JP2549288B2 - Floor covering - Google Patents

Description

TECHNICAL FIELD The present invention relates to a floor coating agent.

The coating composition is mainly used for coating a floor surface or the like and then drying it to form a coating, which keeps the appearance of the floor, prevents water stains, and protects the substrate. The composition can be widely used as a coating material for a wooden flooring material or a chemical flooring material using a raw material of a synthetic resin.

[Conventional technology]

As a conventional floor coating agent, a synthetic resin such as styrene, acryl, vinyl chloride, polyester, epoxy resin or various copolymers thereof is dissolved in a solvent such as thinner and applied to the floor by roll coating or brush coating. The form is widely used.

On the other hand, 90% or more of the floor coverings are chemical floor coverings that use synthetic resins. However, the main raw material for chemical flooring is
Since it is a synthetic resin such as vinyl asbestos resin, vinyl chloride resin, and asphalt, the solvent in the floor covering composition,
That is, the petroleum-based and naphthene-based solvents have the drawback of dissolving and deteriorating the chemical flooring material. Further, such a coating composition has high toxicity to workers and danger to fire. Therefore, the floor covering composition has been changed to an emulsion type using a water-based solvent as a solvent, and a styrene resin emulsion, a styrene-acrylic copolymer emulsion, and an acrylic resin emulsion have been developed. However, the hardness of the emulsion rises slowly, and it takes about one week to completely harden the emulsion, and the coating is contaminated during that time.

[Problems to be solved by the invention]

The present inventor studied a coating material composition using a UV curable resin in order to obtain a floor coating material having various performances superior to those of the emulsion type. As a result, it was confirmed that the UV curable resin currently on the market as it is cannot be used as a floor coating agent for the following reasons.

That is, the coated floor will be scratched by many pedestrians for a long time with any durable coating.
It is unavoidable that stains, abrasion, and yellowing and deterioration due to ultraviolet rays occur. Therefore, from the viewpoint of aesthetics and protection of the floor, it is necessary to remove or peel the coating agent after a certain period of time. However, after coating the floor of UV curable resin, irradiating it with UV, and curing it completely, the film has 3 molecules.
It is tough because it is dimensionally crosslinked, and as a result, it is not easy to peel from the floor. If a solvent having a strong dissolving power is used for peeling, the chemical flooring material will also be dissolved. Also, removal by mechanical polishing results in damaging the flooring material.

Then, the objective of this invention is maintaining the outstanding performance of UV curable resin, and providing the coating material which has the following characteristics (1)-(3).

(1) It is easy to apply to various objects, especially floors, and the coating film formed after UV irradiation for several seconds has toughness and excellent durability in an instant.

(2) If the coating is lightly soiled, it should be possible to wash and remove the soiling on the surface of the coating using a weak alkaline detergent.

(3) When a long time has passed after application and dirt is taken into the coating and the coating turns yellow, it is washed and peeled off using a strong alkaline detergent containing ammonia or amine. Be able to do it.

[Means for solving problems]

The present invention relates to a UV-curable floor coating containing an aqueous urethane photopolymerizable prepolymer having a carboxylate group neutralized with an amine-based substance and / or ammonia, a photoinitiator, and water as a solvent. Regarding agents.

 The present invention will be described below.

The "photopolymerizable prepolymer having a carboxylic acid group and / or a carboxylic acid group" in the present invention means, for example, a compound having a carboxylic acid group such as acrylic acid, methacrylic acid, itaconic acid, succinic acid, adipic acid and phthalic acid. Is a polymer or copolymer obtained by polymerizing or copolymerizing with another monomer and, if necessary, neutralizing the carboxylic acid group. Examples of such polymers or copolymers include polyacrylate, polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, polyol acrylate and the like.

As the photopolymerizable prepolymer in the present invention, various polymers including the above-mentioned polymers and copolymers can be used without particularly limiting the molecular weight and the molecular structure.

The base forming the carboxylate contained in the photopolymerizable prepolymer in the present invention is preferably a substance that is relatively easily volatilized, such as an amine-based substance or ammonia.

The amount of carboxylic acid and / or carboxylic acid salt contained in the photopolymerizable prepolymer can be expressed as an acid value.
In the present invention, the acid value range of the photopolymerizable prepolymer is suitably 10 to 200, preferably 30 to 130. The acid value means m of KOH per 1 g of prepolymer solid content.
is the number of g.

