WO2016018123A1 - Hard coating composition comprising polytetrafluoroethylene, hard coating layer and flooring material comprising same - Google Patents

Abstract

Provided is a hard coating composition including an ultraviolet curable resin, inorganic particles, polytetrafluoroethylene, and a photopolymerization initiator. Provided is a flooring material including a hard coating layer formed by using the hard coating composition on one side of a base layer of a vinyl chloride resin.

Description

Hard coating composition comprising polytetrafluoroethylene, hard coating layer and flooring comprising the same

It provides a hard coating composition comprising a polytetrafluoroethylene, a hard coating layer and a flooring comprising the same.

In general, the flooring material has a configuration laminated sequentially from the bottom to the base layer, the printing layer, and the UV coating layer, and added to the various materials or by changing the configuration to take advantage of the characteristics of the flooring material to highlight the decorative properties And flooring material etc. which emphasized the functionality was obtained and used according to the use.

Looking at the general flooring material, Korean Utility Model Publication No. 195-009683 describes an opaque pearl pigment powder pearl chip, aluminum particles, spherical particles, etc., on the foam layer in the flooring material in which a base layer, a foam layer, a print layer, and a transparent layer are sequentially laminated. A flooring material having a variety of three-dimensional impressions is described by laminating and embossing the impregnated opaque decorative material impregnated layer and applying a transparent layer, a print layer, another transparent layer, and a pollution-resistant treatment layer thereon.

Unlike the conventional flooring, which has been decorated with a decorative function, recently, antimicrobial agents are added to the plurality of layers to obtain a flooring having antimicrobial properties, or an antistatic effect is applied to a flooring material having special functions such as a flooring material having an antistatic effect. Research continues.

One embodiment of the present invention by providing a polytetrafluoroethylene, to provide a hard coating composition, and a hard coating layer to ensure chemical resistance, chemical resistance and stain resistance.

Another embodiment of the present invention provides a flooring material including the hard coating layer on a vinyl chloride resin substrate layer.

In one embodiment of the present invention, it provides a hard coating composition comprising an ultraviolet curable resin, inorganic particles, polytetrafluoroethylene and a photopolymerization initiator.

The polytetrafluoroethylene may be formed from a polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax.

The average particle size of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be about 10um to about 20um.

The polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be formed by copolymerizing polytetrafluoroethylene and polyethylene.

Specific gravity of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be about 1 to about 1.5.

About 5 parts by weight to about 80 parts by weight of the ultraviolet curable resin, about 1 part by weight to about 20 parts by weight of the inorganic particles, and about 1 part by weight to about 20 parts by weight of the polytetrafluoroethylene based on 100 parts by weight of solids By weight, about 1 to about 15 parts by weight of the photopolymerization initiator may be included.

The ultraviolet curable resin may form a network composite after curing, and may include particulate polytetrafluoroethylene present in an entangled manner within the network composite.

The average particle size of the inorganic particles may be about 0.01um to about 1um.

The inorganic particles may include one or more metal oxides selected from the group consisting of silica, alumina, zirconium oxide, and combinations thereof.

Another embodiment of the present invention provides a flooring material including a hard coating layer formed on the one surface of the vinyl chloride resin substrate layer using the hard coating composition.

The hard coating layer may have a thickness of about 10 μm to about 20 μm.

By using the hard coating composition, it is possible to secure a hard coating layer with improved chemical resistance to acids, alkalis, and solvents.

The flooring material may exhibit slipability and flexibility due to the hard coating layer.

Figure 1 shows a schematic diagram of the network structure formed after the ultraviolet curable resin curing.

Figure 2 shows a cross section of the flooring which is an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Hard Coating Composition

In one embodiment of the invention, it provides a hard coating composition comprising an ultraviolet curable resin, inorganic particles, polytetra fluoroethylene and a photopolymerization initiator.

Typically many hard coating agents have been used to protect the surface of the flooring material and to impart wear resistance to the surface. Among them, flooring materials used in the medical and chemical industries need to secure physical properties such as chemical resistance and chemical resistance as well as wear resistance of the surface.

Accordingly, the hard coating composition may include polytetrafluoroethylene to secure chemical resistance and chemical resistance that is not damaged when the flooring material is exposed to acid, alkali, and solvent.

The polytetrafluoroethylene may be included in the form of particles, in the form of granular powder, and may be included in the composition in the form of copolymerization with other materials. For example, the polytetrafluoroethylene contained in the hard coating composition may be formed from a polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax (hereinafter referred to as 'PTFE / PE mixed wax'). .

The average particle size of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be about 10um to about 20um. The PTFE / PE mixed wax has a particle shape in powder form, and the 'average particle size' refers to an average value calculated after measuring the particle diameter in an arbitrary region of the PTFE / PE mixed wax.

