JPS6052181B2 - Method for treating radiation-curable surface coatings and products thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to radiation curable coatings;
In particular, it relates to radiation curable coatings having excellent scratch resistance and easily cleanable surfaces.

Radiation curable and moisture curable coatings are well known in the art and are desirable because they provide finishes that tend to be tough and abrasion resistant.

Nevertheless, these surfaces develop scratches and gouges when subjected to wear, especially as floor coverings. Accordingly, much time and effort has been expended by the industry to develop materials that exhibit superior durability and cleanability. Various references describe UV curable coatings and compositions.

For example, U.S. Pat. No. 4,138,29 to Borgiano discloses (1) a urethane prepolymer essentially ending in -NCO but partially capped with a monohydric acrylate; (2) A liquid coating composition comprising an ethylenically unsaturated acrylate diluent is disclosed. The ethylene functionality is photopolymerized and the -NCO groups are cured with moisture to produce a tough, glossy coating. Tazuke et al.
Tazuke etal. ) U.S. Patent No. 3959521
No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, No. 1, 2003, 2003, discloses a method of applying a composition consisting of ethylenically unsaturated and free isocyanate to a substrate and irradiating it. A resin overcoat consisting of ethylenically unsaturated groups is then applied and the surface is irradiated again. McCan et al.
netal. ), US Pat. No. 4,100,318, discloses a floor covering comprising at least one organic compound having at least two photopolymerizable ethylenically unsaturated groups per molecule. The paint is essentially solvent-free. U.S. Patent No. 4171 to FOgIeta I.
No. 387 discloses a UV curable urethane overcoat consisting of a cellulose substrate coated with a urethane adhesive and a polyacrylate resin. BettOli
U.S. Pat. No. 4,180,615 discloses a vinyl bed having an essentially solvent-free ultraviolet curable overcoat consisting of a urethane having at least two photopolymerizable ethylenically unsaturated groups. US Pat. No. 4,188,455 to HOward discloses unsaturated urethane oligomers that are UV curable in air. The oligomer is derived from at least one active hydrogen-containing compound, at least one isocyanate and at least one polyether ester. Lorenz et al.
U.S. Pat. No. 4,216,267 to Erlzetal discloses a urethane coating composition comprising an oligomer of a specific formula, an acrylic UV absorber, and preferably a vinyl monomer copolymerizable with the oligomer. Tarfertiller et al. discloses ultraviolet or chemically curable addition polymerizable polyethers having pendant, ethylenically unsaturated urethane groups.

While these and other references relate to UV curable compositions useful as flooring materials, there is still a need to develop better flooring materials. One of the objects of the present invention is therefore to provide a method for producing coatings that exhibit excellent toughness, are stain-resistant, stain-resistant and wear-resistant.

Another object of the present invention is to provide a method of treating radiation curable substrates to provide surfaces with superior cleanability. A further object of the present invention is to provide a floor covering which has excellent durability, stain resistance and also has excellent cleaning properties.

These and other advantages of the invention will become apparent from the following detailed description of the preferred embodiments.

In summary, the present invention provides an excellent flooring material and substrate that can be cured by actinic radiation treated with a solution consisting of water, N-vinyl lactam, a suitable surfactant, and, if necessary, an organic solvent. The present invention relates to a method of manufacturing a flooring material by.

Irradiation of the treated substrate forms a tough and durable surface with properties superior to those currently known in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In a first embodiment, the present invention relates to a method of treating a substrate that is cured by irradiation with actinic radiation, the method comprising: where X is an alkylene bridge (group) having 3 to 5 carbon atoms.
) and about 0.1 to 75% by weight of a suitable surfactant.
01 to about 5% by weight, coating the substrate with the solution, and irradiating the coated substrate with actinic radiation.

In a second embodiment, the invention relates to a coated substrate having excellent durability, abrasion resistance, and stain resistance, the substrate having the following structure, where x is 3 to 5 carbon atoms. An aqueous solution consisting of about 0.1 to 75% by weight of an N-vinyl lactam with alkylene bridges) and about 0.01 to 5% by weight of a suitable surfactant was applied to the actinic radiation curable surface. It is then obtained by irradiating the surface with actinic radiation.

Many uses have been found in the prior art for N-vinyl lactams such as N-vinylpyrrolidone.

