KR102269523B1 - Floorings having excellent anti scratch resistance and non-slip property - Google Patents

Abstract

The present invention relates to a flooring material having excellent stain resistance and non-slip properties and a method for manufacturing the same, wherein the flooring material is an acrylic resin composition containing a urethane acrylic oligomer, an oligomer containing a silicon-containing functional group, and a polyfunctional acrylic monomer during production. By irradiating the short-wavelength light step by step to form a coating layer on the outermost surface, high hardness can be realized on the surface, and a fine curved structure in the form of a branched second wrinkle in the first wrinkle is induced throughout the surface to achieve a 60° gloss-meter ( 60° Gloss-Meter), it shows a remarkably low surface gloss, and has excellent scratch resistance and non-slip properties.

Description

Flooring with excellent scratch resistance and non-slip property {Floorings having excellent anti scratch resistance and non-slip property}

The present invention relates to a flooring material having excellent scratch resistance and non-slip property and a method for manufacturing the same, and more particularly, to a flooring material having excellent scratch resistance and non-slip property by inducing a fine wrinkle structure in the form of branching fine wrinkles in the longitudinal direction on the surface; It relates to a manufacturing method thereof.

In general, flooring provides a hygienic space by blocking dust and cold air from the cement floor, and has a decorative effect such as changing the indoor atmosphere cozy according to the customer's taste as beautiful patterns of various colors are printed.

These flooring materials require physical properties such as cushioning, abrasion resistance, durability, scratch resistance, and stain resistance as well as aesthetics, and for this, a certain level of UV-curable matte paint layer is applied to the entire flooring material or the outermost layer of the substrate to be coated. technology to form a coating film with scratch resistance or chemical resistance on the surface by introducing

In the case of the conventional UV curable matte paint composition for PVC flooring, including the prior art, since the focus is only on improving the physical properties of the scratch resistance due to the nature of the flooring, there is an insufficient limit in improving the physical properties of the non-slip property.

In addition, in order to add non-slip properties to the flooring, a method of imparting surface roughness is generally applied to the paint layer formed on the outermost surface. However, in this case, in order to impart surface roughness, inorganic particles are added to the UV curable matte paint composition, or a method of spraying inorganic particles on the surface after coating a coating film through UV curing is performed. There was a problem in that inorganic particles are easily separated to inhibit non-slip properties or provide non-uniform non-slip properties.

Therefore, there is an urgent need to develop a flooring material that is low-gloss, has excellent scratch resistance, and has excellent non-slip properties and improved pedestrian safety.

Republic of Korea Patent Publication No. 2010-0071599 Republic of Korea Patent Publication No. 2014-0089074

It is an object of the present invention to provide a flooring material with improved non-slip properties while exhibiting low gloss by controlling the surface structure of the coating layer located at the outermost layer of the flooring material while implementing scratch resistance.

Accordingly, the present invention in one embodiment,

a foam layer, a base layer, and a coating layer of an acrylic resin composition;

The coating layer may include a first wrinkle having a first directionality; and a surface structure comprising a second pleat branching from the first pleat and having a second directionality,

The second directionality provides a flooring material having an angle of 50 to 140° with respect to the first directionality.

In addition, the present invention in one embodiment,

A first light irradiation step of activating the composition by irradiating the acrylic resin composition with light having a wavelength of less than 300 nm under an inert gas condition;

A second light irradiation step of primary light curing of the composition by irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions; and

It provides a method of manufacturing the flooring material comprising a third light irradiation step of irradiating light of a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary light curing the composition.

The flooring material according to the present invention is produced by irradiating a urethane acrylic oligomer, an acrylic resin composition containing a silicon-containing functional group, and a polyfunctional acrylic monomer with short wavelength light in a specific range stepwise to form a coating layer on the outermost surface, High hardness can be realized on the surface, and a fine curved structure in which the first and second wrinkles are branched is induced over the entire surface, resulting in significantly lower surface gloss in the 60° Gloss-Meter standard. It has the advantage of being excellent in scratch property and non-slip property.

1 is a structural diagram showing an example of a light curing device used in the manufacture of a coating layer according to the present invention.
2 is a scanning electron microscope (SEM) image of the surfaces of the flooring specimens prepared in Examples 1 to 4 and Comparative Example 1 according to the present invention.
3 is a scanning electron microscope (SEM) image of the surface of the coating layer of Comparative Example 6 according to the present invention.

Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and described in detail in the detailed description.

However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In the present invention, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.

In addition, it should be understood that the accompanying drawings in the present invention are enlarged or reduced for convenience of description.

Hereinafter, the present invention will be described in detail with reference to the drawings, and the same or corresponding components are assigned the same reference numerals regardless of reference numerals, and overlapping descriptions thereof will be omitted.

In the present invention, "surface profile" indicates the degree of fine irregularities present on the surface, and may be expressed as "Rz". Here, "Rz" represents the deviation by taking the reference length L as the cross-sectional curve of the surface and measuring the interval between the peak from the highest to the fifth peak of the curved structure and the valley from the deepest to the fifth, " Also called "ten point average roughness".

In addition, in the present invention, "T" is a unit indicating the thickness of each layer or sheet provided in the flooring, and may be the same as the unit "mm".

The present invention relates to a flooring material having excellent stain resistance and non-slip properties and a method for manufacturing the same.

Flooring materials require physical properties such as cushioning, abrasion resistance, durability, scratch resistance, and stain resistance as well as aesthetics, and for this purpose, a certain level of UV-curable matte paint layer is applied to the entire flooring material or the outermost layer of the substrate to be coated. A technology to form a coating film with scratch resistance or chemical resistance on the surface is applied.

In the case of the conventional UV curable matte paint composition for PVC flooring, including the prior art, since the focus is only on improving the physical properties of the scratch resistance due to the nature of the flooring, there is an insufficient limit in improving the physical properties of the non-slip property.

In addition, in order to add non-slip properties to the flooring, a method of imparting surface roughness is generally applied to the paint layer formed on the outermost surface. However, in this case, in order to impart surface roughness, inorganic particles are added to the UV curable matte paint composition, or a method of spraying inorganic particles on the surface after coating a coating film through UV curing is performed. There was a problem in that inorganic particles are easily separated to inhibit non-slip properties or provide non-uniform non-slip properties.

Accordingly, the present invention provides a flooring material excellent in scratch resistance and non-slip properties and a method for manufacturing the same.

