JP2001064592A - Floor polish composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor polish composition having excellent adherability for a floor covering material, black heel mark resistance, impact resistance and wearability. SOLUTION: This floor polish composition comprises (a) an acrylic resin emulsion containing an acrylic resin having a weight-average molecular weight of 10,000-200,000 and a glass transition point of 10-40 deg.C, (b) another acrylic resin emulsion containing another acrylic resin having a weight-average molecular weight of 10,000-200,000 and a glass transition point of 50-100 deg.C and (c) a wax emulsion containing wax having a softening point of 110-160 deg.C.

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 more particularly, to a floor polish composition excellent in adhesion to a floor material, black heel mark resistance and impact abrasion resistance.

[0002]

2. Description of the Related Art In recent years,
With the modernization of office buildings and stores, the performance required for floor polish as a beautiful floor finish to enhance the bright interior aesthetics is increasing. As such a floor polish, a synthetic resin emulsion-based floor polish generally containing a synthetic resin as an active ingredient is widely used. Such a synthetic resin emulsion-based floor polish gives a glossy surface only by being left to dry after application, and has been widely used in recent years. Such synthetic resin emulsion floor polish is required to have various properties such as adhesion to the floor, black heel mark resistance and impact abrasion resistance. Various types of synthetic resin emulsion floor polishes have been studied and developed to improve such performance.

As a floor polish of a synthetic resin emulsion system for improving the performance described above, for example, a coating composition containing an emulsion polymer containing two polymer components whose molecular weight and glass transition temperature are adjusted (Japanese Patent Laid-Open No. No. 204371), a water-based glazing composition for floors containing an acrylic resin emulsion having a glass transition point in a specific range, and a wax emulsion having a melting point in a specific range (Japanese Patent Application Laid-Open No. 10-245524) and a specific range. (For example, Japanese Patent Application Laid-Open No. H11-61048) discloses a floor glazing composition containing a specific ratio of an emulsion composed of two acrylic resins having a Tg. According to the floor polish composition disclosed in the above-mentioned publication, the above-mentioned performance is improved to some extent, but the development of a floor polish composition having the above-mentioned performance further improved is desired. Accordingly, an object of the present invention is to provide a floor polish composition excellent in adhesion to a floor material, black heel mark resistance and impact wear resistance.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an acrylic resin emulsion containing two kinds of acrylic resins having a specific range of a weight average molecular weight and a glass transition point, and a softening point. It has been found that a floor polish composition containing a wax emulsion containing a wax having a specific range can achieve the above object. The present invention has been made based on the above findings, and (a) the weight average molecular weight is 10,000 to 200,000;
Acrylic resin emulsion containing an acrylic resin having a glass transition point of 10 to 40C, (b) an acrylic resin having a weight average molecular weight of 10,000 to 200,000 and a glass transition point of 50 to 100C And (c) a softening point of 110 ° C. to 1
A floor polish composition comprising a wax emulsion containing a wax at 60 ° C.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the floor polish composition of the present invention will be described in detail. The floor polish composition of the present invention has (a) a weight average molecular weight of 10,000 to 2;
An acrylic resin emulsion containing an acrylic resin having a glass transition point of 10 to 40 ° C.,
(B) a weight average molecular weight of 10,000 to 200,000
And an acrylic resin emulsion containing an acrylic resin having a glass transition point of 50 to 100 ° C., and (c)
It contains a wax emulsion containing a wax having a softening point of 110 ° C. or higher.

The glass transition point of component (a) is 10 to 40 ° C.
The acrylic resin emulsion containing the acrylic resin is described below. The acrylic resin emulsion is an emulsion containing an acrylic resin, can be produced by a known emulsion polymerization technique, and has a glass transition point (hereinafter, referred to as “Tg” in the present specification) depending on the composition of a monomer used. Can be adjusted.
Examples of the monomer used for producing the acrylic resin emulsion include styrene, methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, and methacrylic acid 2 -Ethylhexyl, lauryl methacrylate, cyclohexyl methacrylate, methyl acrylate, ethyl acrylate,
Butyl acrylate, hexyl acrylate, acrylic acid 2
-Ethylhexyl, lauryl acrylate, cyclohexyl acrylate, benzyl acrylate, hydroxyethyl methacrylate, acrylic acid, itaconic acid, crotonic acid,
Maleic acid, acrylic acid, methacrylic acid, vinyl acetate,
Examples include acrylamide, methylolacrylamide, dimethylacrylamide, and monomers copolymerizable with the above monomers.

