KR20190046407A - Flooring material - Google Patents

Abstract

The present invention relates to a flooring material which is environmentally friendly and excellent in workability, and the flooring material comprises a transparent layer containing a thermoplastic polyurethane resin.

Description

Flooring {FLOORING MATERIAL}

The present invention relates to a flooring material which is environmentally friendly and excellent in workability.

In general, residential floors are classified into PVC (polyvinyl chloride) and wood based, depending on the material. The PVC-based flooring may be PVC or PVC tile, and the wood-based flooring may include reinforced flooring, plywood flooring, and steel flooring.

The PVC-based flooring has been widely used since the 1970's because it has advantages such as relatively low price, excellent processability, and thermal characteristics suitable for floor heating. However, in the 2000s, PVC-based flooring has been exposed to the following human health hazards.

First, PVC generates harmful hydrogen chloride (HCl) gas and dioxin during combustion. Second, a phthalate plasticizer is added to enhance the flexibility of PVC in the process of manufacturing PVC flooring. In this case, the phthalate plasticizer added to the plasticizer acts as an environmental hormone in the human body to interfere with or disrupt normal metabolism.

To solve this problem, there has been proposed a technique for producing PVC flooring by using terephthalic acid (TPA) or BiO plasticizer as a substitute plasticizer instead of the phthalate plasticizer. However, there is still a doubt about the safety and processability of the above-mentioned technology using the substitute plasticizer.

In addition to the above-mentioned technologies, there has been proposed a technique of a PVC flooring material in which a plasticizer is not used, and the generation of hydrogen chloride (HCl) gas and dioxin is minimized during burning of the flooring material. The de-PVC flooring material may be a flooring material to which a polyolefin-based material, an acrylic-based material, or a polyethylene terephthalate-based material is applied.

The de-PVC-based material is designed so as to block the exposure of the PVC-based material in the lower layer by applying only to the upper layer (for example, transparent layer) of the bottom due to the increase in manufacturing cost and workability.

However, the above structure causes a difference in mechanical properties (for example, elongation and hardness) between the material constituting the upper layer and the PVC material constituting the lower layer, so that the upper and lower parts of the finished product are not balanced, Curling is a problem. Also, there is a problem that a crack occurs when the floor material is bent.

Therefore, it is required to develop an environmentally friendly and highly constructable flooring material.

Korean Patent Publication No. 2015-0131811

The present invention provides a floor material that is environmentally friendly and excellent in workability.

The present invention relates to a thermoplastic resin composition comprising a lower layer comprising a polyvinyl chloride resin, a fiber impregnated layer comprising a polyvinyl chloride resin provided on the lower layer, a printing layer provided on the fiber impregnated layer and a thermoplastic poly A flooring comprising a transparent layer comprising a urethane resin is provided.

Since the flooring material of the present invention is formed by applying a thermoplastic polyurethane resin as a de-PVC material to the transparent layer located on the upper side, exposure of the polyvinyl chloride resin and the plasticizer contained in each layer located under the transparent layer is blocked, Is excellent.

In addition, the flooring of the present invention is superior to the conventional flooring using the de-PVC-based material because of its superior curling (unraveling between the floor and the floor) and 90 ° bending (between the floor and the wall) ) Is minimized and thus the workability is excellent.

1 is a cross-sectional view illustrating a bottom material according to an embodiment of the present invention.

Hereinafter, the present invention will be described.

The present invention relates to a thermoplastic polyurethane resin composition which exhibits mechanical properties (for example, hardness, elongation, etc.) similar to polyvinyl chloride resin and which does not generate hydrogen chloride (HCl) gas and dioxin , TPU) resin is applied to the upper side of the bottom material, which will be described in detail with reference to the drawings. Here, the 'layer' described below may be interpreted as a layer or a film as the case may be. In addition, the 'layer' described below can be interpreted as a layer before the composition for forming each layer is cured, or as a layer after cured.

Referring to FIG. 1, the bottom layer of the present invention includes a bottom layer 10, a fiber impregnated layer 20, a print layer 30, and a transparent layer 40.

