JPS62205168A - Releasable coating agent composition - Google Patents

Abstract

PURPOSE:The titled composition suitable as floor covering materials, etc., having improved luster, wear resistance, black heal mark properties, water resistance and adhesivity, containing an aqueous resin composition and a specific polyurethane resin. CONSTITUTION:The aimed composition containing (A) an aqueous resin composition (e.g., synthetic emulsion, aqueous urethane resin having low acid value, etc.,) and (B) polyurethane resin containing a carboxylic acid and/or carboxylate, having 40-200, preferably 60-120 acid value.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to removable coating compositions. More specifically, the present invention relates to a removable water-based urethane resin coating composition that has improved adhesion and leveling properties by adding a polyurethane resin containing a carboxylic acid and/or a carboxylic acid salt to the water-based resin composition.

[Industrial application field]

Coating compositions are mainly used to form a coating by coating and drying on floors, etc., to maintain the aesthetic appearance of floors, prevent water stains, and protect base materials. It is widely used as a coating for wooden flooring or chemical flooring made from synthetic resin raw materials.

[Conventional technology]

In the past, floor coverings were commonly used on wooden floors by applying wax components such as paraffin wax or carnauba wax dissolved in turpentine oil to the floor surface, letting it dry and then wiping it dry. However, those using wax wax have the disadvantage that the desired performance cannot be obtained at all in terms of durability. Therefore, synthetic resins that have been created through the development of chemical technology in recent years, such as styrene resins, acrylic resins, vinyl chloride resins, polyester resins, epoxy resins, and various copolymers thereof, have been developed as floor covering materials that can improve these defects. A method in which a resin is dissolved in a solvent such as thinner and applied to the floor by rolling, brushing, or the like is becoming widely used. On the other hand, the progress and development of flooring materials to be coated has been remarkable, and from the early 1950s wooden flooring materials in homes and commercial buildings such as offices changed from wooden flooring materials to chemical flooring materials using synthetic resin raw materials. More than 90% of the flooring materials used in Japan are chemical flooring materials. However, since the main raw materials of chemical flooring materials are synthetic resins such as vinyl asbeth, vinyl chloride resin, and asphalt, the solvents in the floor coating composition, i.e., petroleum-based and naphthenic solvents, are not suitable for chemical flooring. It had the disadvantage of melting and deteriorating the material. Furthermore, due to the toxicity to workers during work and the risk of fire, floor coating compositions changed to emulsion-based compositions that use water-based solvents. For these reasons, the progress and development of synthetic resin emulsion coating compositions began in the mid-1930s, with improvements being made to styrene resin emulsions, styrene-acrylic copolymer resin emulsions, and acrylic resin emulsions. However, these emulsion-based coatings have the disadvantage of poor adhesion and abrasion resistance, requiring frequent reapplication.

[Problem that the invention seeks to solve]

The present inventors investigated a coating composition using an aqueous polyurethane resin in order to obtain a floor coating having various properties even better than those of the emulsion type mentioned above. As a result, it was found that the water-based polyurethane resins currently on sale cannot be used as floor coverings for the following reasons. In other words, coated floor surfaces are exposed to a large number of pedestrians, and no matter how durable the coating material is, it is difficult to avoid scratches, dirt, and wear over time, as well as yellowing and deterioration caused by ultraviolet rays. I can't. Therefore, from the viewpoint of aesthetics and protection of the floor, it is absolutely necessary to remove, ie, peel off, the coating layer. However, after a water-based polyurethane resin is applied to the floor surface and completely cured, the film has excellent properties such as adhesion to the floor surface, gloss, and toughness. It is not easy to peel off using

If a solvent with strong dissolving power is used to remove the coating, the chemical flooring material will also be dissolved. Also,
Removal of the coating by mechanical abrasive forces of 1 inevitably results in damage to the flooring. Furthermore, when a water-based polyurethane resin with a high acid value that can be peeled is used, there is a drawback that water resistance deteriorates.