For example, it is used as a comonomer to modify the properties of the monomer, as disclosed in the Lorentz et al.
rLlcnaletaI. ) U.S. Patent No. 387490
6 as a photochemical curing accelerator in UV-curable paints; and in coating compositions used to impart hydrophilicity to hydrophobic substrates as in the Tazuke et al. patent cited above. Ru. However, N
- Nowhere in the prior art is it taught to apply an aqueous solution of vinylpyrrolidone and a surfactant to a radiation-curable substrate and irradiate it with radiation, thereby imparting superior abrasion resistance to the treated substrate. It has not been suggested or implied. Surprisingly, we have coated a radiation-curable substrate with an aqueous solution of N-vinylpyrrolidone or another N-vinyllactam, a suitable surfactant, and an organic solvent if necessary, and exposed it to actinic radiation. It has been discovered that it can be hardened by irradiation.

The resulting cured surface has excellent scratch resistance, dent resistance, and exhibits excellent cleanability. Furthermore, the method can be used in some cases to produce matte surface coverings. Such surfaces are therefore highly suitable for floor coverings. This method of creating a surface with excellent scratch resistance and easy cleanability does not need to be carried out on totally uncured surfaces.

For example, before a radiation-curable surface is coated with an aqueous solution of the invention, the surface is rendered to a tacky finish by irradiation in air or by irradiation with a dose of radiation energy insufficient to fully cure the surface. be able to. The adhesive surface is then treated according to the present invention to provide a surface that is dent-resistant, scratch-resistant, and easy to clean. To practice the invention, the radiation curable substrate is prepared by conventional means.

Virtually any radiation curable substrate can be used. Accordingly, polyurethanes, polyethers, polyesters, polyester acrylates, polyester-urethane-acrylic resins, etc. that are cured by actinic radiation exhibit excellent wear and cleaning properties when treated according to the present invention. These substrates are processed while on the intermediate support surface or while on the finished product. For example, UV-curable urethane wear layers for floor structures may be prepared and processed while supported on a transfer sheet, or when on the flooring itself, such as a PVC flooring. In addition, the substrate consists of oligomers and other reactive diluents alone or in combination. Such materials include, for example, ethyl acrylate, propyl acrylate,
Isopropyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, synclopentynyl acrylate, 2-phenoxyethyl acrylate, N,N-dimethylaminoethyl acrylate, ethyl methacrylate , propyl methacrylate, isopropyl methacrylate, butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, synclopentynyl methacrylate, 2-phenoxyethyl methacrylate, N,N-dimethylamino methacrylate Acrylic and methacrylic esters of ethyl, lactic and stearic acids, hexanediol diacrylate,
Neopentyl diol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexane diol diacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, dimethacrylic acid Butylene Glycol, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; pentaerythritol diacrylate,
Pentaerythritol triacrylate, pentaerythritol tetraacrylate and mixtures thereof; pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and mixtures thereof; acrylated fatty acids such as linseed oil or soybean oil or methacrylate Late fatty acids; acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N-
Propyl acrylamide, etc.; N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, etc.; N-methyl methacrylamide, N-ethyl methacrylamide, N-propyl methacrylamide, etc.; , N-dimethyl●acrylamide,
N,N-diethyl acrylamide, etc.; N,N-dimethyl ●methacrylamide, N,N-diethyl ●methacrylamide, etc.; acrylic acid, methacrylic acid, acrylic acid 2-
Hydroxyethyl, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, allyl acrylate, allyl methacrylate, N-isobutoxyacrylamide, N-methylol acrylamide, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazo vinyl, vinylpyridine, N-vinylpiperidone,
etc. N-vinyl lactam aqueous solution is N-vinyl lactam
It comprises from about 0.1 to about 75% by weight of a lactam and from about 0.01 to about 5% by weight of a suitable surfactant.

