JP3009826B2 - Polishing agent for floor - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a floor polisher containing a vinyl polymer or the like as a main component (hereinafter sometimes simply referred to as a polisher). The floor polish of the present invention can be used particularly for floors with many pedestrians, such as department stores, supermarkets and public facilities.

[0002]

2. Description of the Related Art At present, the mainstream of polishes for floors is an aqueous polymer type, and many types of polishes have been known, but emulsions mainly comprising vinyl polymers and the like are generally used. Is often used. These floor polishes exhibit a beautiful luster, hardly have black heel marks due to the heels of shoes (black heel mark resistance), hard to be stained (stain resistance), and have scratches caused by walking. Various properties such as difficulty in attaching (abrasion resistance) are required.

[0003]

However, none of the conventional polishes for flooring satisfies all of these properties, and further improvement is required. In addition, floor polishes must not be peeled off by ordinary care with a detergent and must maintain excellent gloss (detergent resistance).
Soil that cannot be removed with a detergent gradually accumulates and must be easily removed when the stain becomes unusable (removability).

[0004] In order to obtain a polishes excellent in removability while having a contradictory property as well as forming a tough film and having excellent removability, the molecular weight is 8,000 to 10
A large number of coating compositions containing a high molecular weight polymer of 0000 as a main component have been proposed (JP-B-53-37313, JP-A-55-142044, JP-B-56-466, and JP-A-56-466). 62-294471, JP-A-63-2
86471, JP-A-4-325592 and JP-A-5-5083.

[0005] However, the films comprising the coating compositions disclosed in the above publications still have insufficient black heel mark resistance, stain resistance, abrasion resistance and the like. In particular, when the coating composition is applied to a floor with many pedestrians such as a department store, a supermarket, and a station building, a remarkably large number of black heel marks are attached, abrasions easily occur, and dirt becomes severe within a short time after application. However, there is a disadvantage that the gloss is lost and the appearance is impaired. In addition, for the purpose of improving black heel mark resistance and abrasion resistance, floor polishes containing water-based polyurethane as a main component (Japanese Patent Publication No. 64-11236) have been proposed. There is a disadvantage that it cannot be easily peeled off when repainting.

The present invention solves the above-mentioned problems, and has various characteristics such as excellent black heel mark resistance, stain resistance, abrasion resistance, etc., good removability, and easy peeling. It is an object of the present invention to provide a floor glazing agent having all of them.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and have found that the weight average molecular weight of a vinyl polymer or the like as a main component is set to an ultrahigh molecular weight exceeding 1,000,000. By this, black heel mark resistance,
The present inventors have found that the stain resistance and the like are remarkably improved and the removability is good, and based on this finding, the present invention has been completed.

[0008] The floor polisher of the first invention is CH ₂ = CX
- group (X is a hydrogen or a methyl group) polymer comprising a monomer having a (like that do not or ionic crosslinking prior to ionic crosslinking
Flooring agent mainly composed of a polymer in a state)
The polymer has a weight average molecular weight of more than 1,000,000. Further, the second invention provides that the total amount of the above monomers is 10
When 0% by weight, 2 to 20% by weight is acrylic acid and / or methacrylic acid.
The invention is characterized in that the acid value of the polymer is 10 to 150. Further, the fourth invention provides the floor polishing agent,
It is characterized by containing a wax in a weight ratio of 1: 0.1 to 0.3 with respect to the polymer.

The above-mentioned “monomer having a CH ₂ ＣCX— group (X is hydrogen or a methyl group)” includes methyl acrylate,
Acrylic esters such as ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate, and vinyl monomers such as styrene and vinyl acetate (X in the above formula)
Is hydrogen), methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (when X is a methyl group in the above formula), acrylic acid, and methacrylic acid. No. The acrylic acid and / or methacrylic acid is preferably 2 to 20% by weight, particularly 3 to 17% by weight, based on 100% by weight of the total amount of the monomers. Low and easy to apply
Further, a polishing agent excellent in removability can be obtained. Further, when the content of acrylic acid or the like is 5 to 15% by weight, a polishing agent having excellent performance in all properties can be obtained.