The flooring material according to the present invention is produced by irradiating a urethane acrylic oligomer, an acrylic resin composition containing a silicon-containing functional group, and a polyfunctional acrylic monomer with short wavelength light in a specific range stepwise to form a coating layer on the outermost surface, High hardness can be realized on the surface, and a fine curved structure in which the first and second wrinkles are branched is induced over the entire surface, resulting in significantly lower surface gloss in the 60° Gloss-Meter standard. It has the advantage of being excellent in scratch property and non-slip property.

Hereinafter, the present invention will be described in more detail.

flooring

The present invention in one embodiment,

A foam layer, a base layer, and a coating layer of an acrylic resin composition,

The coating layer may include a first wrinkle having a first directionality; and a surface structure comprising a second pleat branching from the first pleat and having a second directionality,

The second directionality provides a flooring material having an angle of 50 to 140° with respect to the first directionality.

The flooring material according to the present invention is an indoor flooring material used in homes or offices, and includes a foaming layer, a base layer and a coating layer. Here, the coating layer is a cured layer of the acrylic resin composition and is located on the outermost layer of the flooring material, and has a fine curved structure having a constant surface roughness and shape on the surface thereof. Specifically, the curved structure has a fine wrinkle structure including a first wrinkle having a first directionality and a second pleat branched from the first wrinkle and having a second directionality on the surface. Here, the second directionality is based on the first directionality of the first pleats at the point where the second pleats branch from the first pleats. For example, the second directionality may have an angle of 50 to 140° with respect to the first directionality, and 2 to 20 such second wrinkles may exist per unit length (0.5 mm) of the first pleats. Specifically, the second wrinkles are 50 to 130 °, 50 to 120 °, 50 to 110 °, 50 to 100 °, 60 to 140 °, 70 to 140 °, 80 to 140 °, 60 to with respect to the first directionality 130°, 65 to 120°¸70 to 110°¸ 80 to 100° or 85 to 95° may have a second directionality, wherein the corrugations are from 2 to per unit length (0.5 mm) of the first corrugation. 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 4, 3 to 6, 5 to 10, 4 to 18, 6 to 18, 8 to 18, 10 to 18, 12 to 18 ¸15 to 18, 5 to 15 ¸8 to 12, 10 to 15 or 12 to 16 branches may be branched.

In addition, in the wrinkle structure, the second wrinkle is branched from the first wrinkle, and the second wrinkle may have the form of fine fine wrinkles having an average thickness and length equal to or smaller than that of the first wrinkle. For example, the average thickness of the first pleats may be 10 μm to 100 μm, the average thickness of the second pleats may be 1 μm to 50 μm, and the average thickness of the first pleats is equal to or greater than the average thickness of the second pleats. It has a thick thickness, so that Equation 1 below can be satisfied:

[Equation 1] 0.9 ≤ T _1st /T _2nd ≤ 3

In Equation 1, T _1st is the thickness of the first wrinkle, and T _2nd is the thickness of the second wrinkle.

Specifically, the average thickness of the first wrinkle is 10 μm to 90 μm, 10 μm to 80 μm, 10 μm to 70 μm, 10 μm to 60 μm, 10 μm to 50 μm, 10 μm to 40 μm, 20 μm to 100 μm. μm, 30 μm to 100 μm, 40 μm to 100 μm, 50 μm to 100 μm, 60 μm to 100 μm, 30 μm to 80 μm, 40 μm to 70 μm, 20 μm to 40 μm, 70 μm to 90 μm, or 50 to 90 μm; The average thickness of the second wrinkle is 1 μm to 40 μm, 1 μm to 30 μm, 1 μm to 20 μm, 1 μm to 10 μm, 5 μm to 50 μm, 10 μm to 50 μm, 15 μm to 50 μm, 20 μm to 50 μm, 25 μm to 50 μm, 30 μm to 50 μm, 40 μm to 50 μm, 10 μm to 20 μm, 10 μm to 30 μm, 20 μm to 40 μm, 30 μm to 40 μm, 5 μm to 15 μm, or 15 μm to 25 μm; A second average thickness (T _2nd) ratio (T _1st / T _2nd) of the folds of the first average thickness of the average thickness (T _1st) of the first folds of equal or thicker than that compared to the average thickness of the second folds of the wrinkles 0.9 to 3, 0.9 to 2.5, 0.9 to 2, 0.9 to 1.5, 0.9 to 1.2, 1.0 to 3, 1.2 to 3, 1.5 to 3, 2.0 to 3, 1.0 to 2.5, 1.0 to 2.0, 1.1 to 1.9, 1.1 Equation 1 may be satisfied as to 1.8¸1.2 to 1.5¸ 1.1 to 1.8 or 1.0 to 1.4.

In addition, the average length of the first wrinkles may be 200 μm to 5,000 μm, and the average length of the second wrinkles may be 50 μm to 1,000 μm, wherein the average length of the first wrinkles is equal to or longer than the average length of the second wrinkles. can Specifically, the average length of the first wrinkles is 200㎛ to 4,000㎛, 200㎛ to 3,000㎛, 200㎛ to 2,000㎛, 200㎛ to 1,000㎛, 200㎛ to 500㎛, 400㎛ to 2,000㎛, 500㎛ to 1,500 μm, 800 μm to 1,200 μm, 1,200 μm to 1800 μm, 2,200 μm to 3,000 μm, 2,500 μm to 3,800 μm, 2,800 μm to 3,200 μm, 3,100 μm to 3,600 μm, 3,200 μm to 4,000 μm, 4,200 μm to 5,000 μm , 3,900 μm to 4,900 μm, 700 μm to 900 μm, 900 μm to 1,100 μm, 1,300 μm to 1,700 μm, 1,500 μm to 2,000 μm, 800 μm to 2,100 μm or 1,900 μm to 2,600 μm, The average length is 50 μm to 900 μm, 50 μm to 800 μm, 50 μm to 700 μm, 50 μm to 600 μm, 50 μm to 500 μm, 50 μm to 400 μm, 50 μm to 300 μm, 50 μm to 200 μm. , 50 μm to 100 μm, 100 μm to 1,000 μm, 200 μm to 1,000 μm, 300 μm to 1,000 μm, 400 μm to 1,000 μm, 500 μm to 1,000 μm, 600 μm to 1,000 μm, 700 μm to 1,000 μm, 800 μm to 1,000 μm, 150 μm to 300 μm, 200 μm to 500 μm, 400 μm to 800 μm, 500 μm to 700 μm, 600 μm to 900 μm, 700 μm to 900 μm, 100 μm to 400 μm or 50 μm to 180 μm.