Therefore, the present inventors conducted various studies in order to obtain a coating material that maintains the excellent performance of aqueous polyurethane resin and has the following characteristics (1) to (3).

(1) It is easy to apply to various objects, especially floors, and the film formed is strong and has excellent durability. (2) If the film becomes slightly soiled, use a weak alkaline detergent. (3) If dirt is incorporated into the coating or the coating yellows after a long period of time after application, can be washed and removed using a strong alkaline detergent containing ammonia or an alkali metal salt.

As a result, by adding a polyurethane resin containing a carboxylic acid and/or a carboxylic acid salt and having an acid value of 40 to 200 to an aqueous resin composition, it is possible to peel off and form a glossy film with excellent water resistance and good leveling properties. They found a suitable coating composition and completed the present invention.

[Means to solve the problem]

The present invention provides a peelable water-based urethane resin that has improved adhesion and leveling properties by containing a polyurethane resin containing carboxylic acid and/or carboxylate and having an acid value of 40 to 200 in addition to the water-based resin composition. The present invention relates to coating compositions.

The present invention will be explained in detail below.

The 1″ aqueous resin composition of the present invention, referred to as J, contains at least one of acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, ethylene, propylene, etc. Synthetic resin emulsions obtained by copolymerizing vinyl monomers, low acid value aqueous urethane resins, water-soluble polyester resins, water-soluble epoxy resins, polyethylene-
Examples include waxes such as acrylic wax and polypropylene-acrylic wax, and mixtures thereof.

Furthermore, the well-known leveling improvers used to date as a component in coating compositions, namely styrene-maleic acid copolymers, rosin-maleic acid copolymers,
I/belling properties can also be improved by adding an alkali-soluble resin such as a high acid value, low molecular weight acrylic-styrene co-adhesive compound, a high acid value, low molecular weight acrylic ammonium salt, or an alkali metal salt. However, in this case, conventional adhesives have had poor adhesion to vinyl chloride resin flooring materials, particularly to soft vinyl chloride resins which are expected to become mainstream as flooring materials in the future. 7
However, in the present invention, as described above, by adding polyurethane resin to water-based resins containing these alkali-soluble resins, excellent adhesion can be achieved.
A coating composition can be produced which forms a coating with further improved novelability.

In the present invention, "polyurethane resin containing carboxylic acid and/or carboxylate salt-1" refers to a polyurethane resin in which carboxylic acid and/or carboxylate salt is bonded to the chain of the polyurethane resin. .

For example, in the production of (1) a polyurethane resin, a diol having a carboxylic acid group is added to a diol and a diisocyanate, and the carboxylic acid group is neutralized if necessary. (2) It is obtained by reacting a urethane prepolymer having an isocyanate group at the end with an excess of polyalkylpolyamine to produce a polyurethaneurea polyamine, and reacting it with a cyclic dicarboxylic acid anhydride. That is, a polyurethane resin can be made into a water-dispersible or water-soluble aqueous polyurethane resin by introducing a carboxylic acid group as described above.

Moreover, it is also possible to make it aqueous by adding an emulsifier as necessary.

In the present invention, an amine-based substance, ammonia, or an alkali metal is used as the base forming the carboxylic acid salt (contained in the polyurethane resin), but it is preferable to use an amine-based substance or ammonia, which is relatively easily volatile. good.

The amount of carboxylic acid and/or carboxylate contained in the polyurethane resin can be expressed as an acid value. The acid value range of the urethane +51 fat in the present invention is 40 to
200, preferably 60-120. The acid value referred to here is the number of mg of KOH per gram of resin solid content. When a coating composition containing a polyurethane resin with an acid value of less than 40 is applied, it is necessary to use a strong alkali to chemically remove it, which may damage some flooring materials. Furthermore, a coating formed using a coating composition containing a polyurethane resin having an acid value of more than 200 is inferior in reapplicability, water resistance, and detergent resistance.