The polymer (before ion-crosslinking or ion-crosslinking)
Polymers and do not have down crosslinked) "is a homopolymer or copolymer consisting of the monomer, the weight average molecular weight of ultra-high molecular weight of more than 1,000,000, particularly 150
Preferably, it has a molecular weight of 10,000 or more. This molecular weight is 1
If it is less than 100,000, the resulting polishes are inferior in black heel mark resistance, stain resistance, abrasion resistance and the like. The acid value of the vinyl polymer is 10 to 150, especially 20 to 11
It is preferably 0, and if it is in this range, the removability at the time of repainting the polishing agent is excellent, and the viscosity of the polishing agent does not become too high, thereby facilitating the coating operation. Further, when the acid value is 30 to 100, a polisher having excellent performance in all properties can be obtained. The weight-average molecular weight was measured using Shodex manufactured by Showa Denko KK as a column.
Using A-80M, LC- manufactured by JASCO Corporation
It was measured by 800 system high performance liquid chromatography. The obtained molecular weight is in terms of polystyrene. The acid value was determined by dissolving the polymer in acetone and titrating with N / 10 ethanol potassium standard solution using phenolphthalein as an indicator.

In the present invention, the polymer is used as an emulsion. The emulsion may be prepared by suspending the obtained polymer in water or an appropriate solvent, but a method of directly emulsion-polymerizing a vinyl monomer or the like by emulsion polymerization is more preferable. The emulsifier used for the emulsion polymerization is not particularly limited, and it is effective to use a small amount of the polymerization initiator in order to increase the molecular weight of the polymer. The reaction temperature may be at least the decomposition temperature of the polymerization initiator, but is preferably 30 to 50C. The polymerization reaction is
A predetermined amount of the monomer is allowed to proceed while dripping into a reaction vessel charged with water, an emulsifier, an initiator and the like. It is advantageous to add a metal crosslinking agent to the resulting emulsion, as is known.

Using the emulsion obtained as described above, a floor polisher is prepared. The preparation can be carried out in the same manner as in the prior art.
It is preferable to use a mixture of wax emulsions containing paraffin wax, polyethylene wax, carnauba wax and the like, because the black heel mark resistance is further improved. In this case, the two emulsions are preferably mixed so that the solid content weight ratio of the polymer and the “wax” is 1: 0.1 to 0.3, and the weight ratio of the wax is within the above range. A glazing agent having sufficient black heel mark resistance and abrasion resistance is obtained.

In the emulsion for obtaining the floor polish of the present invention, components other than those described above can be added as necessary. Such components include alkali-soluble resins such as styrene-maleic acid copolymers, plasticizers such as dibutyl phthalate and tributoxyethyl phosphate, coalescing agents such as diethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and fluorine-based surfactants. Agents, defoaming agents such as silicones, preservatives such as formalin, etc., and their optimum blending ratio is determined by taking into account the place of use of the polishing agent, required performance, etc.
It can be determined by appropriately preparing a polishing agent.

[0014]

The floor glazing agent of the present invention is used for floors such as plastic flooring such as vinyl floor tiles and vinyl flooring sheets, wood flooring such as flooring, and stone flooring such as marble. It can be applied once or several times to the floor and dried to remove the medium and form a resin film. The resulting film is excellent in gloss and durability and is tough, and the formed film can be easily removed by a physical or chemical method after reaching the use limit.

[0015]

The present invention will be described below more specifically with reference to examples and comparative examples. In the following examples and comparative examples, parts represent parts by weight, and% represents% by weight. (1) Production of Polymer Emulsion Production Example 1 (Emulsion a) 500 parts of deionized water, 10 parts of sodium lauryl sulfate were placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and a nitrogen introduction pipe. 20 parts of a 30 mol adduct of nonylphenol with ethylene oxide, 1.0 part of a reducing agent (sodium thiosulfate) and 0.01 part of copper sulfate were added, and the mixture was stirred while bubbling nitrogen through to remove dissolved oxygen in the water. Thereafter, the mixture was heated to 40 ° C. in a water bath, the reaction temperature was kept at 40 ° C., and the monomer 3 having the composition shown in column A of Table 1 was used.
70 parts were dropped at a substantially constant flow rate over 2 hours. At the same time, a polymerization initiator aqueous solution (0.1 part of potassium persulfate dissolved in 60 parts of ion-exchanged water) prepared in a separate container was dropped at an almost constant flow rate over 3 hours. After dropping, at 40 ° C,
An aqueous solution of a polymerization initiator (0.1 part of potassium persulfate dissolved in 40 parts of ion-exchanged water) was added dropwise at a substantially constant flow rate over 2 hours, and the mixture was aged to complete the reaction. The obtained emulsion a had a nonvolatile content of 40%, a weight average molecular weight of the polymer of 1.8 million, and an acid value of 65.