The lower layer 10 included in the bottom material of the present invention enhances the impact resistance and walking feeling of the floor material and reduces the occurrence of interlayer noise. The lower layer 10 may be formed of a first polyvinyl chloride resin composition comprising a polyvinyl chloride resin.

The first polyvinyl chloride resin composition comprises 45 to 50 parts by weight of a polyvinyl chloride resin, 20 to 30 parts by weight of a plasticizer (for example, dioctylterephthalate), a foaming agent (e.g., diazenedicarboxamide) 2 5 to 10 parts by weight of a filler (e.g., calcium carbonate), 1 to 5 parts by weight of an additive (e.g., nonylphenyl series) and 10 to 20 parts by weight of a flame retardant (e.g., aluminum hydroxide) .

The thickness of the lower layer 10 may be 200 to 2,000 mu m. If the thickness of the lower layer 10 is less than 200 탆, the impact resistance and walking feeling of the bottom material may be deteriorated. If the thickness is more than 2,000 탆, the bottom material may be thicker than necessary.

The fiber impregnated layer 20 included in the bottom material of the present invention is provided on the lower layer 10 and plays a role of improving the dimensional stability by the basic skeleton of the floor material. The fiber impregnated layer 20 may be formed by impregnating a glass fiber with a second polyvinyl chloride resin composition in a sol state including a polyvinyl chloride resin.

The second polyvinyl chloride resin composition comprises 30 to 40 parts by weight of a polyvinyl chloride resin, 20 to 30 parts by weight of a plasticizer (e.g., dioctylterephthalate), a heat stabilizer (e.g., Barium, 1 to 5 parts by weight of zinc carboxylates, 30 to 35 parts by weight of a filler (e.g., calcium carbonate), and 1 to 5 parts by weight of an additive (e.g., nonylphenyl series).

The thickness of the fiber impregnated layer 20 may be 200 to 400 탆. If the thickness of the fiber impregnated layer 20 is less than 200 탆, the dimensional stability of the bottom material may be deteriorated. If the thickness is more than 400 탆, the bottom material may be thicker than necessary.

The printed layer 30 included in the bottom material of the present invention is provided on the fiber impregnated layer 20 and serves to impart a sense of beauty to the bottom material. The printing layer 30 is formed by transferring (for example, gravure transfer) a pattern (for example, a wood grain pattern) printed on a substrate (for example, a polyethylene terephthalate film) onto the fiber impregnated layer 20 As shown in FIG.

The pattern comprises from 35 to 45 parts by weight of medium, from 30 to 40 parts by weight of a solvent (e.g., methyl ethyl ketone), from 10 to 20 parts by weight of ink, ) ≪ / RTI > in an amount of 5 to 15 parts by weight.

The transparent layer 40 included in the bottom material of the present invention is provided on the printing layer 30 and enhances the durability of the bottom material. The transparent layer 40 may be formed of a polyurethane resin composition containing a thermoplastic polyurethane resin, thereby improving wear resistance, flexural resistance, oil resistance, weather resistance, elasticity, etc. in addition to the durability of the flooring. Particularly, since the thermoplastic polyurethane resin included in the transparent layer 40 is similar in mechanical properties to polyvinyl chloride resin included in the lower layer 10 and the fiber impregnated layer 20 and has good compatibility with the polyvinyl chloride resin, And can minimize the generation of cracks during the bending process.

The polyurethane resin composition may be composed of a thermoplastic polyurethane resin alone. The polyurethane resin composition may contain, in addition to the thermoplastic polyurethane resin, a synthetic resin-based resin, an ultraviolet absorber, a heat stabilizer, and a release agent. At this time, the content of the thermoplastic polyurethane resin may be 95 to 99.5 parts by weight based on the total weight of the polyurethane resin composition.

The thermoplastic polyurethane resin contained in the polyurethane resin composition preferably has a hardness (Shore D) of 50 to 75, an elongation of 200% or more (for example, 250 to 400%), a melt viscosity (220 캜) It can be 35,000 Poise. When the hardness, elongation, and melt viscosity of the thermoplastic polyurethane resin are out of the above ranges, curling of the thermoplastic polyurethane resin to the upper part of the bottom material occurs, and cracks may occur during bending of the bottom material.