Desirably, the aqueous solution contains from about 1% to about 50% by weight of the lactam;
and from about 0.01 to about 2% by weight of a surfactant, and more preferably from about 1 to about 15% by weight of a lactam and about 0% by weight of a surfactant.
．． 1 to about 1% by weight. N-vinylpyrrolidone was chosen as the lactam, although lactams such as N-vinyl-5-methylpyrrolidone, N-vinylpiperidone and N-vinylcaprolactam have also been found to be useful. Any suitable surfactant or mixture thereof can be used, the only requirement being that the surfactant is N
- be miscible with aqueous vinyl lactam solutions and be suitable for wetting the surface of radiation-curable substrates;

The excellent results were obtained by the American company GAF using the product name 0 Igepal (Igepal).
It was obtained with a series of alkylphenoxyl polyoxyethylene ethanol nonionic surfactants sold by Gepal. In particular, for UV-curable urethane wear layers when IgePalCO-610 (which is a polyethylene oxide derivative of nonylphenol) is used at a level of 0.5% by weight in an aqueous solution with 1% N-vinylpyrrolidone by volume. Satisfactory results were obtained. However, silicone surfactants, such as the trade name RDO
Other surfactants such as COrninQC-193 (a polyethylene glycol siloxane) can also provide satisfactory results. The aqueous solution is applied to the substrate by conventional methods.

For example, dip coating, flow coating, curtain coating, etc., all well known in the paint industry, give satisfactory results. The specificity of the invention becomes apparent when considering the abnormalities that arise from modifying the method.

For example, excluding N-vinyl lactams or surfactants from aqueous solutions generally results in poorer surface coatings. Similarly, placing the N-vinyl lactam or surfactant in the matrix instead of in the aqueous phase produces similar results. From this it is clear that both components must be present in the aqueous phase to obtain good results. However, the inclusion of these components in both the aqueous layer and the substrate does not have the opposite effect. Also, the aqueous coating solution is free from solvents and other components present in the solution and/or substrate, e.g. It consists of a copolymer polymerized with N-vinyl lactam and/or other crosslinking compounds.

For example, Igepal series, such as IgepalCO-9
90 high molecular weight surfactants are not suitable for wetting the substrate surface, but can be made by adding a water-miscible organic solvent such as isopropyl alcohol, which acts as a leveling agent and wetting promoter. Note that wettability can be increased to obtain suitable results. Similarly, acrylamide, acrylic acid, 2-hydroxyethyl acrylate, vinyl acetate, methylol, acrylamide, methacrylic acid, potassium acrylate, zinc acrylate, ethoxy/ethoxyethyl acrylate, methacrylamide chloride, trimethylammonium, etc. Copolymers can be incorporated as viscosity modifiers, pigments, anti-foaming agents and flow agents. Furthermore, since the present invention can be applied over a wide pH range, an agent can be added to adjust the pH to a desired level. Photoinitiators can also be included in the aqueous phase, although the presence of photoinitiators is not necessary to obtain the excellent results obtained with the present invention. Although surfaces produced in accordance with the present invention exhibited excellent durability and stain resistance, they sometimes exhibited a tendency to become slightly slippery when wet. In some applications, such properties may be undesirable. Surprisingly, however, we have shown that such ease can be achieved by including in the aqueous phase one or more aqueous or partially aqueous diacrylate or triacrylate esters of polyfunctional alcohols. We found that it can be avoided or reduced. Even more surprisingly, the inclusion of these diacrylic esters and triacrylic esters increases the stain resistance of the resulting surface. These materials (hereinafter referred to as polyfunctional acrylates)
from about 0.5 to about 25% by weight (referred to as esters) in the aqueous phase.
Surface properties were improved when included at levels desirably from about 1% to about 5% by weight. Typical multifunctional acrylate
Examples of esters include tetraethylene glycol diacrylate, diethylene glycol diacrylate,
They are ethylene●glycol diacrylate, triethylene●glycol diacrylate, glycerol diacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Another feature of the invention is the gloss of the resulting surface.

The reduction in gloss of the resulting surface is due to the N-vinyl chloride in the aqueous phase.
It tends to occur as the amount of lactam increases. For example, the amount of N-vinylpyrrolidone is N-vinylpyrrolidone, I
1 in an aqueous phase containing only gepal CO-610 and water.
% to 10%, the gloss of the cured surface decreases sharply. However, the presence of comonomers in the aqueous phase tends to counteract this effect. Therefore, acrylamide is 1
When added to the above solution containing 0% N-vinylpyrrolidone, the gloss of the cured product is superior to the gloss of a sample treated with a solution containing N-vinylpyrrolidone and no acrylamide. Such gloss measurements can be performed using well-known methods, e.g.
Performed by ANSI/ASTM (American National Standards Institute and American Patent Testing Society) D523-78, which describes a method for measuring specular gloss. The following examples are illustrative and do not limit the scope of the invention.