Production Example 2 (Emulsion b) An emulsion was produced in the same manner as in Production Example 1 except that a monomer having the composition shown in column B of Table 1 was used. The nonvolatile content of the obtained emulsion b was 40%, the weight average molecular weight of the polymer was 1.6 million, and the acid value was 33. Production Example 3 (Emulsion c) An emulsion was produced in the same manner as in Production Example 1 except that a monomer having a composition shown in column C of Table 1 was used. The nonvolatile content of the obtained emulsion c was 40%, the weight average molecular weight of the polymer was 1.7 million, and the acid value was 98.

Production Example 4 (Emulsion d) An emulsion was produced in the same manner as in Production Example 1, except that 0.05 parts of potassium persulfate in the polymerization initiator aqueous solution was used. The non-volatile content of the obtained emulsion d was 40%, the weight average molecular weight of the polymer was 2.6 million, and the acid value was 65. Production Example 5 (Emulsion e) An emulsion was produced in the same manner as in Production Example 1 except that the amount of potassium persulfate in the aqueous polymerization initiator solution was changed to 0.03 part. The obtained emulsion e had a nonvolatile content of 40%, a weight average molecular weight of the polymer of 3.2 million, and an acid value of 65.

Production Example 6 (Emulsion f) An emulsion was produced in the same manner as in Production Example 1 except that a monomer having a composition shown in column D of Table 1 was used. The resulting emulsion f had a nonvolatile content of 40%, a weight average molecular weight of the polymer of 1.7 million, and an acid value of 7. Production Example 7 (Emulsion g) An emulsion was produced in the same manner as in Production Example 1 except that a monomer having a composition shown in column E of Table 1 was used. The nonvolatile content of the obtained emulsion g was 40%, the weight average molecular weight of the polymer was 1.7 million, and the acid value was 160.

Comparative Production Example 1 (Emulsion h) An emulsion was produced in the same manner as in Production Example 1, except that potassium persulfate in the aqueous polymerization initiator solution was changed to 0.2 part.
The nonvolatile content of the obtained emulsion h was 40%, and the weight average molecular weight of the polymer was 980,000. Comparative Production Example 2 (Emulsion i) An emulsion was produced in the same manner as in Production Example 1 except that the amount of potassium persulfate in the polymerization initiator aqueous solution was changed to 0.3 part.
The non-volatile content of the obtained emulsion i was 40%, and the weight average molecular weight of the polymer was 520,000.

Comparative Production Example 3 (Emulsion j) An emulsion was produced in the same manner as in Production Example 1 except that the amount of potassium persulfate in the aqueous polymerization initiator solution was changed to 1.0 part.
The nonvolatile content of the obtained emulsion j was 40%, and the weight average molecular weight of the polymer was 180,000. Comparative Production Example 4 (Emulsion k) An emulsion was produced in the same manner as in Production Example 2 except that the amount of potassium persulfate in the aqueous polymerization initiator solution was changed to 0.3 part.
The nonvolatile content of the obtained emulsion k was 40%, and the weight average molecular weight of the polymer was 480,000. Comparative Production Example 5 (Emulsion 1) An emulsion was produced in the same manner as in Production Example 3 except that the amount of potassium persulfate in the aqueous polymerization initiator solution was changed to 0.3 part.
The obtained emulsion 1 had a nonvolatile content of 40% and a weight average molecular weight of the polymer of 450,000.