As an example, the wrinkle structure has a first wrinkle having an average thickness of 60 to 70 μm and an average length of 1,200 μm to 1,600 μm, and a second wrinkling having an average thickness of 15 to 30 μm and an average length of 300 μm to 700 μm is the first wrinkle. may have a branched form of 80 to 110° with respect to the first directionality of

In addition, the flooring material according to the present invention may include a wrinkle-shaped fine curved structure on the surface at a certain frequency per unit area, for example, in a certain number. Specifically, the flooring material may have 1 to 20 fine wrinkle structures per unit area (2 mm X 2 mm) of the coating layer, and more specifically, 1 to 18 pieces per unit area (2 mm X 2 mm) of the coating layer. , 1-16, 1-14, 1-12 1-10 1-8, 1-6, 1-5, 1-4, 2-20, 5-20, 10 to 20, 15 to 20, 2 to 7, 1 to 9, 1 to 3 or 3 to 8 fine wrinkle structures.

In addition, as shown in FIG. 2 , in the fine wrinkle structure, one or more other first wrinkle adjacent to the first wrinkle may contact to form a cell, but the number of cells thus formed has a unit area (2 mm X 2). less than 5 per mm). Since the non-slip property may not be sufficiently implemented as the number of the cells increases, the present invention may improve the non-slip property of the flooring material by controlling the number of cells per unit area within the above range. Here, one or two cells may be formed per unit area (2 mm X 2 mm) with an average size of 0.5 to 2.0 mm, or 0.8 to 1.2 mm.

Furthermore, the coating layer may have a constant surface roughness by having a fine wrinkle structure formed on the surface. Specifically, the coating layer may have an average value of the surface roughness "Rz" of 10 μm to 30 μm including the fine wrinkle structure present on the surface, and more specifically, 10 μm to 28 μm, 10 μm to 26 μm, 10 μm to 24 μm, 15 μm to 30 μm, 20 μm to 30 μm, 25 μm to 30 μm, 15 μm to 25 μm, 18 μm to 30 μm, 18 μm to 25 μm, 15 μm to 24 μm, 18 μm to 24 μm, 10 μm to 15 μm, 11 μm to 13 μm, 21 μm to 26 μm, 11 μm to 23 μm, 20 μm to 24 μm, or 23 μm to 27 μm.

The flooring material according to the present invention has as the outermost layer a coating layer including a wrinkle-shaped fine curved structure having the shape and frequency as described above as the outermost layer to more easily control physical properties such as surface glossiness, non-slip property, and scratch resistance. can

As an example, the flooring material according to the present invention induces scattering of light incident on the surface through the fine wrinkle structure formed on the surface of the coating layer, so that the coating layer contains a very small amount of matting agent or in some cases does not contain a very low gloss. can be implemented Specifically, the flooring material may have a surface gloss of 1 to 6 when measuring 60 ° gloss (gloss 60 ° condition) using a gloss meter, and more specifically, an upper limit of 6 or less, 5.5 or less, 5 or less, 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, or 2.3 or less, and the lower limit may be 1 or more, 1.1 or more, 1.5 or more, 2 or more, or 2.5 or more. For example, the average surface glossiness of the flooring material is 1.0 to 5.5, 1.0 to 5.2, 1.0 to 4.8, 1.0 to 4.5, 1.0 to 4, 1.0 to 3.5, 1.0 to 3, 1.0 to 2.8, 1.0 to 2.4, 1.0 to 1.8, 4.5 to 5.0, 4.2 to 4.7, 4.4 to 4.6, 3.9 to 5.0, 4.5 to 5.2, 3.85 to 4.2, 2.9 to 4.3, 3.2 to 4.7, 2.1 to 3.5, 2.7 to 3.1, 2.9 to 3.6, 2.1 to 3.1, 2.3 to; 2.8, 1.9 to 2.9, 1.1 to 2.8, 1 to 2.5, 1 to 2.2, 1.7 to 2.9, 1.1 to 1.9, 1.3 to 2.2, 1.2 to 1.7, 1.8 to 2.2, 1.3 to 2.4. The flooring material of the present invention can improve the aesthetic effect and reduce the user's eye fatigue by controlling the surface glossiness in the above range, and introduce an embossed structure (depth: about 0.1 to 2.0mm) to give a three-dimensional effect to the surface. In this case, it is possible to prevent the visibility of the emboss from being deteriorated due to the very low glossiness.

As another example, the flooring material according to the present invention has improved non-slip properties, so that the grade of the inclination angle at which slip occurs during a ramp test according to DIN 51130 may be R10 or more, specifically R11 or more, or R10 to R11. Here, R10 represents a case in which the angle of inclination at which slip occurs is 10° or more and less than 19°, and R11 represents a case in which the angle of inclination at which slip occurs is 19° or more and less than 27°.

As another example, the flooring material according to the present invention has excellent scratch resistance, so it may be less than B2 grade in which less than 10 light scratches occur on the surface when micro-scratch resistance is evaluated according to the B procedure of EN 16094. As a result, it may be a B1 grade that does not cause scratches. This means that the surface hardness is increased by providing a coating layer having a structure in which oligomers are crosslinked including a polyfunctional acrylic monomer including two or more polymerizable functional groups on the outermost layer of the flooring material.

Furthermore, as another example, the flooring material according to the present invention may have excellent low-temperature breaking strength of the hardened layer, and thus may have excellent durability even at low temperatures. Specifically, the flooring material has excellent durability at low temperatures, so when a falling object weighing 2.5 kgf is dropped on the surface, damage to the surface of the flooring material does not occur near -25°C, and at a lower temperature, for example, -35°C to -25 °C, -32 °C to -25 °C, -30 °C to -25 °C, -30 °C to -27 °C, -28 °C to -25 °C, -27 °C to -25 °C, or -26 °C to Surface damage such as cracks, cracks, and pinholes may occur at -25.5℃.

The coating layer may have an average thickness in an appropriate range that does not affect durability. For example, the coating layer may have an average thickness of 5 μm to 30 μm so as not to be torn or lost by external stimuli, more specifically 5 μm to 30 μm, 5 μm to 15 μm, 10 μm to 20 μm, 10 μm to 30 μm, 20 μm to 30 μm, 8 μm to 17 μm, 11 μm to 20 μm, or 12 μm to 18 μm.