Example 1 The following reaction components were stirred and charged to a dry air purged reactor: The above mixture was heated to 130'F.
) and 1401.3y of 2-hydroxyethyl diacrylate was metered into the reactor at such a rate that the temperature did not exceed 54.4°C.

After 1 hour, the next polyester was heated to 48.9°C (120°F).
) was added to the cooled reaction mixture: Note (1): Toluol was purchased from HOOker Chemical & Plas, USA.
I used F2O39-180 from tic, which has 1 mole of glycerol and a ratio of adipic acid to isophthalic acid of 71.
A reaction product of 3 moles of a mixture of 3 and 3 moles of 1,6-hexanediol, with a molecular weight of 9601 hydroxyl NO
．． is 175.

Note (2): PCPO of UniOnCarblde in the United States
2OO is used, which has a molecular weight of 540 and hydroxyl NO
．． Polycaprolactone with 2O7. It is a diol.

There was a slight exotherm, but then the reaction mixture reached 60'C.
(140'F) for 4 hours.

Infrared data at the end of this period showed the absence of isocyanate. The reaction mixture is 32.
Cooled to 2°C (90°F), the product (Product A) was placed in a Heresite lined drum. Based on 10 parts by weight of product A, 2. % benzophenone photoinitiator was added along with 0.1% by weight polyethylene glycol siloxane (DC-193 from DOwCOrning). The paint thus produced has a viscosity of approximately 12,000 centiboads at room temperature and 33
．． It consisted of a urethane prepolymer capped with 6% reactive diluent and 66.4% acrylate. 3 mil (
Approximately 0.075wr1! Coat vinyl floor tiles using a part-blade applicator of (energy dose of 3 Joules/Cli as measured with an international light exposure meter).

Although the coating on the tile was non-adhesive, hard and shiny, the coating was subjected to excessive scuffing and staining under simulated abrasion conditions using a rotating abrasion wheel, making it durable and tough for consumer use. This was not desirable as a transparent coat.
Example 7.5y of acrylic acid, 2f of benzophenone and -1930.1y were added to (1) part of product A1.

The paint was applied to vinyl floor tile using a part blade applicator and a 3 mil thick coating was cured in the same manner as Example 1. Although the cured coating was tough and scratch resistant, the performance of this coating in the simulated abrasion test of Example 1 indicated that it had undesirable abrasion properties due to excessive dirt and scratches. EXAMPLES The example compositions were applied to floor tiles to a wet 3 mil thickness.
Before the uncured coating was cured with UV light, it was overcoated with an aqueous solution of N-vinylpyrrolidone containing a nonionic surfactant.

The composition of the water-based top coat (protective film) was as follows.
The protective film was applied by dipping the coated tile in an aqueous solution for about 1 second.

Tiles coated with water-based paint over non-aqueous paint (wet-on-wet) were immediately cured with UV light as described in Example 1, washed with water to remove excess water-based paint, and air-dried. The result was a hard, tough, and durable coating with excellent properties as an abrasion-resistant abrasion coating for floors. The coating was particularly desirable as a floor coating because it was stain resistant and easier to clean than the products of Example 1 and above. The specular gloss of the coating sample is D523-78 of the American National Standards Institute and the American Society for Testing and Materials.
It was measured using the method described in .

Light was directed at the sample surface at an angle of incidence of 60 degrees, and gloss was measured relative to a comparison standard using a Gardner glossmeter. The sample had a specular gloss of 34 when compared to a comparison standard which had a gloss of 94. Fourier infrared spectroscopy examination of the surface of a coating prepared by curing a wet-on-wet coating revealed that the surface of the cured film contained a significant amount of N-vinylpyrrolidone component in the crosslinked film. , the lower surface of the membrane showed no evidence of N-vinylpyrrolidone monomer units being contained in the polymer matrix. From this, it is considered that N-vinylpyrrolidone diffused to the surface of the non-aqueous layer and copolymerized with the polymerizable component there. It is particularly surprising and unexpected that such a significant surface improvement was obtained in the presence of water and in the absence of photoinitiator in the aqueous phase. EXAMPLES The compositions of the examples were applied to vinyl floors using a part blade applicator and a 3 mil thick coating was cured with ultraviolet light as described in Example 1.