[0021]

[Table 1]

(2) Preparation of floor polishes Using emulsions a to l, floor polishes were prepared as follows. Example 1 320 parts of emulsion a and 3 parts of water were placed in a container equipped with a stirrer.
After adding and stirring 00 parts, 40 parts of the following zinc ammonium carbonate complex solution was added, and after further stirring, 50 parts of the following wax emulsion, 80 parts of an aqueous alkali-soluble resin solution, 20 parts of tributoxyethyl phosphate, 20 parts of diethylene glycol 40 parts of monoethyl ether, 0.5 part of a fluorine-based surfactant (trade name “Rhodein S-100” manufactured by Ciba Geigy), and formalin (preservative)
0.5 parts were sequentially added and stirred. Then, water for adjustment was added so that the finish was 1000 parts, thereby preparing a polisher for floor.

Zinc ammonium carbonate complex solution: prepared by adding 7 parts of zinc oxide, 12 parts of ammonium carbonate and 14 parts of aqueous ammonia to 67 parts of water and stirring. Wax emulsion: A polyethylene wax (trade name “AC-392” manufactured by Allied Chemical Co., Ltd.) was emulsified using polyoxyethylene nonylphenyl ether.
The polyethylene wax in the emulsion is 30%. Aqueous solution of alkali-soluble resin: "SMA2625A" (styrene-maleic anhydride copolymer) manufactured by Alcochemical Co., Ltd. was dissolved using aqueous ammonia. The effective resin component is 15%.

Example 2 Using the emulsion a, the wax emulsion was
A polisher for floor was prepared in the same manner as in Example 1 except that the parts were used. Example 3 A floor polish was prepared in the same manner as in Example 1, except that the emulsion b was used and the zinc ammonium carbonate complex solution was changed to 20 parts.

Example 4 A floor polisher was prepared in the same manner as in Example 1 except that the emulsion c was used and the zinc ammonium carbonate complex solution was changed to 60 parts. Example 5 A floor polish was prepared in the same manner as in Example 1 except that the emulsion d was used. Example 6 A floor polish was prepared in the same manner as in Example 1 except that the emulsion e was used.

Example 7 A floor polish was prepared in the same manner as in Example 1 except that the emulsion f was used and the zinc ammonium carbonate complex solution was changed to 4 parts. Example 8 A floor polish was prepared in the same manner as in Example 1 except that the emulsion g was used and the amount of the zinc ammonium carbonate complex solution was changed to 100 parts.

Example 9 A floor polish was prepared in the same manner as in Example 1 except that the wax emulsion was used in an amount of 35 parts. Example 10 Example 1 except that the wax emulsion was changed to 140 parts.
A polisher for floor was prepared in the same manner as described above.

Comparative Example 1 A floor polish was prepared in the same manner as in Example 1 except that the emulsion h was used. Comparative Example 2 A floor polish was prepared in the same manner as in Example 1 except that the emulsion i was used. Comparative Example 3 A floor polish was prepared in the same manner as in Example 2 except that emulsion j was used.

Comparative Example 4 A floor polish was prepared in the same manner as in Example 3 except that emulsion k was used. Comparative Example 5 A floor polish was prepared in the same manner as in Example 4 except that the emulsion 1 was used. As described above, the compositions of the floor polishes of Examples are shown in Tables 2 and 3.
Table 4 shows the composition of the floor polish of each comparative example. In addition, in Tables 2 to 4, the parenthesis of each emulsion represents (weight average molecular weight / acid value) of the polymer.

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

(3) Performance Evaluation of Floor Polishing Agent The following performances were evaluated according to JIS K 3920. Regarding stain resistance and wear resistance, Akira Takeda et al.
"Environmental Management No.5", Japan Society for Environmental Management, 199
The evaluation was made with reference to 0.11, pages 97 and 98. Storage stability: JIS K 3920 12 Glossiness: JIS K 3920 14 (3 coatings, 6
(0 degree specular gloss) Black heel mark resistance: 15 of JIS K 3920 (heel mark adhesion amount: ；; almost none, ；: small, Δ; slightly large, ×; large)