On the other hand, the flooring material according to the present invention may further include a separate layer in addition to the foam layer, the base layer and the coating layer. Specifically, the flooring material may further include any one or more of a printing layer and a dimensionally stable layer between the foam layer and the base layer. For example, the flooring may have a structure in which a foaming layer, a printed layer, a base layer and a coating layer are sequentially stacked, or a foamed layer, a dimensionally stable layer, a printed layer, a base layer and a coating layer are sequentially stacked. can

Here, the base layer, the printing layer, the dimensionally stable layer and the foam layer are, for example, a binder resin, an initiator, a curing agent, other additives, and each composition comprising at least one selected from the group consisting of photocuring or It may be formed by thermosetting, or may be formed as a film or sheet using an extrusion method, a calendaring method, or the like. In addition, each of the compositions may appropriately control the types and contents of the components included therein according to the properties and functions of each layer, and is not particularly limited. Specifically, the flooring material is formed by applying a predetermined composition to one surface of any one layer and then photocuring or thermal curing, or forming each layer as a film or sheet, and then forming them in a plywood process known in the art, etc. It can be formed using, but is not limited thereto. In addition, the binder resin may include a synthetic resin, a bio-resin, or both, for example, a polyvinyl chloride (PVC)-based resin, a polyurethane-based resin, a polylactic acid-based resin, a polyolefin resin, etc. .

In addition, the base layer may have a thickness of about 0.05 mm to about 3.0 mm as a transparent or translucent polyvinyl chloride (PVC) layer, and by having a thickness within the above range, without excessively increasing the total thickness of the flooring material, which will be described later. As shown, it is possible to sufficiently protect the pattern or pattern of the printed layer laminated on the bottom.

In addition, the printing layer may include a white layer forming a base and a transfer layer implementing a pattern, for example, various types of transfer printing, gravure printing, screen printing, offset printing, rotary printing or flexographic printing, etc. It can be formed by imparting a pattern in this way. In this case, the printed layer may have an average thickness of about 1 μm to about 10 μm.

In addition, the dimensionally stable layer may be formed of a composite material in which glass fibers are impregnated in a binder resin. The dimensionally stable layer thus formed realizes excellent dimensional stability by reducing dimensional strain even under high-temperature, high-humidity conditions, while maintaining high level of adhesion with other layers laminated on the top and bottom to realize excellent durability. In this case, the average thickness of the dimensionally stable layer may be about 0.1 mm to about 2.0 mm.

Furthermore, the foam layer is a layer located at the bottom of the flooring, and while supporting the coating layer, the substrate layer, the printing layer, the dimensional stability layer, etc., it contains pores of a certain size to absorb the impact and noise of the upper or lower part. have a function In this case, the average size of the pores may be 100 to 900 μm, specifically 100 to 800 μm, 100 to 700 μm, 100 to 600 μm, 100 to 500 μm, 200 to 900 μm, 300 to 900 μm, 400 to 900 μm, 500 to 900 μm, 600 to 900 μm, 200 to 800 μm, 500 to 800 μm, 600 to 700 μm, 200 to 400 μm, or 750 to 900 μm. In addition, the average thickness of the foam layer may be 0.5 to 10T, more specifically 0.5 to 8T, 0.5 to 6T, 0.5 to 4T, 4 to 10 T, 6 to 10 T, 8 to 10T, 3 to 6T, 4 to 7T, 7 to 9T, 2 to 3T, or 0.5 to 1.5T. In addition, the composition of the foam layer is not particularly limited, but polyvinyl chloride (PVC), thermoplastic polyurethane (TPU), nitrile-butadiene rubber (NBR), polyvinylether (polyvinylether, PVE), ethylene vinylacetate (EVA), polyurethane (polyurethane, PU), and the like may be included.

Method of manufacturing flooring

In addition, the present invention in one embodiment,

A first light irradiation step of activating the composition by irradiating the acrylic resin composition with light having a wavelength of less than 300 nm under an inert gas condition;

A second light irradiation step of primary light curing of the composition by irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions; and

It provides a method for producing a flooring material comprising a third light irradiation step of irradiating light of a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary light-curing the composition.

The method of manufacturing a flooring material according to the present invention has a step of curing the acrylic resin composition by irradiating the acrylic resin composition with short-wavelength light in a specific range under different conditions in three steps.

Specifically, the first light irradiation step is a first step of irradiating light to the acrylic resin composition applied on the base layer, and the excimer generated by the irradiated light is applied to the acrylic resin composition and/or its diameter. This is a step of increasing the scattering rate of light incident on the surface by shrinking the cargo surface to form fine wrinkles. The present invention can increase the scattering rate of light by shrinking the surface of the acrylic resin composition and/or the cured product thereof to the above-mentioned fine wrinkle structure using an excimer. degree can be reduced. _{To this end, the first light irradiation step is a nitrogen (N 2} ) containing a small amount of _{oxygen (O 2} ) by using light having a wavelength of less than 300 nm, specifically 100 to 200 nm or 150 to 195 nm having high energy. It can be carried out in an atmosphere. Specifically, the concentration of oxygen (O _{2 ) contained in nitrogen (N 2} ) in the first light irradiation step may be 10 to 30,000 ppm, specifically 10 to 20,000 ppm, 10 to 5,000 ppm, 1,000 to 2,000 ppm , 2,000 to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 10 to 2,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 50 to 150 ppm, 80 to 120 pp, 500 to 2,000 ppm , 500 to 1,500 ppm or 800 to 1,200 ppm. In addition, the distance between the acrylic resin composition and the light source in the first light irradiation step may be 5 to 100 mm, specifically 5 to 80 mm, 5 to 60 mm, 5 to 40 mm, 10 to 70 mm, 10 to 50 mm , 10-30 mm, 20-80 mm, 20-60 mm, 20-50 mm, 20-30 mm, 25-75 mm, 50-80 mm, 40-60 mm, or 45-55 mm.

In addition, the light irradiation amount in the first light irradiation step may be 25 mJ/cm 2 to 75 mJ/cm 2 , specifically 25 mJ/cm 2 to 70 mJ/cm 2 ¸25 mJ/cm 2 to 50 mJ/cm 2 , 50 mJ /cm to 75 mJ/cm, 40 mJ/cm to 60 mJ/cm, 25 mJ/cm to 45 mJ/cm, 35 mJ/cm to 45 mJ/cm, or 38 mJ/cm to 43 mJ/cm .

As an example, in the first light irradiation step, light having a wavelength of 172±2 nm is applied to the composition to form an excimer in the acrylic resin composition, and 100 ppm of oxygen (O ₂ ) is included in nitrogen (N ₂ ) condition 37 It can be carried out by irradiating for a very short time of 1 to 2 seconds with a light amount of ~44 mJ/cm 2 (ie, light irradiation amount).