After hardening, water 90y. ．． A solution consisting of N-vinylpyrrolidone 10y and Igepar CO-6100.5f1 was applied to the cured film by flow coating. The resulting composition was immediately treated with UV light as described in Example 1. The product was washed with water, dried and evaluated for stains and scratches by simulated floor abrasion tester and soil tester. As a result, the performance of the coating was determined to be nearly identical to the example and therefore was determined to be undesirable as a floor coating due to excessive staining and scuffing. Therefore, it appears that treatment of cured substrates according to the present invention does not produce satisfactory surface coverage. EXAMPLES The example compositions were applied to vinyl floors with a part blade applicator to give a 3 mil thick coating of 0.31 mm.
The coating was exposed to the energy output of a single 200 watt medium pressure mercury lamp to receive an energy dose of Joules/Clt.

This dose was obtained by using a line speed of 40 feet/min and a 118 inch thick window pane filter between the sample and the lamp. The resulting sticky surface is water 9
0 g, N-vinylpyrrolidone, 10 g, and Igepar CO-6100.5 f by pouring and immediately passing it through the radiation output of two 200 watt medium pressure mercury lamps at a rate of 15 ft/min. An energy dose of 3.0 Joules/Cfi was received. Stain, scratch and cleanability evaluations showed that this product had better performance than the example and the one. Example: In the product AlOO part, 7.5f1 irgaquia acetic acid (I
rgacure) 651 photoinitiator (2,2-dimethoxyphenyl acetophenone) 1y1 and DC-193
0.1y was added.

The paint was applied to vinyl floor tiles using a part blade applicator and a 3 mil thick coating was applied to the 200 watts described in the example so that the sample received an energy dose of 0.31 joules/al. Exposure to the power of a medium pressure mercury lamp. The resulting sticky surface was coated with 90 y of water, . N
-Vinylpyrrolidone 10y and Igepal CO-61
A solution consisting of 0.00.5y was flow coated and immediately exposed to 3.0 Joule/d UV light from two medium pressure mercury lamps. The product was washed with water and dried. The hard, glossy coating was found to be better than the product of Example and Example as a floor abrasion coating because it was less soiling, more scratch resistant, and easier to clean. Example ~X Aqueous coating phase on top of non-aqueous coating phase. The following aqueous compositions were prepared to demonstrate the suitability of the wet-on-wet coating method using: used for.

A 3 mil wet drawdown (stretched film) of a non-aqueous composition on vinyl tile was applied by dip coating with four different aqueous compositions for 1 second each. Wet On Wet The coated tiles were immediately passed under a medium pressure mercury lamp as described in Example 1. After washing and drying, the treated samples were made stain and drag resistant as described in Example 1 by using a rotating abrasion wheel. A scratchability test was conducted. All four samples performed better than the sample without water-based paint.

Each of the four samples was significantly easier to clean than the example composition after the stain test.

These results demonstrate that comonomers with N-vinylpyrrolidone can be used in the aqueous phase (Examples and Examples) and that soluble polymers such as polyvinylpyrrolidone and polyacrylic acid (Examples and Examples) can also be used wet-on-wet. It shows that it can be present in the aqueous phase without reducing the excellent performance of UV-cured coatings. Examples M-X The following series of mixtures demonstrate the wide range of N-vinylpyrrolidone variations that are acceptable in the aqueous phase while retaining the advantages of the present invention.

-Sumi'1 'VVυ υlυ υ●J υ
．． J υ. υThese aqueous compositions were used to coat the photocurable non-aqueous compositions described in the examples.

A 3 mil wet drawdown of the non-aqueous composition on the vinyl tile was coated with the aqueous composition and each wet-on-wet two-phase coating was immediately cured with UV light as described in Example 1. Ta. After washing with water and drying, the film was evaluated for stain resistance, stickiness resistance, and washability, and it was found that all three exhibited the expected behavior. The performance was essentially the same as that obtained with the 10% aqueous N-vinylpyrrolidone solution described in Example H; that is, the non-aqueous UV-curable coating described in Example H (wet-on with N-vinylpyrrolidone solution・Excellent performance when compared to those that were not wet coated. Furthermore, for Examples and Examples, specular gloss values were measured by the method shown in the Examples.