The synthetic rubber-based resin included in the polyurethane resin composition may be at least one selected from the group consisting of ABS (acrylonitrile-butadiene-styrene) resin, NBR (acrylonitrile butadiene rubber) resin and SEBS (styrene-ethylbutylene-styrene) resin.

The thickness of the transparent layer 40 may be 100 to 300 탆. If the thickness of the transparent layer 40 is less than 100 탆, the durability, abrasion resistance and elasticity of the bottom material may be lowered, and if it exceeds 300 탆, the raw material cost may excessively increase.

Meanwhile, the bottom material of the present invention may further include a reinforcing layer 50 provided under the lower layer 10. The reinforcing layer 50 plays a role similar to the lower layer 10 in that it plays the role of enhancing the strength, impact resistance and walking feeling of the flooring material and reducing the generation of interlayer noise. This reinforcing layer 50 may be formed of a third polyvinyl chloride resin composition containing a polyvinyl chloride resin.

The third polyvinyl chloride resin composition comprises 45 to 50 parts by weight of a polyvinyl chloride resin, 20 to 30 parts by weight of a plasticizer (e.g. dioctylterephthalate), 2 to 30 parts by weight of a foaming agent (e.g., diazenedicarboxamide) 2 5 to 10 parts by weight of a filler (e.g., calcium carbonate), 1 to 5 parts by weight of an additive (e.g., nonylphenyl series) and 10 to 20 parts by weight of a flame retardant (e.g., aluminum hydroxide) .

The thickness of the reinforcing layer 50 may be 100 to 5,000 [mu] m. If the thickness of the reinforcing layer 50 is less than 100 탆, the strength and impact resistance of the flooring may be lowered. If the thickness exceeds 5,000 탆, the flooring may be thicker than necessary.

In addition, the bottom material of the present invention may further include a surface protective layer 60 provided on the transparent layer 40. The surface protective layer 60 serves to adjust the surface gloss of the bottom material and improve the anti-staining property and slip resistance. The surface protective layer 60 may be formed of a photocurable resin composition.

The photocurable resin composition contains 40 to 50 parts by weight of a urethane acrylate resin, 30 to 40 parts by weight of an acrylate monomer, 1 to 10 parts by weight of an additive (for example, a dispersing agent, a leveling agent) 1 to 5 parts by weight of a quencher (for example, SiO ₂ ), and 1 to 5 parts by weight of a photoinitiator.

The thickness of the surface protection layer 60 may be 5 to 30 탆. If the thickness of the surface protective layer 60 is less than 5 탆, the appearance and stain resistance of the bottom material may be deteriorated, and if it exceeds 30 탆, a surface crack may occur.

The flooring material of the present invention is applied to the transparent layer 40 by applying the thermoplastic polyurethane resin as the de-PVC-based material so that the surface exposure of the polyvinyl chloride resin and the plasticizer contained in each layer provided under the transparent layer 40 is blocked, It can exhibit excellent environmental friendliness. Therefore, the flooring of the present invention can be usefully used as a residential flooring.

Also, by applying a thermoplastic polyurethane resin having mechanical properties similar to those of polyvinyl chloride resin to the transparent layer 40, it is possible to prevent uneven settlement (curling between the floor and floor) and 90 ° bending work The occurrence of cracks is minimized in the case of the present invention, and the floor material of the present invention can exhibit excellent workability.