The acrylic resin of component (a) has a Tg of 1
It is 0-40 degreeC, Preferably it is 20-30 degreeC.
If the acrylic resin (a) has a Tg of less than 10 ° C., the coating formed on the flooring material becomes soft, and dirt and heel marks are easily formed. In this specification, “Tg” refers to a glass transition temperature, which is a temperature at a boundary where a glassy polymer starts to soften. The Tg of the copolymer can be determined as follows from the Tg of the homopolymer of the component monomer. 1 / Tg = W ₁ / Tg ₁ + W ₂ / Tg ₂ or Tg = V ₁ Tg ₁ + V ₂ Tg ₂ Tg ₁ , Tg ₂ : Tg W ₁ , W _{2 of} homopolymer of composition monomer: composition 1, 2 V ₁ , V ₂ : volume fraction of compositions 1 and 2 Tg in the above formula is a value represented by K.

Next, the glass transition point of component (b) is 50-1.
An acrylic resin emulsion containing an acrylic resin at 00 ° C. will be described. The acrylic resin emulsion is an emulsion containing an acrylic resin, and can be produced by a known emulsion polymerization technique, and the Tg can be adjusted by the composition of the monomer used. As the monomer used for producing the acrylic resin emulsion, the same monomer as that used for producing the acrylic resin emulsion of the component (a) described above is used. The Tg of the acrylic resin of the component (b) is 50
To 100 ° C, preferably 60 to 80 ° C.
If the Tg of the acrylic resin as the component (a) exceeds 100 ° C., the film-forming properties deteriorate, and cracks occur and a tough film cannot be obtained.

The acrylic resin (a) and the acrylic resin (b) have a weight average molecular weight of 10,000 to
200,000, preferably 70,000 to 15
000, more preferably 90,000 to 12
It is 0000. When the weight average molecular weight is less than 10,000, the strength of the formed film is not obtained, and a film having no durability is formed. When the weight average molecular weight exceeds 200,000, a heel mark is easily formed on the formed film. Examples of the method for adjusting the molecular weight of the acrylic resin include a method in which a chain transfer agent (such as an alkyl mercaptan) or a polymerization initiator is added to the reaction system to cause a reaction, a method in which the polymerization temperature or the type of the solvent is changed, or the like. No. The difference between the Tg of the acrylic resin (a) and the Tg of the acrylic resin (b) is preferably 20 to 60 ° C, more preferably 20 to 40 ° C, and most preferably. Is 20 to 30C. (A) Tg of acrylic resin
If the difference between the Tg of the acrylic resin and the Tg of (b) is less than 20 ° C., the film-forming properties and the adhesion between the floor material and the film may be poor. Stainability, heel mark resistance, and film-forming property may be inferior in some cases.

The weight ratio of the solid content of the acrylic resin emulsion (a) to the solid content of the acrylic resin emulsion (b) is preferably 90:10 to 1
0:90, more preferably 70:30 to 30: 7.
0. If the weight ratio of the solid content of the acrylic resin emulsion of (a) to the solid content of the acrylic resin emulsion of (b) is out of the above range, the adhesion between the flooring material and the coating is poor or formed. Since the gloss retention and abrasion resistance of the coating may be poor, it is preferable to be within the above range.
Further, the preferable blending amount of the acrylic resin emulsion of the above (a) and the acrylic resin emulsion of the above (b) is a solid content weight in the floor polish composition.
5 to 30 parts by weight, more preferably 10 to 2 parts by weight.
5 parts by weight. When the blending amount of the acrylic resin emulsion of (a) and the acrylic resin emulsion of (b) is less than 5 parts by weight in terms of solid content, the film thickness to be applied becomes thin and a film having no durability is formed. When the amount exceeds 30 parts by weight, the viscosity of the floor polish composition becomes high, and it may be difficult to apply the composition to the floor.