A coating film formed using a composition containing a photopolymerizable prepolymer having an acid value of less than 10 tends to have a slightly inferior releasability.

On the other hand, a coating formed using a composition containing a photopolymerizable prepolymer having an acid value of more than 200 tends to have poor water resistance and detergent resistance. However, by blending a photopolymerizable prepolymer having an acid value of less than 10 or more than 200 and another photopolymerizable prepolymer, those having an acid value in the range of 10 to 300 are well used in the composition of the present invention. be able to.

As the "photoinitiator" used in the present invention, those conventionally known can be used as they are without any problem. For example, either a radical reaction type photoinitiator or an ion reaction type photoinitiator can be used, and examples thereof include a carbonyl compound, a sulfur compound and an azo compound. Specifically, biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoisobutyl ether, benzyl dimethyl ketal, tetramethyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, di-tett-butyl peroxide, 1-hydroxy. Cyclohexyl phenyl ketone, 2-chlorothioxanthone, methyl benzoyl formate, etc. are mentioned. However, it is not limited to these.

A solvent may be added to the composition of the present invention in addition to the photopolymerizable prepolymer and the photoinitiator. Examples of the solvent include photopolymerizable monomers and water. As the photopolymerizable monomer, either a monofunctional monomer or a polyfunctional monomer can be used. The photopolymerizable monomer is also referred to as a reactive diluent and, after UV curing, becomes a part of the structure of the cured product and does not go out of the system, and the UV curable resin can be solventless. The photopolymerizable monomer is exemplified below.

(1) Monofunctional 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acroyl phosphate, tetrahydrofurfryl acrylate, etc. (2) Bifunctional dicyclopentenyl acrylate, 13-butanediol diacrylate, diethylene glycol acrylate, Polyethylene glycol 400 diacrylate, tripropylene glycol diacrylate, etc. (3) Trifunctional or higher trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, etc. Incidentally, the photopolymerizable monomer may be carboxylic acid and / or
Alternatively, it may have a carboxylate group. The acid value of the photopolymerizable prepolymer can be adjusted by using a photopolymerizable monomer having a carboxylic acid (salt).

The composition of the present invention can be made into a system in which a photopolymerizable prepolymer is emulsified in water by using water as a solvent. Depending on the base material and maintenance conditions, an emulsion type may be preferable, and in such a case, it can be used properly.

Further, the composition of the present invention may contain a synthetic resin (including an alkali-soluble resin) other than the photopolymerizable prepolymer. The synthetic resin can be used properly according to the type of the photopolymerizable prepolymer. In a system using a photopolymerizable monomer, a synthetic resin is generally used by dissolving it in the photopolymerizable monomer. Further, in the system in which the photopolymerizable prepolymer is emulsified,
It is suitable that the synthetic resin is also used in a water-solubilized or emulsified state.

As the synthetic resin, for example, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, ethylene, obtained by copolymerizing at least one or more vinyl monomers such as propylene The synthetic resin can be mentioned. Representative examples of the alkali-soluble resin include styrene-maleic acid copolymer resin, rosin-maleic acid copolymer resin, water-soluble acrylic resin, water-soluble polyester resin and water-soluble epoxy resin. Various additives can be added to the composition of the present invention, if desired.

For example, when the minimum film forming temperature of the composition of the present invention is room temperature or higher, it is preferable to add a fusing agent, a plasticizer, or the like in order to enable the film to be formed at room temperature. Examples of the fusing agent and the plasticizer include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, N-methyl-2pyrrolidone, dibutyl phthalate and tributoxyethyl phosphate. You can

However, it goes without saying that it is not necessary to use these fusing agents and plasticizers for the composition capable of forming a film at room temperature.

Further, a surfactant can be appropriately used in consideration of the stability of the composition of the present invention, the wettability when applied to a substrate, and the like. Further, if it is necessary to improve the black heel mark resistance, additives such as a slip agent and a leveling agent may be added.