Such flooring materials of the present invention can be produced conventionally by a known method. Concretely, the fiber-impregnated layer 20, which serves as a skeleton of the floor material, is formed by laminating the glass fiber containing the second polyvinyl chloride resin composition and the polyvinyl chloride film formed by the first polyvinyl chloride resin composition through heat and pressure, Thereby forming a bottom layer 10 which imparts cushioning and durability to the flooring. Next, the print pattern printed on the polyethylene terephthalate film is transferred onto the fiber impregnated layer 20 to form the print layer 30. [ Then, a transparent film formed of a polyurethane resin composition is placed on the print layer 30, and the transparent layer 40 is formed by laminating the transparent film to protect the print layer 30 and to enhance the durability of the bottom material. Next, a third polyvinyl chloride resin composition is applied under the lower layer 10 to form a reinforcing layer 60 that improves the cushioning and seating properties of the flooring. Then, the flooring material of the present invention can be manufactured through the process of applying the photocurable resin composition on the transparent layer 40 to form the surface protective layer 50.

Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example  One]

80 parts by weight of a plasticizer (Dioctyl Terephthalate), 3 parts by weight of a heat stabilizer (Ba series, Zn series), 3 parts by weight of Epoxidized Soybean Oil, and 100 parts by weight of a polyvinyl chloride (PVC) 120 parts by weight of a filler (calcium carbonate), 6 parts by weight of a white pigment (titanium dioxide), and 3 parts by weight of an additive (viscosity controlling agent) were mixed to prepare a second polyvinyl chloride resin composition in a sol state. Thereafter, 45 g of the glass fiber was impregnated with the second polyvinyl chloride resin composition thus prepared.

Next, 45 parts by weight of a plasticizer (dioctyl terephthalate), 5 parts by weight of a foaming agent (Azodicarbonamide), 5 parts by weight of a foam stabilizer (Ba-based, Zn-based) 2 And 50 parts by weight of a filler (calcium carbonate) were mixed to prepare a first polyvinyl chloride resin composition. The first polyvinyl chloride resin composition was processed with a calender roll at about 180 ° C to prepare a polyvinyl chloride (PVC) film (sheet).

Then, the polyvinyl chloride film was laminated on the lower part of the glass fiber, and a fiber impregnated layer (thickness: 300 mu m) and a lower layer (thickness: 500 mu m) were formed through a process of passing through a drum of about 185 DEG C .

Next, a polyethylene terephthalate film (PET film) on which a printed pattern was printed was placed on the fiber impregnated layer, and the printed pattern was transferred onto the fiber impregnated layer to form a printed layer.

Next, a polyurethane resin composition comprising 99 parts by weight of a thermoplastic polyurethane (TPU) resin having a hardness (Shore D) of 60, a elongation of 250% and a melt viscosity (Poise / 220 캜) of 30,000 And the transparent film prepared by co-extrusion was placed on the printing layer and thermally joined to form a transparent layer (thickness: 150 mu m).

Next, 60 parts by weight of a plasticizer (dioctyl terephthalate), 3 parts by weight of a heat stabilizer (Ba-based, Zn-based), 3 parts by weight of a filler (calcium carbonate) were added to 100 parts by weight of a polyvinyl chloride 6 parts by weight of a white pigment (titanium dioxide) and 1 part by weight of a colored pigment were mixed to prepare a third polyvinyl chloride resin composition in a sol state. Thereafter, the prepared third polyvinyl chloride resin composition was applied to the lower layer to form a reinforcing layer (thickness: 100 mu m).

Then, a photo-curing resin composition in which 50 parts by weight of a urethane acrylate resin, 39 parts by weight of an acrylate monomer, 3 parts by weight of a photoinitiator, 1 part by weight of an additive and 7 parts by weight of a quencher were applied, (Thickness: 17 占 퐉) was formed under the conditions of a light output of 140 W / cm 2, a light energy of 700 mJ / cm 2 and a light energy arrival time of 8 seconds while irradiating light of a wavelength of? Respectively.

[ Example  2]

Except that a transparent film made of a composition comprising a thermoplastic polyurethane resin having an elongation of 200% was used.

[ Example  3]

Except that a transparent film made of a composition comprising a thermoplastic polyurethane resin having an elongation of 170% was used.

[ Example  4]

Except that a transparent film made of a composition comprising a thermoplastic polyurethane resin having an elongation of 140% was used as a base material.

[ Example  5]

Except that a transparent film made of a composition comprising a thermoplastic polyurethane resin having an elongation of 120% was used.