Next, the softening point of (c) is 110-160 ° C.
The wax emulsion containing the wax is described below. The above wax emulsion has a softening point of 110.
An emulsion containing a wax that is at least ℃,
It can be produced by a conventionally known method. For example, it can be produced by adding an emulsifier to the wax shown below and emulsifying and dispersing with an emulsifying device or the like. Examples of the wax used for producing the wax emulsion include hydrogenated hardened waxes such as tallow and lard, animal waxes such as lanolin, beeswax, and spermaceti, carnauba wax, candelilla wax, montan wax, and montan. Derived wax, ceresin wax, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, amide wax, polyethylene wax or its carboxyl-modified wax, polyethylene oxide or its carboxyl-modified wax,
Examples thereof include a polypropylene wax or a carboxyl-modified wax thereof, an oxidized polypropylene wax or a carboxyl-modified wax thereof, a glycol-modified oxidized polypropylene wax, and an ethylene-acrylic acid copolymer wax.

The above wax has a softening point of 110 to 110.
Use the one at 160 ° C. The preferred range of the softening point is 1
20-140 ° C. When a wax having a softening point of less than 110 ° C. is used, the formed film becomes soft and heel marks are easily formed. The softening point of the wax is
A value measured according to ASTM E-28. Also,
The preferred blending amount of the wax emulsion of the above (c) is 0.1% by solid weight in the floor polish composition.
The amount is 5 to 9 parts by weight, and the more preferable compounding amount is 2 to 5 parts by weight. Also, the weight ratio of the total weight of the solid content of the acrylic resin emulsion of (a) and the solid content of the acrylic resin emulsion of (b) to the weight of the solid content of the wax emulsion of (c). Is 95: 5-5
0:50, preferably 85:15 to 70: 3
More preferably, it is 0. The weight ratio of the total weight of the solid content of the acrylic resin emulsion of (a) and the solid content of the acrylic resin emulsion of (b) to the weight of the solid content of the wax emulsion of (c) is out of the above range. When, the heel mark is easily attached to the formed film, and the floor material on which the film is formed becomes slippery,
Since there may be a problem in stability, it is preferable to be within the above range. Further, the acrylic resin in the component (a) contained in the floor polish composition of the present invention,
The acrylic resin in the component (b) may or may not be crosslinked.

Examples of the cross-linking agent for forming the cross-link include polyvalent metal ions and ammonia and amine complexes of polyvalent metal ions (and particularly those to which NH ₃ is coordinated). The polyvalent metal ion can be added to the composition in the form of an oxide, hydroxide or basic salt, acidic salt or neutral salt having a remarkable solubility of at least about 1% by weight in water. , Beryllium, cadmium, copper, calcium, magnesium, zinc, zirconium, barium, strontium, aluminum, bismuth, antimony, lead, cobalt, iron, nickel or other polyvalent metal ions. Examples of the amine capable of forming a complex of the ammonia and the amine complex of the polyvalent metal ion include morpholine, monoethanolamine, diethylaminoethanol, and ethylenediamine. Further, a polyvalent metal complex (salt) of an organic acid that can be solubilized in an alkaline pH range can also be used.
Also, acetate ion, glutamate ion, formate ion,
Carbonate ion, salicylate ion, glycolate ion,
Anions such as octonate, benzoate, gluconate, oxalate and lactate can also be used. A polyvalent metal chelate whose ligand is a bidentate amino acid such as glycine or alanine is also used.