Furthermore, the film formed using the composition of the present invention can be easily removed chemically without resorting to mechanical polishing. That is, the coating can be easily removed by treating it with a removal solution. The removal solution usable in the present invention is, for example, an alkaline solution containing a surfactant. Examples of the alkaline solution include those containing, as an alkaline substance, ammonia, amine, caustic soda, caustic potassium, sodium metasilicate, sodium orthosilicate, potassium silicate, sodium pyrophosphate, potassium pyrophosphate, potassium triphosphate and the like. it can. Further, the surfactant includes, for example, anionic type (higher alcohol sulfate ester salt, fatty acid salt, alkylbenzene sulfonate, polyoxyethylene ether sulfate salt, etc.), nonionic type (polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether). , Polyoxyethylene acyl ether, etc.) and amphoteric (eg, alkyl betaine) surfactants.

Hereinafter, the present invention will be described in more detail with reference to Examples. The amount of each component in each table of Examples and Comparative Examples is shown in parts by weight.

Reference Example 1 (Production of Polymerizable Prepolymer) (1) Acrylic Prepolymer After filling a three-necked flask equipped with a thermometer, a reflux and a dropping funnel with nitrogen, 25 parts by weight of toluene was added to 60 ° C. in an oil bath. Heated. Table 1 shows the remaining 25 parts by weight of toluene.
The toluene solution obtained by dissolving 2-hydroxyethyl acrylate, acrylic acid, and methyl methacrylate in the amounts described in 1 above was continuously added to toluene in the flask from a dropping funnel to start polymerization.

After completion of the polymerization, while maintaining the reactor at 100 ° C., the amount of glycidyl methacrylate described in Table 1 was added to the obtained polymer, reacted with the hydroxyl group (—OH) in 2-hydroxyethyl acrylate, and then depressurized. The toluene was removed to obtain acrylic prepolymers A, B and C.

(2) Aqueous urethane prepolymer Amount of polytetramethylene ether glycol (molecular weight 1000), tolylene diisocyanate or dicyclohexylmethane diisocyanate, dimethylolpropionic acid and toluene in the amounts shown in Table 2 are reflux condensers, thermometers, and stirring devices. I took it to the equipped reactor. The urethanization reaction was carried out while maintaining the reactor at 100 ° C. Then, while maintaining the temperature of the reactor at 80 ° C., 2-hydroxyethyl acrylate in an amount shown in Table 2 was continuously added to the reaction mixture so that the hydroxyl group (—OH) in 2-hydroxyethyl acrylate and the urethanization reaction product were free. A prepolymer was produced by reacting with (-NCO). Then, triethylamine was added to neutralize the reaction product, and then distilled water was added to obtain aqueous urethane prepolymers D, E, and F.

Examples 1 to 15 The photopolymerizable prepolymer prepared in Reference Example 1, a photoinitiator, a photopolymerizable monomer, additives such as diethylene glycol monoethyl ether, and water were stirred and mixed at a mixing ratio shown in Table 3. , The compositions of the present invention (Examples 1 to 15) were obtained.

After applying the obtained compositions (Examples 1 to 15) to a substrate, UV irradiation (340 to 460n) was performed for 3 seconds using a Handy Cure Lab (UV irradiation device, HLR-100T) manufactured by Sen Special Light Source Co., Ltd.
m) was performed to obtain a coating. Various performance evaluations (storage stability, water resistance, removability, detergent resistance, leveling property, black heel mark resistance, abrasion resistance, durability, hardness rising property) of the obtained coating film were performed. The results are shown in Table 4.

Comparative Examples 1 to 5 Performance evaluation was performed on the compositions using the non-oxidizing photopolymerizable prepolymers shown in Table 3 and the aqueous acrylic floor polishes (Comparative Examples 1 to 5) currently used in the general market. The results are shown in Table 4.

In addition, only in Comparative Example 1, as in Examples 1 to 15,
UV irradiation (340 to 460 nm) was performed to evaluate the performance. For Comparative Examples 2 to 5, performance evaluation was performed after drying at room temperature.

Epoxy resin with the epoxy group esterified with acrylic acid to make the functional group an acryloyl group.

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

(Note-3) Oxidation type polyethylene wax emulsion Oxidation type polyethylene wax manufactured by Allied Chemical Co., USA, trade name AC-392, acid value 40, softening point 138 ° C, penetration less than 0.5 (ASTM D5), nonionic surface active. A polyethylene wax emulsion containing 40% of the active ingredient emulsified with an agent.

(Note-4) Styrene-maleic acid copolymer aqueous solution manufactured by Arco Chemical Company, USA, trade name SMA2625A, acid value 22
A 20% aqueous solution of a styrene-maleic acid copolymer resin having a molecular weight of 1900 and dissolved with ammonia.