[ Comparative Example  One]

Except that a film (PVC film) containing polyvinyl chloride resin was used in place of the transparent film made of the composition comprising the thermoplastic polyurethane resin.

[ Comparative Example  2]

Except that a film (polypropylene film) comprising a polyolefin resin was used in place of the transparent film made of the composition containing the thermoplastic polyurethane resin.

[ Comparative Example  3]

Except that a film containing an acrylic resin (PMMA film) was used instead of a transparent film made of a composition containing a thermoplastic polyurethane resin.

[ Comparative Example  4]

Except that a film (PET film) containing polyethylene terephthalate resin was used in place of the transparent film made of the composition containing the thermoplastic polyurethane resin.

[ Experimental Example  One]

The physical properties of the flooring prepared in each of Examples and Comparative Examples were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.

1. Curling: The specimens were held at 80 ± 2 ℃ for 6 hours and then allowed to stand at 25 ± 2 ℃ for 1 hour.

2. Crack resistance: The lowest temperature at which a crack occurred after 180 ° bending of a specimen was measured.

3. Abrasion resistance: The flooring specimens for the Taber abrasion tester (5155 Abraser) were evaluated by measuring the reduced weight with respect to the initial weight after rotating the test piece through a 1 kg load bearing wheel (Taber H18) 500 times.

4. TVOC Emission Amount: It was measured according to indoor air quality process test (Ministry of the Environment Notice No. 2017-11).

division unit Example 1 Example 2 Example 3 Example 4 Example 5 Curling Mm 1 or less 1 or less 2.5 or more 3 or more 4 or more Crack resistance ℃ -30 or less -20 or less -below 10 -5 or higher -5 or higher Abrasion resistance Mg 5 or less 5 or less 5 or less 5 or less 5 or less TVOC emission ㎎ / ㎡ · h 0.05 or less 0.05 or less 0.05 or less 0.05 or less 0.05 or less

division unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Curling Mm 1 or less over 10 over 10 7 or more Crack resistance ℃ -20 or less 8 or more 8 or more 8 or more Abrasion resistance Mg Less than 50 Less than 50 Less than 50 Less than 50 TVOC emission ㎎ / ㎡ · h 0.1 or less 0.05 or less 0.05 or less 0.05 or less

Referring to Table 1, the flooring materials of Examples 1 to 5, which are the flooring materials of the present invention, minimize the seizure (floating between the floor and the flooring) by curling and minimize the occurrence of the flooring There is no problem in the degree of occurrence of cracks, and thus it can be confirmed that the workability is excellent. In addition, the emission of TVOC is very low.

On the other hand, referring to Table 2, Comparative Example 1 in which a PVC film is applied to a transparent layer is inferior in abrasion resistance and environment friendliness, and Comparative Examples 2 to 4 in which a de-PVC material film is applied have curling and crack resistance It can be confirmed that the workability is deteriorated due to a problem.

10: Lower layer
20: fiber impregnated layer
30: Printed layer
40: transparent layer
50: reinforced layer
60: surface protective layer

Claims (4)

A lower layer comprising polyvinyl chloride resin,
A fiber impregnated layer comprising a polyvinyl chloride resin provided on the lower layer,
A printed layer provided on the fiber impregnated layer and
And a transparent layer comprising a thermoplastic polyurethane resin provided on the printing layer. The method according to claim 1,
Wherein the thermoplastic polyurethane resin has a hardness (Shore D) of 50 to 75, an elongation of 200% or more, and a melt viscosity (220 캜) of 25,000 to 35,000 Poise. The method according to claim 1,
Wherein the transparent layer is formed of a composition comprising a thermoplastic polyurethane resin, a synthetic rubber-based resin, an ultraviolet absorber, a heat stabilizer and a releasing agent. The method of claim 3,
Wherein the synthetic rubber resin is at least one selected from the group consisting of ABS (acrylonitrile-butadiene-styrene) resin, NBR (acrylonitrile butadiene rubber) resin and SEBS (styrene-ethylbutylene-styrene) resin.

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