Further, the acrylic resin emulsion may be crosslinked by adding 0.05 to 0.9 chemical equivalent of a calcium compound to the acid value of the polymer and reacting the calcium compound. Examples of the calcium compound include, but are not limited to, calcium oxide, calcium hydroxide, calcium carbonate, calcium acetate, calcium chloride, and mixtures thereof. Among the above calcium compounds, it is preferable to use calcium oxide, calcium hydroxide or calcium carbonate. Further, a small amount of a metal compound or a metal complex compound such as zinc, cobalt, cadmium, nickel, chromium, zirconium, tin, tungsten and aluminum may be used in combination.
As the calcium compound, a commercially available powdery one can be used, and a fine-grade calcium compound having a particle size of 0.2 to 0.5 μm is preferably used.

The floor polish composition of the present invention has the weight average molecular weight (a) of 10,000 to 200,000.
0, an acrylic resin emulsion containing an acrylic resin having a glass transition point of 10 to 40 ° C, (b) a weight average molecular weight of 10,000 to 200,000, and a glass transition point of 50 to 100 ° C. An acrylic resin emulsion containing a certain acrylic resin emulsion and a wax emulsion containing (c) a wax having a softening point of 110 to 160 ° C. are dispersed in water. The water used in the present invention is not particularly limited, and purified water, distilled water, tap water, and the like can be used. The floor polish composition of the present invention may contain additives which are added to a normal floor polish composition. Such additives include film forming agents, plasticizers, penetrants, dispersants, fragrances, defoamers, fungicides, acaricides, dyes and pigments. When the above additives are added, the amount of the additives is preferably 5% of the total weight of the floor polish composition.
７０70% by weight.

[0016]

The present invention will be described in more detail with reference to the following examples. It goes without saying that the scope of the present invention is not limited to the examples. In the following description, parts mean parts by weight unless otherwise specified. Synthesis Example 1 Synthesis was performed using a flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer, and a nitrogen inlet tube. 2
One of the dropping funnels contains 4.8 methacrylic acid.
12.6 parts, isobutyl methacrylate 22.6 parts, butyl acrylate 12.6 parts, lauryl mercaptan 0.12 parts, sodium lauryl sulfate 0.16 parts and deionized water 19.
A solution obtained by mixing 6 parts and emulsifying with a homomixer was added, and a solution obtained by dissolving 0.2 part of ammonium persulfate as a catalyst in 20.0 parts of deionized water was added to the other dropping funnel. Also, 0.16 parts of sodium lauryl sulfate and 20.0 parts of deionized water were placed in the flask. The atmosphere in the flask was changed to a nitrogen atmosphere, the flask was heated to 80 ° C. in a water bath, and the solution in the two dropping funnels was dropped into the flask over 4 hours while stirring at 250 rpm to carry out a reaction. After completion of the dropwise addition, the mixture was further stirred for 1 hour, and the pH was adjusted to 2.
An acrylic resin emulsion containing 0, an acrylic resin having a solid content of 40.0% was obtained. The weight average molecular weight of the obtained acrylic resin was 120,000. In addition, the calculated Tg is 20 ° C.

Synthesis Example 2 Synthesis was carried out using the same flask as used in Synthesis Example 1. One of the two dropping funnels was charged with 4.8 parts of methacrylic acid, 25.6 parts of isobutyl methacrylate, 9.6 parts of butyl acrylate, and 0.12 of lauryl mercaptan.
Part, 0.16 part of sodium lauryl sulfate and 19.6 parts of deionized water were mixed and emulsified with a homomixer, and 0.2 part of ammonium persulfate as a catalyst was deionized in the other dropping funnel. A solution dissolved in 20.0 parts of water was added. Next, the same operation as in Synthesis Example 1 was performed except that the reaction temperature was 90 ° C., and the pH was 2.0 and the solid content was 4%.
A 0.0% acrylic resin emulsion was obtained. The weight average molecular weight of the obtained acrylic resin was 70,000. The Tg calculated is 30 ° C.