When the average particle size of the PTFE / PE mixed wax is less than about 10 μm, the roughness may be small, and thus the stain resistance may be significantly reduced. When the average particle size exceeds about 20 μm, the wax may be desorbed when the average particle size is larger than the thickness of the hard coating layer. It may be desirable to maintain the range in that the wax does not protrude and maintains a certain level of roughness.

The polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be formed by copolymerizing polytetrafluoroethylene and polyethylene.

On the other hand, when the wax formed only of the polytetrafluoroethylene (PTFE) is used, the specific gravity of the wax itself is high, so the sedimentation rate is increased, and thus the hard coating layer may be uneven when the flooring is formed, and the wax formed of polyethylene (PE) is used. In case of doing so, the effect was insufficient in the fouling resistant part. Accordingly, by copolymerizing polyterrapuloethylene (PTFE) to polyethylene (PE), it is possible to minimize the non-uniformity of the hard coating layer composition, it is possible to easily implement the dispersion effect of the composition. In addition, due to PTFE containing fluorine, it is possible to secure chemical resistance and stain resistance at the same time.

Specific gravity of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax may be about 1 to about 1.5. The specific gravity refers to the ratio between the density of the PTFE / PE mixed wax and the density of water. When the specific gravity of the PTFE / PE mixed wax is small, the specific gravity of the PTFE / PE mixed wax does not disperse in the coating composition but floats upward. If there is a fear that the hard coating layer will be uneven when forming the product later.

Therefore, to maintain the specific gravity of the above range, the wax in the composition can be dispersed, thereby allowing the composition to be uniformly applied and dried.

About 100 parts by weight of solids, the PTFE may include about 1 part by weight to about 20 parts by weight. Due to the hard coating composition including the PTFE between the spaces generated after curing the UV curable resin, the structure of the hard coating layer may be more dense, and the hard coating layer may exhibit slipability and flexibility due to the compactness. The properties may be adjusted according to the PTFE content.

Specifically, when the PTFE is included in less than about 1 part by weight, there is a concern that the effect due to wax may be insufficient, and when it contains more than about 20 parts by weight, there is a problem of compatibility with other materials due to the increase in viscosity of the composition. It is preferable to maintain the above range in that the effect by the wax can be optimized and expressed.

The ultraviolet curable resin may form a network composite after curing, and may include particulate PTFE that is entangled in the network composite.

1 is a diagram illustrating a network structure formed after curing of the UV curable resin, and referring to FIG. 1, the UV curable resin may be formed into a network complex by curing the UV curable resin, wherein the network has a crosslinking point. UV curable resin refers to a three-dimensional network of chains. There are spaces between the chains and the chains in the network composite bar, PTFE may be present between the spaces. In addition, there may be PTFE intertwined with the chain in the space.

Since PTFE is entangled in the network composite, the hard coating layer composition becomes more dense, and the hard coating layer formed by the composition may have slipability and flexibility.

Furthermore, the hard coating layer formed due to the dense structure of the composition can minimize the input of external solvents and contaminants, thereby ensuring chemical resistance and contamination resistance at the same time.

Since the PTFE is present in the network composite, it may be high density in comparison with the density of the network composite formed by a conventional UV curable resin after curing.

The hard coating composition may include an inorganic particle other than PTFE and a photopolymerization initiator.

The average particle size of the inorganic particles may be about 0.01um to about 1um. The inorganic particles may include one or more metal oxides selected from the group consisting of silica, alumina, zirconium oxide, and combinations thereof. For example, an inorganic particle whose surface is silane coupled or titanium coupled may also be used, and a surface treating agent having a functional group capable of reacting with a component included in the composition on the surface of the inorganic particle may be used.

The composition may include about 1 part by weight to about 20 parts by weight of the inorganic particles based on 100 parts by weight of solids. When the inorganic particles are included in less than about 1 part by weight, there is a problem that the composition may not implement wear resistance, and when the inorganic particles are included in an amount of about 20 parts by weight or more, the inorganic particles may not be dispersed in the composition. By maintaining, dispersibility and wear resistance can be realized simultaneously.

The hard coating layer formed of the composition is to be formed on one surface of the vinyl chloride resin base layer, bar to ensure a certain level of hardness, it may include an ultraviolet curable resin.

As the ultraviolet curable resin, those having an acrylate-based functional group, for example, a polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, a spiro acetal resin, a polybutadiene resin, And (meth) acrylate resins of polyfunctional compounds such as polythiol polyene resins and polyhydric alcohols.