As a result, values of 92 and 82 were obtained, respectively. These results, in combination with the values obtained in the examples, show that the gloss values tend to decrease with increasing amount of N-vinylpyrrolidone in the aqueous solution. Examples x-X The following are compositions that vary the amount of acrylic acid in the non-aqueous phase of the final coating.

A 3 mil thick drawdown of these compositions is applied to vinyl tile and the tile is treated with 90% water, N-
Vinylpyrrolidone 10y and Igepal CO-6100
．． An aqueous solution consisting of 5y was overcoated (wet-on-wet). The sample was UV cured, washed and dried as described in Example 1. Evaluation of the cured coating film by a simulated walking abrasion test showed excellent performance in all three rows. Cleanability was also improved compared to cured coatings not overcoated with the solution. Examples X-X The following three examples use acrylic acid as the water-soluble comonomer with N-vinylpyrrolidone for coating product A;
and 2% by weight of benzophenone, 1% by weight of Irgaquia 651 photoinitiator, and DC6l93O. % by weight.

A 3 mil thick drawdown of this composition was coated (wet◆on wet) with the aqueous composition shown below by dip coating, and the coated surface was immediately exposed to ultraviolet light as described in Example 1. Hardened. Evaluation of the cured film showed that it was sharp, shiny, scratch resistant, and had excellent cleaning properties with mild detergents. On the other hand, the control sample was as described in Example 1 and had poor performance. Example XX The composition of the example was applied to a flexible vinyl sheet floor using a 3 mil part blade applicator.

The wet uncured coating was coated (wet-on-wet) with an aqueous solution containing 90 y of water, 10 y of N-vinylpyrrolidone, and 0.5 y of Igepar CO-6100. The product was immediately treated with ultraviolet light as outlined in Example 1 and evaluated for abrasion resistance and cleanability using the uncured vinyl floor substrate of the example as a control sample. The sample to be coated was superior to the control sample when subjected to a scratch test using a simulated abrasion test.
It was also significantly easier to clean than the control sample. Example XX
A 3 mil thick layer of the composition of Example I was applied to the floor tile and 90 y. ．． N-
It was overcoated by flow coating with an aqueous solution containing vinylpyrrolidone 10y1, 2g of tetrabutylammonium bromide, and Igepar CO-5300.5y1, another polyethylene oxide derivative of nonylphenol.

The wet-on-wet coating was immediately exposed to UV light as described in Example 1. Excess water-based paint was removed by washing with water, and after air drying a hard, tough and wear-resistant coating was obtained. It is particularly desirable as a floor covering because it is low-fouling, easy to clean, has good heat and light stability, and has a non-wax abrasion layer that is better than the coatings of Example 1 and Example. . This example shows that phase inversion agents such as tetrabutylammonium bromide can also be included without adversely affecting the aqueous solution. Example X The composition of Example 1 was applied to floor tile using a 3 mil part blade.
It was applied using an applicator, and the uncured film was coated with 90 y of water. An aqueous solution consisting of 5y1 of N-vinylpyrrolidone, 5y1 of acrylic acid, and 6100.5q of Igepar CO-1 was curtain coated.

The coated tiles were passed under a 200 watt medium pressure mercury lamp in air according to the method described in Example 1. The product was washed with water and dried to yield a hard, glossy, easily cleaned, abrasion resistant coating which was found to have superior performance to the coating of Example 1. This example shows that other comonomers such as acrylic acid can also be included in the aqueous solution. Example XX The following composition was prepared to demonstrate the use of a co-solvent to help obtain a homogeneous aqueous phase using a water-insoluble comonomer.

Without the addition of ethanol, tetrahydrofurfuryl acrylate was insoluble in the mixture of other listed ingredients.

The composition was poured onto a 3 mil uncured coating of the UV curable composition of the example on the floor tile, and the aqueous coating on the non-aqueous coating was immediately cured with UV light as described in Example 1. . After washing with water and air drying, the hard, glossy surface was evaluated as a protective wear coat using the simulated abrasion test of Example I. As a result, this product had better performance than the cured product in the example, and had good stain resistance and scratch resistance. EXAMPLE XX The composition of the example was applied to vinyl floor tiles with a wetness of 3 mils.
Prior to curing the uncured film with UV light, the following compositions were flow coated to provide a wet two-phase coating with a smooth, evenly distributed aqueous coating arranged on top of a non-aqueous coating.