Synthesis Example 3 Synthesis was carried out using the same flask as used in Synthesis Example 1. One of the two dropping funnels contains 4.8 parts of methacrylic acid, 24.8 parts of isobutyl methacrylate, 10.4 parts of methyl methacrylate, and 0.1 part of lauryl mercaptan.
A solution obtained by mixing 2 parts, 0.16 part of sodium lauryl sulfate and 19.6 parts of deionized water and emulsifying with a homomixer was added, and 0.2 part of ammonium persulfate as a catalyst was removed from the other dropping funnel. A solution dissolved in 20.0 parts of ionic water was added. Next, the same operation as in Synthesis Example 1 was performed to obtain an acrylic resin emulsion having a pH of 2.0 and a solid content of 40.0%. The weight average molecular weight of the obtained acrylic resin emulsion was 100,000. Also,
The calculated Tg is 80 ° C. Synthesis Example 4 Synthesis was performed using the same flask as used in Synthesis Example 1. One of the two dropping funnels was charged with 4.8 parts of methacrylic acid, 10.6 parts of isobutyl methacrylate, 24.6 parts of methyl methacrylate, and 0.1 part of lauryl mercaptan.
2 parts, 0.16 part of sodium lauryl sulfate and 19.6 parts of deionized water were mixed and emulsified with a homomixer. The other dropping funnel was deionized with 0.2 part of ammonium persulfate as a catalyst. A solution dissolved in 20.0 parts of water was added. Next, the same operation as in Synthesis Example 1 was performed except that the reaction temperature was 90 ° C., and the pH was 2.0 and the solid content was 4%.
A 0.0 group acrylic resin emulsion was obtained. The weight average molecular weight of the obtained acrylic resin was 50,000. In addition, the calculated Tg is 100 ° C.

Synthesis Example 5 Synthesis was carried out using a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube. 4.25 parts of methacrylic acid and methyl methacrylate are added to the dropping funnel.
A solution obtained by mixing 34 parts and 31.96 parts of butyl acrylate was added. 0.92 parts of sodium lauryl sulfate, 1.38 parts of nonylphenol ethylene oxide 30 mol adduct, 0.12 parts of ammonium persulfate and 55.1 parts of deionized water were placed in the flask. The atmosphere in the flask was set to a nitrogen atmosphere, and the flask was heated to 75 ° C. with a hot water bath,
While stirring at 0 rpm, the solution in the dropping funnel was dropped over 3 hours to carry out a reaction. After the completion of the dropwise addition, the reaction was further performed for 1 hour to obtain an acrylic resin emulsion having a pH of 2.0 and a solid content of 42.5%. The weight average molecular weight of the obtained acrylic resin was 450,000. The Tg calculated is 70 ° C. Synthesis Example 6 Synthesis was performed using a flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen inlet tube. 4.25 parts of methacrylic acid and methyl methacrylate 2 were added to the dropping funnel.
A solution obtained by mixing 3.62 parts and 14.68 parts of butyl acrylate was added. Next, the same operation as in Synthesis Example 5 was performed to obtain an acrylic resin emulsion having a pH of 2.0 and a solid content of 42.5%. The weight average molecular weight of the obtained acrylic resin was 450,000. The Tg calculated is 30 ° C.

Examples 1 to 5 and Comparative Examples 1 and 2 Floor polish compositions having the compositions shown in Table 1 were prepared.

[0021]

[Table 1]