Specific examples thereof include ethylene glycol diacrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acryl Polyester (meth) acryl which can be obtained by esterifying the polyol poly (meth) acrylate, the di (meth) acrylate of bisphenol A- diglycidyl ether, polyhydric alcohol, polyhydric carboxylic acid, and its anhydride, and acrylic acid Latex, polysiloxane polyacrylate, urethane (meth) acrylate, pentaerythritol tetra methacrylate, glycerin tri methacrylate, and the like, but are not limited thereto.

The UV curable resin may be formed of any one of the above compounds, or may be formed by mixing two or more kinds thereof. For example, the UV curable resin may include a urethane acrylate oligomer having a molecular weight of about 1,000 to about 20,000, It may be formed by mixing acrylate monomers to lower the viscosity of the composition and facilitate adhesion.

The amount of the ultraviolet curable resin may include about 5 parts by weight to about 80 parts by weight based on 100 parts by weight of the solid content. When the resin content is less than about 5 parts by weight, cracks of the hard coat layer are likely to occur, and when it exceeds about 80 parts by weight, the viscosity of the hard coating composition may increase.

The composition may comprise a photopolymerization initiator, for example, acetophenone, benzophenone, mihiraketone, benzoin, benzyl methyl ketal, benzoin benzoate, hydroxycyclohexylphenyl ketone, 2-methyl-1 -(4- (methylthio) phenyl) -2- (4-morpholinyl) -1-propane and the like can be used.

The composition may further include a UV increasing agent, a thermoplastic resin, a leveling agent, a wetting agent, and the like in a range that does not impair the hardness of the hard coating layer formed of the composition.

For example, n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be used as said ultraviolet sensitizer.

Further, as the thermoplastic resin, cellulose derivatives such as acetyl cellulose, nitrocellulose, acetyl butyl cellulose, ethyl cellulose, methyl cellulose, vinyl acetate and copolymers thereof, vinyl chloride and copolymers thereof, vinylidene chloride and copolymers thereof, and the like Acetal resins, such as a vinyl resin, polyvinyl formal, and polyvinyl butyral, an acrylic resin, its copolymer, acrylic resin, such as methacryl resin and its copolymer, polystyrene resin, polyamide resin, linear polyester resin, Polycarbonate resin and the like can be used.

The wetting agent may be an anionic or nonionic surfactant used as a conventional leveling agent, and specifically, sodium dialkyl sulfosuccinate compound, alkyl-phenol polyethylene glycol derivative compound, alkyl sulfonate compound, or alkyl A benzene sulfonate type compound etc. can be used.

Flooring

Another embodiment of the present invention provides a flooring material including a hard coating layer formed on the one surface of the vinyl chloride resin substrate layer using the hard coating composition.

2 is a cross-sectional view of a flooring material according to an embodiment of the present invention. Referring to FIG. 2, the flooring material may include a laminated structure of a vinyl chloride resin base layer, and a hard coating layer. The flooring material may exhibit slipability and flexibility due to the hard coating layer.

The base layer may include, for example, CaCO 3 as a vinyl chloride resin base layer. The hard coating layer is formed by coating and drying the hard coating composition on the base layer, the coating composition for a hard coating is as described above.

The hard coating layer may have a thickness of about 10 μm to about 20 μm. Wear resistance may be weak when the thickness of the hard coating layer is less than about 10um, it may be difficult to express the effect due to the PTFE when it exceeds about 20um, maintaining the thickness of the range to maintain the wear resistance of the hard coating layer It can be, and the stain resistance by the PTFE can be expressed.

The hard coating layer is formed by the hard coating composition containing PTFE in a suitable distribution by forming a high density network composite by the presence of PTFE in the network composite formed after curing the ultraviolet curable resin, in a conventional hard coating layer It can maintain a high basis weight.

The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto.

<Examples and Comparative Examples>

Example

20 parts by weight of dipentaerythritol hexaacrylate, 60 parts by weight of ultraviolet curable acrylate (trade name HX-920UV, Kyoeisha), 15 parts by weight of silica fine particles (trade name XBA-ST, Ilsan Chemical), and photopolymerization initiator based on 100 parts by weight of total solids 5 parts by weight of Irgacure-184 (Ciba) and 5 parts by weight of polytetrafluoroethylene formed from a PTFE / PE mixed wax having an average particle size of 10 μm were mixed to prepare a hard coating composition having a solid content of 100%.

The composition was applied to one surface of a vinyl chloride resin base layer having a thickness of 2 mm and dried to form a hard coating layer having a thickness of 10 μm, thereby preparing a flooring material.

Comparative Examples 1 to 4

Excluding PTFE / PE mixed wax (Comparative Example 1), Alumina (Comparative Example 2), fluorine compound (MD-700, solvay) (Comparative Example 3), PE without PTFE formed from PTFE / PE mixed wax A flooring material was manufactured in the same manner as in the above example, except that wax (Comparative Example 4) was added.