The present invention can easily control the average size and/or frequency of fine wrinkle structures formed on the surface of the coating layer by controlling the gas conditions, the distance between the composition and the light source, and/or the amount of light irradiation in the above ranges when performing the first light irradiation step. can

In addition, the method of applying the composition on the substrate may be performed by a method known in the art, for example, Mayer (Mayer), D-bar (D-bar), rubber roll (rubber roll), G /V roll (G / V roll), an air knife (air knife), slot die (slot die), it can be performed using a micro gravure.

In addition, the second light irradiation step is a step of applying ultraviolet (UV) energy to the surface-contracted composition and/or coating layer to temporarily harden it, and has a wavelength of 200 to 400 nm or more, specifically 250 to 380 nm, 280 to 380 nm, It may be carried out by irradiating light with a wavelength of 250 to 350 nm, or 280 to 320 nm in air conditions. At this time, the surface temperature of the pre-cured composition and/or the coating layer may be 20 to 90 ℃, specifically 20 to 80 ℃ or 30 to 70 ℃.

As an example, the second light irradiation step is performed by irradiating light having a wavelength of 300±5 nm to the composition and/or coating layer at a light amount of 20 to 800 mJ/cm 2 in air conditions for a very short time of 1 to 2 seconds. In this case, the distance between the composition and/or coating layer and the light source may be 0.5 to 10 mm.

In addition, the third light irradiation step is a step of performing deep curing by additionally irradiating ultraviolet (UV) to the temporarily cured composition and/or coating layer, and has a wavelength of 400 nm or less, specifically 100 to 400 nm, 200 to 400 nm, 200 to 300 nm, 300 to 400 nm, 150 to 300 nm, 200 to 250 nm, or 270 to 320 nm using light at a wavelength of oxygen (O ₂ ) In a nitrogen (N ₂ ) atmosphere containing a small amount can be performed. Here, the concentration of oxygen (O ₂ ) contained in nitrogen (N ₂ ) may be 10 to 30,000 ppm, specifically, 10 to 5,000 ppm, 1,000 to 2,000 ppm, 2,000 to 3,000 ppm, 3,000 to 4,000 ppm, 4,000 to 5,000 ppm, 100 to 1,000 ppm, 100 to 500 ppm, 100 to 200 ppm, 10 to 2,000 ppm, 10 to 1,000 ppm, 10 to 500 ppm, 100 to 300 ppm, 10 to 200 ppm, 50 to 150 ppm, 80 to 120 ppm, 15,000 to 25,000 ppm, 500 to 5,000 ppm, 500 to 3,000 ppm, or 500 to 1,500 ppm. The present invention can improve the curing rate of the composition and / or coating layer by controlling the concentration of _{oxygen (O 2} ) in the above range in the third light irradiation step in which the deep _{curing is performed, as well as oxygen molecules (O 2} ) of ozone ( O ₃ ) It can induce the effect of cleaning the surface of the coating layer through conversion.

As an example, the third light irradiation step may be performed by irradiating light having a wavelength of 300±5 nm to the composition and/or coating layer at an amount of 400 to 800 mJ/cm 2 for a very short time of 1 to 2 seconds, and , wherein the distance between the composition and/or coating layer and the light source may be 50±10 mm.

The light irradiated in the present invention may be irradiated according to a known method capable of irradiating light of a wavelength required in each step. For example, light having a wavelength of 400 nm or less in the UV region may be irradiated using a mercury or metal halide lamp.

In addition, in the present invention, the time the light is irradiated may be a very short time of 1 to 2 seconds, and this light irradiation time is controlled by the speed at which the composition moves when irradiated with light, for example, the moving speed of the composition coated on the substrate. can For example, the moving speed of the composition and/or the substrate coated with the composition may be 1 to 50 m/min, specifically 5 to 40 m/min, 10 to 40 m/min, 20 to 40 m/min. min, 30-40 m/min, 15-25 m/min, 5-15 m/min, 15-20 m/min, 35-40 m/min or 18-22 m/min.

The present invention can exhibit a high curing rate even when a small amount of the initiator is included in the above range by using short wavelength light in a specific range step by step under different conditions when curing the composition.

On the other hand, the acrylic resin composition to be formed on the coating layer is a urethane acrylic oligomer; oligomers comprising silicon-containing functional groups; an acrylic monomer having a reactive functional group; and a polyfunctional acrylic monomer including two or more polymerizable functional groups.

Specifically, the urethane acryl-based oligomer is an oligomer obtained using a monomer including an acryl group, and has a structure including a urethane group therein. The acrylic resin composition including the urethane acrylic oligomer has an advantage in that there is no problem with respect to yellowing due to the benzene ring compared to the conventional coating agent for flooring including the epoxy acrylic oligomer. In addition, the urethane acrylic oligomer contained in the acrylic resin composition rapidly undergoes radical polymerization due to the initiation reaction of the photoinitiator, provides a coating film excellent in elasticity and toughness, and in particular, a base material containing a vinyl chloride resin (PVC) Excellent adhesion to the layer.

These urethane acrylic oligomers are synthesized with polyisocyanate, polyol, and an acrylate compound having a hydroxy group. In this case, the polyisocyanate is 5-isocyanate-1-(isocyanatemethyl)-1,3,3-trimethylcyclohexane, 4,4-dicyclohexylmethane diisocyanate, 1,6-diisocyanate hexane, 1,6-diisocyanate hexane derivative, etc. can be used, and as the polyol, polyester polyol, polyether polyol, polycarbonate polyol, etc. can be used. and, as the acrylate compound having a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and the like may be used. In addition, the urethane acrylic oligomer may be a polyfunctional oligomer including two or more polymerizable functional groups, specifically, at least one of a difunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. can do.

In addition, the urethane acrylic oligomer may be a bio-oligomer extracted from plants. The acrylic resin composition according to the present invention further includes a bio-oligomer extracted from a plant as a urethane acrylic oligomer, thereby satisfying the physical properties of the coating layer implemented when existing petroleum-based synthetic resins have, while producing carbon dioxide or volatile organic compounds (Volatile organic compounds). compounds, VOC), etc., and does not cause odor of harmful compounds, so it is eco-friendly and has the advantage of being able to be recycled for other uses through regeneration processing.