Slip resistance: 16 according to JIS K 3920 (applied three times, left for 4 days, measured temperature: 25 ° C.
Humidity: 65%) Water resistance: 17 of JIS K 3920 Detergent resistance: 18 of JIS K 3920 Removability: 19 precision method of JIS K 3920 Stain resistance: White glazing agent for white vinyl tiles three times It was applied and immediately laid in the corridor, and the lightness difference (ΔL) with time before and after the walking test was determined and evaluated. The larger the difference in lightness (the larger the decrease in lightness), the stronger the degree of darkening and the more the contamination. The degree of darkening was visually evaluated. Walking days = 14 days. Degree of darkening: ◎; almost none, ○: small, Δ; slightly large, ×; large Abrasion resistance: apply a glazing agent for floor to white homogeneous vinyl tile three times, immediately lay it in the hallway, and walk test The difference (ΔG) in glossiness before and after aging was determined. ΔG
(The greater the decrease in glossiness), the more the scratches and the lower the abrasion resistance. The degree of abrasion was visually evaluated. Walking days = 14 days. Scratch condition: ；; almost none, ；: little, Δ; slightly more, ×; more The above evaluation results are shown in Table 5 for each example and Table 6 for a comparative example.

[0035]

[Table 5]

[0036]

[Table 6]

According to the results shown in Table 5, the floor polishes of Examples 1 to 6 were excellent in black heel mark resistance, stain resistance, etc., and also excellent in removability, and were very high quality polishes. It turns out that it is an agent. Further, in Example 7 in which the acid value of the polymer was as low as 7, although the removability was slightly difficult, other properties were very excellent, and in Example 8 in which the acid value was as high as 160, water resistance, Although the detergent resistance is slightly inferior, the other properties are excellent, and it can be seen that all of them are sufficiently usable. Further, the weight ratio of wax to polymer 1 is 0.0
In Example 9 as low as 8, the black heel mark resistance was slightly inferior and the weight ratio of wax was as high as 0.33 in Example 10.
In this case, although the abrasion resistance is slightly inferior, it can be seen that each of them has a practically no problem.

On the other hand, according to the results in Table 6, although the composition of the polishing agent was slightly different, in Comparative Example 1 in which the weight average molecular weight was slightly lower than 980,000 and 1,000,000, the black heel mark resistance and the abrasion resistance And Comparative Examples 2, 4 and 5 having low molecular weights of 520,000, 480,000 and 450,000, respectively, are inferior in black heel mark resistance, stain resistance and abrasion resistance, In Comparative Example 3 having a very low molecular weight of 180,000, the black heel mark resistance, stain resistance, and abrasion resistance were further reduced, and it was found that the compound could not be used.

[0039]

The floor polishes of the first invention are excellent in various properties required for floor polishes, such as black heel mark resistance, abrasion resistance and stain resistance, and reach the limit of use. When it is done, it is easy to peel off from the floor surface, and repainting work is also easy. Further, in the second invention and the third invention, the polymer of the first invention is copolymerized with a specific amount of acrylic acid or the like as a comonomer, and the acid value is set in a specific range, thereby providing a floor material having more excellent performance. Polishing agents can be obtained. Further, in the fourth invention, a higher-performance polishing agent can be obtained by using a specific amount of wax in combination with the polymer.

────────────────────────────────────────────────── (5) References JP-A-53-39987 (JP, A) JP-A-54-32188 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09G 1/16 C09G 1/10

Claims (4)

(57) [Claims] 1. A polymer comprising a monomer having a CH ₂ ＣCX— group (X is hydrogen or a methyl group) (before ion-crosslinking)
Or a polymer which is not ion-crosslinked) , wherein the weight average molecular weight of the polymer exceeds 1,000,000. 2. The floor polisher according to claim 1, wherein the total amount of the monomers is 100% by weight, and 2 to 20% by weight is acrylic acid and / or methacrylic acid. 3. The floor glazing agent according to claim 1, wherein the acid value of the polymer is from 10 to 150. 4. The floor polishing agent according to claim 1, wherein the floor polishing agent contains a wax in a weight ratio of 1: 0.1 to 0.3 with respect to the polymer. Agent.