Experimental Example-Chemical Resistance and Pollution Resistance of Flooring

1) Chemical resistance: After preparing a specimen having a horizontal X length of 100mmX 100mm as the flooring material of the above Examples and Comparative Examples, rubbing using methyl ethyl ketone and ethanol solvent, using 5% HCl solution and 5% KOH solution After rubbing, the hard coat layer was visually inspected for damage. After observation, no damage was described as OK and NG at the time of damage.

In addition, the damage area of the flooring damaged by the solvent, acid and base aqueous solution was evaluated by dividing it into 5 grades. If the damage area per unit area of the specimen was 20% or less, 1st grade, 20% to 50% grade 2, 50% The evaluation level was set to 3 grades, 70 to 90%, 4 grades, and 5 grades to 90% or more.

Table 1 additive solvent 5% HCl aqueous solution, 5% KOH aqueous solution Example PE / PTFE Wax OK, Level 1 OK, Level 1 Comparative Example 1 Except PE / PTFE Wax OK, Level 1 NG, Class 3 Comparative Example 2 Alumina OK, Level 1 NG, Class 2 Comparative Example 3 Fluorine compounds OK, Level 1 NG, Class 3 Comparative Example 4 PE wax OK, Level 1 NG, Class 2

According to Table 1, the hard coating layer of the Example was not damaged to the solvent, acid, and base aqueous solution, the hard coating layer of Comparative Examples 1 to 4 was damaged to the acid, and the base aqueous solution.

Example hard coating layer was formed by a hard coating composition comprising a PTFE formed from PE / PTFE wax, it was confirmed that the chemical resistance is secured by the PTFE.

2) Pollution resistance: After the flooring materials of Examples and Comparative Examples were contaminated by contacting external contaminants such as ballpoint pens, shoe polish, cement paste, and the like, the degree of contamination was visually observed. After observation, depending on the degree of contamination, O: no contamination, △: normal contamination, X: contamination.

TABLE 2 additive Pen Bitumen Cement paste Example PE / PTFE Wax O O O Comparative Example 1 Except PE / PTFE Wax X X X Comparative Example 2 Alumina △ △ △ Comparative Example 3 Fluorine compounds X △ X Comparative Example 4 PE wax △ △ △

According to Table 2, the flooring of the embodiment did not cause contamination of the contaminants of the ballpoint pen, bitumen, and cement paste, so that the hard coating composition includes PTFE formed from PE / PTFE wax to ensure contamination resistance. there was.

On the other hand, the flooring material of Comparative Example 1 was contaminated with the contaminants of the ballpoint pen, bitumen, and cement paste, so that the hard coating composition did not include PTFE, and thus, it was found that the flooring material did not secure contamination resistance.

The flooring material of Comparative Examples 2 and 4 including a hard coating layer formed of a hard coating composition including alumina, a fluorine compound, and PE wax had contaminated material, and thus the additives did not secure contamination resistance compared to PE / PTFE wax. It was confirmed.

Claims (11)

UV curable resin, inorganic particles, polytetrafluoroethylene and photopolymerization initiator Hard coating composition. The method of claim 1, The polytetrafluoroethylene is formed from a polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax Hard coating composition. The method of claim 2, The average particle size of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax is 10um to 20um Hard coating composition. The method of claim 2, The polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax is formed by copolymerizing polytetrafluoroethylene and polyethylene Hard coating composition. The method of claim 2, Specific gravity of the polytetrafluoroethylene / polyethylene (PTFE / PE) mixed wax is 1 to 1.5 Hard coating composition. The method of claim 1, 5 parts by weight to 80 parts by weight of the ultraviolet curable resin, 1 parts by weight to 20 parts by weight of the inorganic particles, 1 part by weight to 20 parts by weight of the polytetrafluoroethylene, and the photopolymerization initiator based on 100 parts by weight of solids. To include 1 part by weight to 15 parts by weight Hard coating composition. The method of claim 1, The ultraviolet curable resin to form a network composite after curing, Containing particulate polytetrafluoroethylene intertwined and present in the networked composite Hard coating composition. The method of claim 1, The average particle size of the inorganic particles is 0.01um to 1um Hard coating composition. The method of claim 1, The inorganic particles include at least one metal oxide selected from the group consisting of silica, alumina, zirconium oxide, and combinations thereof. Hard coating composition. 10. A hard coating layer formed on one surface of a vinyl chloride resin substrate layer using the hard coating composition according to any one of claims 1 to 9. Flooring. The method of claim 10, The thickness of the hard coating layer is 10um to 20um Flooring.

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