The bio-oligomer may include a fatty acid (bio oil) extracted from a plant, and the fatty acid may include a diacid compound having a long hydrocarbon chain through a chemical bond between the hydrocarbon chains. Here, the diacid compound may have a structure in which at least one of monofunctional acrylates and polyfunctional acrylates such as acrylate and methacrylate is substituted at the terminal. That is, the bio-oligomer may be obtained by introducing acrylate, which is a reactive functional group, at the end of a hydrocarbon chain after extending a hydrocarbon chain through a chemical bond between fatty acids derived from plants. In addition, the bio-oligomer may be included in an amount of 50 to 90 parts by weight in 100 parts by weight of the total urethane acrylic oligomer, specifically, 60 to 90 parts by weight, 70 to 90 parts by weight, 80 to 90 parts by weight in 100 parts by weight of the total urethane acrylic oligomer. parts, 50 to 80 parts by weight, 50 to 70 parts by weight, 60 to 80 parts by weight, 70 to 80 parts by weight, 65 to 85 parts by weight, 55 to 75 parts by weight, 70 to 85 parts by weight, 72 to 83 parts by weight, It may be included in 74 to 80 parts by weight or 72 to 78 parts by weight.

In addition, the fatty acids extracted from the plant are rapeseed oil, avocado oil, camellia oil, taro oil, macadamia nut oil, corn oil, sunflower oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil , Arabidopsis oil, castor oil, linseed oil, safflower oil, grapeseed oil, cottonseed oil, perilla oil, soybean oil, peanut oil, thioyl, bija oil, rice bran oil, dong oil, Japanese oilseed oil, jojoba oil, germ oil, evening primrose oil, It may include, but is not limited to, extracts from one or more of cacao oil and palm oil.

Meanwhile, the urethane acrylic oligomer used in the acrylic resin composition according to the present invention may have an average weight average molecular weight of 1,000 to 50,000, and more specifically, 1,000 to 30,000, 1,000 to 20,000, 1,500 to 20,000, 1,000 to 10,000, 5,000 to 8,000, 8,000 to 12,000, 10,000 to 15,000, 15,000 to 20,000, 1,000 to 5,000, or 1,500 to 3,500. The present invention can further improve the durability of the coating layer by adjusting the weight average molecular weight of the urethane acrylic oligomer within the above range.

In addition, the acrylic resin composition used in the present invention includes an oligomer including a silicon-containing functional group together with a urethane acrylic oligomer. The oligomer including the silicon-containing functional group functions to lower the surface tension of the resin composition, and the acrylic resin composition having the reduced surface tension may form a cured product having a low surface energy upon curing. A cured product with low surface energy has excellent stain resistance, so it is difficult to adsorb contaminants such as fine dust, moisture, and oil on the surface.

The oligomer containing such a silicon-containing functional group is an acrylic monomer such as alkyl acrylate and alkyl (meth) acrylate and 3-methacryloxypropyltrimethoxysilane (MPTS) having a silicon (Si)-containing functional group, etc. It may be an oligomer obtained by polymerizing an alkoxysilane-based acrylic monomer of, or a silicone urethane acrylate polymer or silicone polyester acrylate polymer obtained by modifying a urethane acrylate polymer or polyester acrylate with silicon (Si). In addition, the oligomer including the silicon-containing functional group may be a polyfunctional oligomer including two or more polymerizable functional groups, specifically, one of a difunctional oligomer, a trifunctional oligomer, a tetrafunctional oligomer, and a hexafunctional oligomer. It may include more than one species, and in this case, the average weight average molecular weight (Mw) of the oligomer including the silicon-containing functional group may be 500 to 20,000, specifically 1,000 to 30,000, 1,000 to 20,000, 1,000 to 10,000, 1,000 to 5,000 , 1,500 to 3,500 or 1,000 to 2,000.

In addition, the oligomer including the silicon-containing functional group may be included in an amount of 10 to 40 parts by weight based on 100 parts by weight of the urethane acrylic oligomer, specifically, 10 to 20 parts by weight, 20 to 30 parts by weight, 30 to 40 parts by weight, 5 to 40 parts by weight. parts by weight, 15 to 40 parts by weight, 25 to 40 parts by weight, 20 to 35 parts by weight, 15 to 37 parts by weight, 19 to 25 parts by weight, 31 to 35 parts by weight, 21 to 34 parts by weight, 18 to 29 parts by weight , 21 to 30 parts by weight, or 23 to 27 parts by weight may be included.

In addition, the acrylic resin composition used in the present invention includes an acrylic monomer having a reactive functional group.

For example, the acrylic monomer having a reactive functional group is (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 2-hydroxyethylene glycol (meth)acrylate or 2-hydroxypropylene glycol (meth)acrylic Late, acrylic acid, methacrylic acid, 2-(meth)acryloyloxyacetic acid, 3-(meth)acryloyloxypropyl acid, 4-(meth)acryloyloxybutyric acid, 1,6-hexanedioldi It may include at least one selected from the group consisting of acrylate, acrylic acid double, itaconic acid, maleic acid, and caprolactone modified hydroxyl acrylate (CHA).

The acrylic monomer having the reactive functional group may be included in an amount of 20 to 60 parts by weight based on 100 parts by weight of the urethane acrylic oligomer, specifically 20 to 55 parts by weight, 25 to 40 parts by weight, 25 to 35 parts by weight, 20 to 30 parts by weight. , 20 to 40 parts by weight, 30 to 50 parts by weight, 40 to 60 parts by weight, 22 to 40 parts by weight, 25 to 37 parts by weight, 21 to 26 parts by weight, 24 to 33 parts by weight, 31 to 39 parts by weight, 35 to 47 parts by weight, 45 to 55 parts by weight, 43 to 58 parts by weight, 41 to 51 parts by weight, 49 to 58 parts by weight, 48 to 52 parts by weight, or 23 to 28 parts by weight.

Furthermore, the acrylic resin composition used in the present invention includes a polyfunctional acrylic monomer including two or more polymerizable functional groups. For example, the polyfunctional acrylic monomer is 1,6-hexanediol diacrylate (HDDA), tetraethylene glycol diacrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate Bifunctional acrylic monomers, such as a rate and polyethylene glycol diacrylate (Mw=100-600, PEGDA); Tetramethylolmethane triacrylate, trimethanolpropane triacrylate, trimethylolpropaneethoxy triacrylate, 1,6-bis(3-acryloyloxy-2-hydroxypropyloxy)hexane, pentaerythritol triacrylic Trifunctional acrylic monomers, such as a rate; tetrafunctional acrylic monomers such as tetramethylolmethane tetraacrylate and pentaerythritol tetraacrylate (PETA); and dipentaerythritol hexaacrylate (DPHA), etc. may include at least one selected from the group consisting of hexafunctional acrylic monomers.