In Table 1, the acrylic resin emulsion, polyolefin wax, alkali-soluble resin, fluorocarbon surfactant and zinc ammonium carbonate are as follows. Acrylic resin emulsion: obtained in Synthesis Example 1,
Weight average molecular weight is 120,000, Tg is 20 ° C
Acrylic resin emulsion: Acrylic resin emulsion: obtained in Synthesis Example 2,
Acrylic resin emulsion having a weight average molecular weight of 70,000 and Tg of 30 ° C. Acrylic resin emulsion: obtained in Synthesis Example 5,
The weight average molecular weight is 450,000 and the Tg is 70 ° C.
Acrylic resin emulsion Acrylic resin emulsion: obtained in Synthesis Example 3,
Weight average molecular weight is 100,000 and Tg is 80 ° C
Acrylic resin emulsion acrylic resin emulsion: obtained in Synthesis Example 4,
Weight average molecular weight is 50,000, Tg is 100 ° C
Acrylic resin emulsion acrylic resin emulsion: obtained in Synthesis Example 6,
The weight average molecular weight is 450,000 and the Tg is 30 ° C.
Acrylic Resin Emulsion Polyolefin Wax: Polyethylene Wax Emulsion Hitec E-10 manufactured by Toho Chemical Industry Co., Ltd.
3N (active ingredient 25%, softening point 104 ° C) Polyolefin wax: polyethylene wax emulsion Hitec E-4B manufactured by Toho Chemical Industry Co., Ltd.
(Active ingredient 40% softening point 138 ° C) Alkali-soluble resin: Acrylic alkali-soluble resin
Primal B-644 manufactured by Rohm and Haas of the United States
(Active ingredient 42%) Fluorocarbon surfactant: Dainippon Ink and Chemicals, Inc.
Manufactured by Megafac F-812 (active ingredient 15%) Zinc ammonium carbonate: zinc oxide in 68.14 parts of water.
0 part was dispersed, and a solution prepared by adding 12.28 parts by weight of ammonium carbonate and 12.58 parts of 28% aqueous ammonia (zinc content: 5.6236% by weight)

The obtained floor polish compositions were evaluated according to the following [Evaluation criteria for floor polish compositions]. Table 2 shows the results. [Evaluation criteria for floor polish composition] (1) Adhesion to floor material JIS K 3920 (floor polish test method)
The test was performed as follows according to the preparation of the test piece in 6.5. After drying the coated film for three hours at room temperature for 48 hours, the surface of the polished film was cut 11 lines vertically and 1 line horizontally with a cutter.
One line was scratched to make 100 surfaces, and cellophane tape was stuck on the surface, completely adhered, and then strongly peeled off at an angle of 45 degrees with the floor surface, and the number of surfaces remaining at that time was counted. (2) Black heel mark resistance JIS K 3920 (floor polish test method)
The heel mark resistance of 15 was evaluated according to the ranking. (3) Impact abrasion resistance Evaluation was performed according to ASTM D 3714-87.
That is, the abrasion property of the floor polished film surface impacted by the rubber test block was visually observed and evaluated according to the following evaluation criteria. ：: The film was not damaged at all. Δ: The coating was slightly damaged and scraped. X: The film is completely shaved.

[0024]

[Table 2]

[0025]

As described above in detail, the floor polish composition of the present invention has (a) a weight average molecular weight of 10.0 or less.
00 to 200,000 and a glass transition point of 10 to 4
An acrylic resin emulsion containing an acrylic resin at 0 ° C., (b) a weight average molecular weight of 10,000 to 20
An acrylic resin emulsion including an acrylic resin having a glass transition point of 50 to 100 ° C.
And (c) By containing a wax emulsion containing a wax having a softening point of 110 to 160 ° C., excellent adhesion to flooring, black heel mark resistance and impact wear resistance are obtained.

Claims (4)

[Claims] (1) a weight average molecular weight of 10,000 to
An acrylic resin emulsion containing an acrylic resin having a glass transition point of 10 to 40 ° C., and (b) a weight average molecular weight of 10,000 to 200,0
Floor polish composition containing an acrylic resin emulsion containing an acrylic resin having a glass transition point of 50 to 100 ° C. and (c) a wax having a softening point of 110 to 160 ° C. . 2. The floor polish composition according to claim 1, wherein a difference between the glass transition point of the acrylic resin (a) and the glass transition point of the acrylic resin (b) is 20 to 60 ° C. object. 3. The weight ratio of the solid content of the acrylic resin emulsion (a) to the solid content of the acrylic resin emulsion (b) is 90:10 to 10:90. 3. The floor polish composition according to item 2. 4. The total weight of the solid content of the acrylic resin emulsion of (a) and the solid content of the acrylic resin emulsion of (b), and the weight of the solid content of the wax emulsion of (c). Is 90:10 to 50:
The floor polish composition according to any one of claims 1 to 3, which is 50.