However, even if the polyurethane resin has an acid value of less than 40 or more than 200, other polyurethane resins with different acid values may be added to reduce the overall acid value to 40 to 20.
Of course, if it is adjusted within the range of 0, it will be included in the polyurethane resin used in the composition of the present invention.

In addition, the molecular weight of the polyurethane resin in the present invention,
All kinds of urethane resins, aqueous polyurethane resin and acrylic acid, regardless of the molecule f+1 construction, manufacturing method (combination method, use of solvent or type of solvent),
An aqueous polyurethane copolymer resin copolymerized with at least one vinyl monomer such as acrylic acid ester, methacrylic acid, methacrylic ester, vinyl chloride, styrene, vinyl acetate, etc., and an aqueous polyurethane copolymer resin copolymerized with a copolymer of the above vinyl monomer. Aqueous polyurethane resins obtained by reaction with polyurethane resins can be used.

Note that various additives can be added to the composition of the present invention if desired. For example, when using an aqueous polyurethane resin whose minimum film formation temperature is room temperature or higher, it is preferable to add a coalescing agent, a plasticizer, etc. to enable film formation at room temperature.

Examples of coalescents and plasticizers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, N-methyl-2-pyrrolidone,
Examples include dibutyl phthalate and tributoxyethyl phosphate. However, it goes without saying that it is not necessary to use these coalescing agents and plasticizers for aqueous polyurethane resins that can form a film at room temperature.

Further, in order to form a tough film, for example, zinc ammonia carbonate, calcium carbonate ethylenediamine-ammonia, zinc ammonia acetate, zinc ammonia acrylate, etc. can be added to form a complex between carboxylic acid and metal to form a crosslink.

Furthermore, if it is desired to improve the stability of the aqueous polyurethane resin and the wettability when applied to a substrate, a surfactant can be used as appropriate.

When the coating composition of the present invention is used as a floor finish or polish, additives such as a slip agent may be added if necessary to improve black heel mark properties. The composition of the present invention lowers the surface tension with the substrate during application, contributes to improved wettability and leveling properties, forms a favorable film after application, and is effective when used as a coating material. Physical properties are significantly improved.

The composition of the present invention can be used on any substrate. For example, it can be used as a paint, a metal rust preventive, or as a polishing agent that can be removed using chemical action. The composition of the present invention using an aqueous urethane resin having an acid value in the range of 40 to 80 has particularly good water resistance,
It has excellent detergent resistance, low viscosity, and reapplicability, and is suitable for outdoor paints and resin waxes, as well as indoor paints and resin waxes for kitchens that use water, entrances where rainwater easily enters, etc.

In addition, compositions using aqueous urethane resins with acid values in the range of 120 to 200 have particularly excellent leveling properties, removability, etc.
It can be used on base materials that cannot be used with strong alkaline agents or solvents, such as wall and floor materials such as linoleum, rubber tiles, cork, and wood.

That is, even if the substrate is contaminated after being coated, it can be easily removed using a neutral or weak alkaline detergent without damaging the substrate.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, the "active ingredient" in Examples and Comparative Examples indicates the content rate (a degree) of each resin, and the unit is weight %.

Reference example [Manufacture of water-based polyurethane resin] (1) Polypropylene glycol (molecule 1l100
0)49. dicyclohexylmethane diisocyanate) 1
76 g of dimethylolpropionic acid, 70 g of dimethylolpropionic acid, and 196 g of N-methylpyrrolidone were placed in a reactor equipped with a reflux condenser, a thermometer, and a stirring device, and a urethanization reaction was carried out while maintaining the temperature at 80 to 100° C. to produce a prepolymer. .

Next, 48 g of triethylamine was added to the prepolymer to neutralize it, and then 5.0 g of hexamethylene diamine was added to the prepolymer.
and while adding distilled water, the temperature inside the reactor was raised to 35℃.
The polymerization reaction was carried out while maintaining the following conditions, and a total of 456 g of distilled water was added until the reaction was completed to obtain aqueous polyurethane resin C.