(Note-5) Fluorocarbon surfactant, manufactured by Sumitomo 3M Limited, fluorocarbon surfactant, trade name Fc-120, anionic.

The active ingredient in Note 2 to 4 indicates the content rate (concentration) of each resin, and its unit is% by weight.

[Performance Test Method and Comparative Performance Evaluation] The floor covering test methods of Test Methods 1 and 2 were performed according to the Japan Floor Polish Industry Association JFPA standard.

In addition, the test method of performance not specified in the standard (removability,
For the detergent resistance, leveling property, recoatability, black heel mark resistance, abrasion resistance, and durability), a performance test was performed and evaluated by the following methods.

1. Storage stability Put about 100 ml of sample into a vertical cylindrical, uncolored bottle of about 120 ml and stopper tightly. After storing in an incubator at a temperature of 45 ± 2 ° C for 24 hours, check for layer separation.

2. Water resistant JFPA standard test standard tile (vinyl asbestos tile)
Apply the sample to 10 ± 2 ml per square meter. The coated test piece is allowed to stand overnight at room temperature with a relative humidity of 80% or less. Rest the test piece on a horizontal surface of 23 ± 10 ℃, add 0.1 ml of distilled water and cover it with a cover glass. 3
After standing for 0 minutes, absorb the water and let it stand for 1 hour, and visually measure the whitening state.

3. Removability The test piece applied according to the water resistance measurement method is 38 ± 2
After leaving it in the incubator at ℃ for 6 hours and immersing it in distilled water at room temperature for 1 hour, take out the test piece and put it in the incubator at 38 ± 2 ℃ for 18 hours.
Leave for hours. The stripper is 5.00g potassium hydroxide (KOH85
%) And 17.7 g oleic acid in 50 ml ammonia water (NH ₄ OH
(28%) containing 1000 ml of distilled water dissolved in distilled water, soak the pork bristle brush of Guard Donor Straight Line Washability Tester in the stripping solution for 2 minutes,
Pour 10 ± 2 ml onto the test piece and soak for 5 minutes to start the test. After reciprocating 200 times, the test piece was rinsed with clean water and then judged whether it was completely removed. The washability tester is based on ASTM-D-1792-66.

4. Detergent resistance The test piece applied according to the water resistance measurement method is 38 ± 2
Leave for 18 hours in a constant temperature oven. The cleaning solution was 0.1 g of sodium dodecylbenzene sulfonate and 0.2 g of sodium tripolyphosphate dissolved in 200 ml of distilled water (pH 9.0 ±
0.2), soak a pig donor brush of Guard Donor Straight Line Washability Tester in the stripping solution for 2 minutes, then pour 10 ± 2 ml on the test piece and start the test after soaking for 5 minutes. After 100 round trips, the test piece is rinsed with fresh water, air-dried and evaluated. Related Standards ASTM-D-3207-73 5. Leveling Property The leveling state of the test piece applied according to the water resistance measurement method is visually evaluated.

6. Black heel mark resistance 24 test pieces applied to JFPA standard test standard white tiles (vinyl asbestos tiles) according to the water resistance measurement method.
After drying at room temperature for an hour, the test piece is screwed to the mounting surface of a Snell type dirty capsule containing 6 pieces of 30 × 30 mm square rubber and rotated in both directions at a speed of 50 rpm for 2.5 minutes each. The amount of black heel marks attached to the tile is visually observed and evaluated.

7. Wear resistance A test piece coated five times by the same operation method as the water resistance measurement is left to dry at room temperature for 168 hours, and then left to wear with a Taber tester (wear wheel CS-17, load 1000g). Is measured and evaluated.

8. Durability The overall performance is evaluated based on the water resistance, abrasion resistance, and black heel mark resistance.

〔The invention's effect〕

The composition of the present invention is capable of instantaneously forming a tough and durable coating film by UV irradiation for several seconds. Further, when the surface of the obtained coating film becomes dirty, only the surface dirt can be appropriately washed and removed. When the entire coating film is contaminated, a beautiful coating film can be formed by peeling the floor surface without damaging it and then newly applying the composition of the present invention.

Claims (1)

(57) [Claims] 1. A UV curable floor containing an aqueous urethane photopolymerizable prepolymer having a carboxylate group neutralized with an amine substance and / or ammonia, a photoinitiator, and water as a solvent. Coating agent.