was added and filtered through a 200 mesh nylon cloth. Filter cloth residue 0.5, residual monomer 80
ppm, PH9.2, viscosity 8 cps, non-volatile content 40
．． An emulsion polymer having a bluish opalescent appearance with a particle size of 1% and a particle size of 0.07 micrometers was obtained.

Example 4. Preparation of acid product for floor polish layer (i) The following ingredients were added to a beaker of approximately 10 kl and mixed with sufficient stirring during this period.

water
53 Tributoxyethyl phosphate 1.5
Oiri Kagaku Product Florado FC-149 (1% effective content aqueous solution) 0.5 Jujutsu 3M product aqueous solution Ethyl Carpitol Daicel Chemical Industry Product Binder Polymer (40% solid content) 30 Example 3 Pinder Polymer Hytic E -4B (40% solid content) 5 Toho Chemical Industry Layered Polyethylene Wax Aqueous Emulsion Sumilite Resin PR-19788 (20% solid content) 5 Juretsu Product Ammonia Water Dissolved (5) Conducted on the above formulation 100 Example 1 (iii)
The obtained concealing polymer (40.0% solid content) 50% and water were added and blended, pH 9, solid content 19.8%, viscosity 3.
A cps floor polish composition was obtained. In a similar manner, floor polish compositions were obtained by changing the binder polymer and hiding polymer, and are summarized in Table 1.

Table 1 Example 5. Performance evaluation of floor polish composition The polish composition obtained in Example 4 was applied to vinyl tiles "High Plain White" and "High Plain Black J (Shin-Etsu Polymer Products).
Uniform coating at a rate of 10 g/rrf and drying at room temperature were repeated three times to give three coats. The tiles were then polished 20 times with one hand under a constant load using a cotton cloth. The obtained tiles were subjected to the evaluation of the following performance items, which are summarized in Table 2.

(1) Gloss The obtained black tile was measured with a 60° specular reflection gloss meter.

(2) Black heel mark resistance (durability) The obtained white tile was manufactured using C3MA BULLETIN NQ9-
Black heel mark resistance was examined using a Snell capsule tester based on No. 73. The percentage of black adhesion on the soles of shoes was visually compared.

(3) Observe the state of the film surface of the black tile that has obtained water resistance in accordance with the Japanese Floor Polish Industrial Standard JFPA Standard-06,
A relative comparison was made.

(4) Adhesion After 12 hours, the coated piece was pressed onto the black tile surface with cellophane tape, and the cellophane tape was instantly removed by 90° peeling, and the degree of the polishing agent film remaining on the tile surface was compared visually.

(5) Concealability The whiteness of the black tiles was compared visually. (The larger the white skin, the better) (6) Leveling property The uneven coating and smoothness of the coating film were visually compared using black tiles.

Table 2 0: Excellent △: Slightly inferior, but practically possible As a result of its effectiveness, it has been found that it hides stains on the floor surface and maintains the performance as a conventional polishing agent, resulting in the effect of regenerating and maintaining the cleanliness of the floor surface.

Claims (1)

[Claims] 1. It is characterized by containing an aqueous polymer obtained by copolymerizing an α,β-monoethylenic carboxylic acid monomer and a vinyl monomer, and an aqueous polymer having a hiding property. Floor polish composition 2, a polishing method using the floor polish composition according to claim 1