This aqueous polyurethane resin had an acid value of 98 per resin solid content.

(2) Water-based polyurethane resins A, B, D, and E using the raw materials and usage amounts shown in Table 1 in the same manner as (1).

F were produced respectively.

Examples 1 to 10 The aqueous urethane resins produced in Reference Examples A to F and other additives (slip agents), etc., were stirred and mixed into the aqueous resin composition in the proportions shown in Table 2 to prepare the composition of the present invention. (Examples 1-1
0) was obtained.

Comparative Examples 1 to 4 Compositions containing no aqueous urethane resin in the aqueous resin composition (
Comparative Examples 1 to 4) are shown in Table 2.

Various performance comparison evaluations (storage stability, gloss, water resistance, removability, detergent resistance, leveling property, repaintability, black resistance, etc.)
(heel mark resistance, abrasion resistance, adhesion). The results are shown in Table 3.

(Note-1) Acrylic resin emulsion monomer composition [
A polyacrylic resin emulsion consisting of 10% methacrylic acid, 30% butyl acrylate, and 60% methyl methacrylate, and having an acid value of 65 and an active ingredient of 40%, obtained by a conventional emulsion polymerization method using sodium lauryl sulfate.

(Note-2) Acrylic-styrene resin emulsion monomer composition [3% methacrylic acid, 40% ethyl acrylate, 37% methyl methacrylate, 20% styrene], obtained by a conventional emulsion polymerization method using sodium laurylbenzenesulfonate. A polyacrylic resin emulsion with an acid value of 20 and an active ingredient of 40%.

(Note-3) Oxidized type polyethylene wax emulsion manufactured by Allied Chemical Co., USA, oxidized type polyethylene wax, product name AC-392, oxidized 40, softening point 138°C, penetration less than 0.5 (ASTMD5), nonionic interface. Polystyrene wax emulsion with 40% active ingredient emulsified using an activator.

(Note-4) Styrene-maleic acid copolymer aqueous solution Manufactured by Alco Chemical Company, USA, product name 5M A2623A, acid value 220, molecular weight 1900 styrene-maleic acid copolymer Combined resin, dissolved using ammonia An aqueous solution containing 17% of the active ingredient.

(Note-5) Rosin-maleic acid copolymer aqueous solution manufactured by Ziegler Chemical & Mineral Co., USA, product name 1 ecoIac 802, acid value 200
, a rosin-maleic acid copolymer with a softening point of 175°C, which is an aqueous solution containing 17% of the active ingredient dissolved in ammonia.

(Note-6) Acrylic alkali-soluble resin Acrylic alkali-soluble resin manufactured by Rohm & Haas, USA, trade name Prifle B-644, solid content 42%, minimum film forming temperature 15°C.

(Note-7) Slip agent manufactured by Dow Corning Co., Ltd., silicone-based wear resistance imparting, flattening improver, trade name, Paintat F S X B -2725° [Performance test method and comparative performance evaluation] Test method 1 ~ The floor coating test method in No. 5 is based on Nippon Floor-・
This was done in accordance with the Polish Industry Association JFPA standards.

In addition, test methods for performance not specified in the standards (leveling property, reapplyability, black heel mark resistance, abrasion resistance, etc.)
Regarding durability), a performance test was conducted and evaluated using the following method.

1. Storage stability: Approximately 100 mj in a vertical cylindrical, uncolored bottle with a storage stability of approximately 120 mj'
' Add the sample and seal it tightly. After storing in a thermostat at a temperature of 45±2° C. for 24 hours, the presence or absence of layer separation is examined.

2. Apply the sample to a standard tile (vinyl asbestos tile) for glossiness JFPA standard testing at a concentration of 1O±2ml per square meter. After drying for 30 minutes at room temperature, the gloss is measured. Using the same method, apply three coats and five coats, and measure the gloss of each coat. Glossiness measuring device is JIS
-287411 basis, the angle of incidence is 60°.

3゜ A test piece coated according to the water resistance gloss measurement method is left overnight at room temperature with a relative temperature of 80% or less.