Samples treated with a similar solution without isopropyl alcohol did not completely wet the non-aqueous phase. The tiles, coated with the aqueous phase over the non-aqueous phase, were immediately cured with UV light as described in Example 1, washed with water, and air dried to yield a hard, stick-resistant surface.

The product was then evaluated as a protective wear coat by the simulated abrasion test of Example 1 and showed superior performance to the cured product of Example, with good stain and stick resistance. . Example XX This example shows that the wet-on-wet coating method of the present invention also enhances the floor wear performance of other UV-curable coatings.

The preparation and use of acrylic polyester instead of the acrylic polyester/urethane used in the previous example will be explained. The acrylic polyester was prepared in two steps: step 1, a polyesterification reaction, and step 2, the acrylation of a hydroxyl-terminated polyester. Step 1 Product B was prepared by charging the following ingredients to a 5e14 neck round bottom flask.

The flask was equipped with a metal stirrer, nitrogen concentration, Ii meter, and a vertical steam/heating column filled with a glass spiral. The temperature of the pot was gradually increased to 220°C (428°F). The nitrogen flow rate was maintained at 1.2 cubic feet of Ar (SCFH) for the duration of the reaction. Water as a by-product was removed until the acid value became 1 or less. As a result of analysis of product B, the hydroxyl value was 84.2 and the acid value was 0.3. Step 2 Acrylic acid polyester (Product C) The following ingredients were charged to a 2e14 neck round bottom flask.

The temperature of the reaction mixture was increased to 105° C. (22 rF) while maintaining the nitrogen flow rate at 1.25 SCFH.

A total of 21.7 ml of water was removed using a pallet trap and water cooled condenser. The acrylic polyester was then cooled to room temperature and the playing cards and condenser were replaced with distillation heads. The temperature was raised until the mixture was stirred and 1.33 f of magnesium oxide and 11.6 f of butyl benzyl phthalate were added. Set the temperature to 105℃ (
A vacuum (5hHy) was applied (22rF); 170ml of organic distillate was removed. The final acrylic polyester (Product C) has a viscosity of 112,000 CPS 1 acid number 1
9.56, and a hydroxyl number of 10.6. The acrylic polyester was mixed as follows: A 3 mil thick drawdown of mixed Product C was UV cured on a tile substrate as described in Example 1.

It was tested in simulated walking conditions (poorly performed) and showed excessive scratches and stains and poor cleanability.
The same coating on the tile was soaked in water for 90 y before curing. ．． N-vinylpyrrolidone 10y and Igepal CO-6100.
When a solution containing 5y was applied by dip coating and cured in the same manner, the resulting coating had excellent cleanability, low staining properties, and good stickiness. Example XX This example shows that the inclusion of a multifunctional acrylide ester in the aqueous phase improves surface properties.

A solution consisting of the following components was prepared: This solution was coated onto the 3 mil wet, uncured film described in Example I, and the coating was immediately cured with UV light as described in Example I.

The wear performance of the surfaces obtained was comparable to that of surfaces obtained for example, but this surface was
It is resistant to ordinary household stains such as shoe polish. Moreover, the surface of the cured coating exhibited superior burr resistance when compared to samples prepared according to the examples. The present invention is not limited solely to what has been described and described above, but includes all modifications and variations contemplated by the claims.

Claims (1)

[Claims] 1 Water and an N-vinyl lactam having the following structure ▲ Numerical formula, chemical formula, table, etc. ▼ (where X is 3 carbon atoms)
~5 alkylene bridges) approximately 0.1
~75% by weight and a suitable surfactant from about 0.01% to about 5% by weight.
% by weight, applying a layer of said solution onto a substrate to be cured by actinic radiation, and irradiating the thus treated substrate with actinic radiation. A method for treating a substrate that is cured by actinic radiation. 2 N-vinyl lactam with the following structure ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (where X is 3 carbon atoms)
~5 alkylene bridges) approximately 0.1
~75% by weight and a suitable surfactant from about 0.01% to about 5% by weight.
Excellent durability, abrasion resistance and stain resistance obtained by irradiating the surface with actinic radiation after applying an aqueous solution consisting of coated substrate with.