The polyfunctional acrylic monomer may be included in an amount of 40 to 80 parts by weight based on 100 parts by weight of the urethane acrylic oligomer, specifically 40 to 70 parts by weight, 40 to 60 parts by weight, 40 to 50 parts by weight, 50 to 80 parts by weight, 60 to 80 parts by weight, 70 to 80 parts by weight, 45 to 55 parts by weight 45 to 65 parts by weight, 50 to 70 parts by weight, 55 to 75 parts by weight, 70 to 78 parts by weight, 48 to 53 parts by weight, 58 to 64 parts by weight parts, 62 to 66 parts by weight, or 72 to 79 parts by weight. The present invention can control the surface hardness of the coating layer by controlling the content of the polyfunctional acrylic monomer in the above range. In particular, among 100 parts by weight of the polyfunctional acrylic monomer included in the acrylic resin composition, 40 parts by weight or more of the polyfunctional acrylic monomer including three or more polymerizable functional groups, specifically 40 parts by weight to 80 parts by weight, 45 parts by weight to The surface hardness of the coating layer by including 80 parts by weight, 45 parts by weight to 55 parts by weight, 45 parts by weight to 60 parts by weight, 55 parts by weight to 80 parts by weight, 60 parts by weight to 80 parts by weight, or 70 parts by weight to 80 parts by weight. can be significantly improved, and through this, it is possible to improve the scratch resistance of the flooring material.

The acrylic resin composition according to the present invention may include each of the aforementioned components in a specific amount. Specifically, the acrylic resin composition comprises 100 parts by weight of a urethane acrylic oligomer; 10 to 40 parts by weight of an oligomer having a silicon-containing functional group; 20 to 60 parts by weight of an acrylic monomer having a reactive functional group; and 40 to 80 parts by weight of a polyfunctional acrylic monomer including two or more polymerizable functional groups.

As an example, the acrylic resin composition may include 100 parts by weight of a urethane acrylic oligomer; 22 to 27 parts by weight of an oligomer having a silicon-containing functional group; 45 to 55 parts by weight of an acrylic monomer having a reactive functional group; and 44 to 54 parts by weight of a polyfunctional acrylic monomer including two or more polymerizable functional groups.

As another example, the acrylic resin composition may include 100 parts by weight of a urethane acrylic oligomer; 22 to 27 parts by weight of an oligomer having a silicon-containing functional group; 21 to 29 parts by weight of an acrylic monomer having a reactive functional group; and 71 to 77 parts by weight of a polyfunctional acrylic monomer including two or more polymerizable functional groups.

On the other hand, the composition according to the present invention may further include a filler having high strength in order to improve durability while partially performing a role of a seed of a fine wrinkled structure formed on the surface of the coating layer. For example, as the filler, one capable of improving surface strength without affecting the gloss of the coating layer after curing of the composition may be used. Specifically, colloidal silica, alumina, glass beads, organic beads (polymer particles, etc.) may be used as the filler, and their average diameter may be 1 µm to 30 µm, more specifically 1 µm to 25 µm μm, 1 μm to 20 μm, 1 μm to 15 μm, 10 μm to 30 μm, 15 μm to 30 μm, 20 μm to 30 μm, 1 μm to 12 μm, 1 μm to 10 μm, 2 μm to 13 μm, 3 μm to 10 μm, 3 μm to 7 μm, 9 μm to 12 μm, 11 μm to 15 μm, 4 μm to 11 μm, or 6 μm to 9 μm. In the present invention, by controlling the average diameter of the filler within the above range, it is possible to prevent cracks in the coating layer without affecting the gloss of the coating layer and increase the adhesion between the coating layer and other layers to improve durability. In addition, the filler may be included in an amount of less than 10 parts by weight based on 100 parts by weight of the composition so as not to impair glossiness and stain resistance of the coating layer. For example, the filler may include 10 parts by weight or less based on 100 parts by weight of the composition, and more specifically, the content of the filler has an upper limit of less than 10 parts by weight, less than 9 parts by weight, less than 8 parts by weight, and 7 parts by weight. It may be less than parts by weight, less than 6 parts by weight, less than 5 parts by weight, or less than 4 parts by weight, and the lower limit may be 0.01 parts by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.5 parts by weight or more, or 1 part by weight or more. As an example, the filler is 0.1 to 3 parts by weight, 0.1 to 2.5 parts by weight, 0.5 to 2.5 parts by weight, 1 to 3 parts by weight, 1.5 to 3 parts by weight, 2.5 to 3 parts by weight, 1.5 to 2 parts by weight, It may be included in an amount of 2 to 2.5 parts by weight, 2.2 to 2.7 parts by weight, 3 parts by weight to 6 parts by weight, 4 parts by weight to 6 parts by weight, or 4.5 parts by weight to 5.5 parts by weight.

In addition, the composition used in the present invention contains a very small amount or does not contain a matting agent for reducing the gloss of the coating layer compared to the existing composition, including an acrylic monomer containing an alkyl group having 6 to 20 carbon atoms with low viscosity. 100 to 600 cps, specifically 100 to 500 cps, 100 to 400 cps, 150 to 350 cps, 170 to 330 cps, 200 to 300 cps, 240 to 290 cps, 180 to 220 cps, 280 to 320 cps, 300 to 360 cps, 330-380 cps, 340-420 cps, 340-360 cps, 380-490 cps¸390-440 cps, 390-430 cps, 400-430 cps, 410-460 cps, 430-490 cps, or 460 It may have a low viscosity of to 490 cps, and may exhibit a low viscosity of 500 cps or less even if a filler is further included to improve the durability of the coating layer. The composition has an advantage of excellent workability by having a low viscosity of 500 cps or less.

Hereinafter, the present invention will be described in more detail by way of Examples and Experimental Examples.

However, the following Examples and Experimental Examples only illustrate the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

Preparation Examples 1 to 5. Preparation of acrylic resin composition

First urethane acrylic oligomer (trifunctional oligomer, Mw: 7,000±10), second urethane acrylic oligomer (biooligomer, Mw: 3,000±10), oligomer having a silicon-containing functional group (Mw: 5,000±10), hydroxy Propyl acrylate (HPA), 1,6-hexanediol diacrylate (HDDA), pentaerythritol tetraacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), colloidal silica as filler (average diameter: 5-10 μm) and a dispersant were mixed with Irgacure 754 as an initiator as shown in Table 1 below to prepare a solvent-free type acrylic resin composition.