The test piece was placed on a horizontal fixed table at 23 ± 10°C, and
．． 1mj! of distilled water and cover with a cover glass for 30 minutes.
After allowing it to stand for a minute, absorb the water, leave it for an hour, and visually measure the degree of whitening.

4. A test piece coated according to the removability gloss measurement method was 38±2
After being left in a thermostat at 38±2°C for 6 hours and immersed in distilled water at room temperature for 1 hour, the test piece was taken out and left in a thermostat at 38±2°C for 18 hours.

The stripping solution was 3.97 g of potassium hydroxide (KO885%).
) and 17°7g of oleic acid 5m! Using soap water dissolved in too ml of distilled water containing ammonium water (NH40H28%) y'i-, soak the boar bristle brush of the Guard Donor Straight Line Washability Tester in the stripping solution for 2 minutes, and then Pour 2 ml onto the test piece and start the test immediately. After 25 reciprocations, the specimen is rinsed with clean water and then determined whether it has been completely removed.

For washability testers, please refer to ASTM-D
1792 66.

5. A test piece coated according to the detergent resistance gloss measurement method was 38±2
Leave in an incubator at °C for 18 hours. Washing i is O, 1g sodium dodecylbenzenesulfonate and 0.2g)
Using a cleaning solution (pH 9.0 ± 0.2) in which sodium lipolyphosphate was dissolved in 200 ml of distilled water, the boar bristle brush of the Guard Donor Straight Line Washability Tester was immersed in the stripping solution for 2 minutes, and then 10 ± 21 Tli
Pour onto the specimen and begin the test immediately. After reciprocating 100 times, the test piece was rinsed with clean water, air-dried, and evaluated.

The leveling state of the coated test piece is visually evaluated in accordance with the related standard ASTM-D-32076, leveling property, recoatability gloss measurement method. The reapplicability test is evaluated by visually observing whether the base is re-emulsified during the second application.

7. Black heel mark resistance A test piece was coated on a standard white tile (vinyl asbestos tile) for JFPΔ standard testing according to the gloss measurement method, and after drying at room temperature for 24 hours, 30 x 30111111
The test piece is screwed onto the mounting surface of a Snell-type dirt capsule containing six square rubber pieces, and rotated in both directions at a speed of 50 rpm for 2.5 minutes each. Visually observe and evaluate the amount of black heel marks attached to the tile.

8. Abrasion Resistance Using the same method as the gloss measurement method, the recently coated test piece is left to dry for 168 hours at room temperature, and then the degree of abrasion is measured and evaluated using a taper tester.

9. Adhesion Black heel mark resistance The top surface of the coating of the dried test piece was coated using the same method as the black heel mark resistance.
After making a cut so that there is a zero frame and adhering the cellophane tape to the top surface of the board, it is peeled off at once at an angle of 45° with the base material, and the number of parts of the board that has been peeled off is measured and expressed as a quantity.

〔Effect of the invention〕

As shown in Table 3, the composition of the present invention showed excellent evaluation in all performances. In particular, the presence or absence of polyurethane resin is determined in Example (1) (2) and Comparative Example (1) (2).
This is clear when comparing the results with That is, the composition of the present invention has excellent gloss, abrasion resistance, black heel mark resistance, water resistance, and adhesion. Example αO and 1 Comparative Example (4)
Comparison of the results shows that the removability and leveling properties can be significantly improved by using the polyurethane resin of the present invention.

Furthermore, from the results of Example (3) and Comparative Example (2), adding the polyurethane resin of the present invention to a composition containing a conventional leveling agent improves gloss, water resistance, detergent resistance, reapplyability, and resistance. It can be seen that black heel mark resistance and abrasion resistance are improved.

Claims (1)

[Claims] A removable aqueous urethane resin coating composition comprising an aqueous resin composition and a polyurethane resin containing a carboxylic acid and/or a carboxylic acid salt and having an acid value of 40 to 200.