Unit: g Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 1st urethane acrylic type
oligomer 10 10 10 10 10 2nd urethane acrylic type
oligomer 30 30 30 30 30 silicon-containing functional groups
oligomers with 10 10 10 10 10 HPA 20 20 10 20 10 HDDA 20 10 10 10 10 PETA - 10 20 - - DPHA - - - 10 20 colloidal silica 5 5 5 5 5 dispersant One One One One One Irgacure 754 4 4 4 4 4 Viscosity (25±0.5℃) 350±5 cps 400±5 cps 430±5 cps 420±5 cps 480±5 cps

Examples 1 to 4.

A polyvinyl chloride (PVC) foam sheet (average thickness: 1T, average pore size: 300-400 μm) and a transparent polyvinyl chloride (PVC) substrate each having a size of 10 cm X 10 cm are laminated, and a transparent polyvinyl chloride Each of the acrylic resin compositions prepared in Preparation Examples 2 to 5 was applied on a (PVC) substrate and fixed to a photocuring device having the structure shown in FIG. 1 . Thereafter, as shown in Table 3 below, light irradiation was performed step by step while moving the substrate at a moving speed of 20 ± 1 m/min to prepare a flooring specimen. At this time, the average thickness of the coating layer was 15 ± 1㎛.

Example 1 Example 2 Example 3 Example 4 acrylic resin
composition type Composition of Preparation Example 2 Composition of Preparation Example 3 Composition of Preparation Example 4 Composition of Preparation Example 5

Curing condition 1 first light irradiation Wavelength range 172±5 nm irradiance 40±2 mJ/cm2 distance from light source 50±1mm gas condition N ₂ conditions (O ₂ 1,000 ppm) 2nd light irradiation wavelength range 250-400 nm irradiance 300±5 mJ/cm2 distance from light source 100±1mm gas condition air condition Third light irradiation wavelength range 250-400 nm irradiance 600±10 mJ/cm2 distance from light source 100±1mm gas condition N ₂ conditions (O ₂ 1,000 ppm)

Comparative Examples 1 to 4.

A flooring specimen was prepared in the same manner as in Example 1, except for curing the composition under the curing conditions as shown in Tables 4 and 5 below. At this time, the average thickness of the coating layer was 15 ± 1㎛.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Acrylic composition type Composition of Preparation Example 1 Composition of Preparation Example 2 Composition of Preparation Example 2 Composition of Preparation Example 2 Curing conditions Curing condition 1 Curing condition 2 Curing condition 3 Curing condition 4

Curing condition 2 Curing condition 3 Curing condition 4 first light irradiation Wavelength range 172±5 nm - 172±5 nm irradiance 20±2 mJ/cm2 - 120±2 mJ/cm2 distance from light source 50±1mm - 50±1mm gas condition N ₂ conditions (O ₂ 1,000 ppm) - N ₂ condition
(O ₂ 1,000 ppm) 2nd light irradiation wavelength range 250-400 nm 250-400 nm 250-400 nm irradiance 300±5 mJ/cm2 300±5 mJ/cm2 300±5 mJ/cm2 distance from light source 100±1mm 100±1mm 100±1mm gas condition air condition air condition air condition Third light irradiation wavelength range 250-400 nm 250-400 nm 250-400 nm irradiance 600±10 mJ/cm2 600±10 mJ/cm2 600±10 mJ/cm2 distance from light source 100±1mm 100±1mm 100±1mm gas condition N ₂ condition
(O ₂ 1,000 ppm) N ₂ condition
(O ₂ 1,000 ppm) N ₂ condition
(O ₂ 1,000 ppm)

Experimental Example 1

In order to confirm the surface structure of the coating layer, which is the outermost layer of the flooring material according to the present invention, scanning electron microscope (SEM) analysis was performed on the flooring specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 4, and the results were 2 and 3 are shown.

Referring to FIG. 2 , the flooring specimens of Examples 1 to 4 according to the present invention include a fine wrinkle structure at a predetermined size and frequency on the surface, and the fine wrinkle structure is a form in which the second wrinkle is branched around the first wrinkle. It can be seen that has

In addition, looking at the flooring specimens of Example 1 and Comparative Example 1, the specimen of Example 1 including a polyfunctional monomer having three or more polymerizable functional groups in the acrylic resin composition during the formation of the coating layer showed clear first and second wrinkles. It was found that the number of cells formed by the junction between the first folds was less than three. In contrast, in the specimen of Comparative Example 1 including a polyfunctional monomer having two polymerizable functional groups, it can be seen that the first and second wrinkles are unclear and cells having an average size of 0.05 to 0.3 mm are continuously distributed.

In addition, looking at the flooring specimens of Example 1 and Comparative Examples 2 to 4, it was confirmed that the fine wrinkle structure was strongly formed as the amount of light irradiated in the first light curing step during the formation of the coating layer increased. In addition, it was found that the specimen of Comparative Example 3, which was not subjected to the first photo-curing step, did not have a fine curved structure on the surface. In addition, referring to FIG. 3 , although the first light curing step was performed, the specimen of Comparative Example 4 in which the amount of light irradiated was significantly higher. Although the surface had a large amount of curved structure, the degree of bending was very large. It was confirmed that it had a structure continuously formed without a certain direction. became

From these results, the first light irradiation step of irradiating light with a wavelength of less than 200 nm generates an excimer, and the generated excimer generates short-wavelength UV to rapidly accelerate surface curing of the composition and/or coating layer, and thus the composition and It can be seen that the surface of the coating layer is contracted to form a fine wrinkled structure. In addition, the acrylic resin composition constituting the coating layer contains a certain amount of a polyfunctional monomer including three or more polymerizable functional groups, so that the average size and frequency of the wrinkle structure formed on the surface when irradiated with the first light as well as the fine shape can be controlled. it can be seen that there is

Experimental Example 2.

In order to evaluate the glossiness, stain resistance, non-slip property and low-temperature durability of the flooring material according to the present invention, the surface roughness, glossiness, scratch resistance and non-slip properties of the specimens prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were evaluated. A sex test was performed. Specific measurement methods are as follows, and the measurement results are shown in Table 6 below:

A) Surface roughness evaluation

Surface roughness (Rz) according to ISO 4287 was measured using a surface roughness measuring instrument (Model: 178-560-02K Model, Manufacturer: Mistutoyo).

B) Glossiness evaluation

For the specimens of Examples and Comparative Examples, 60° glossiness (gloss 60° conditions) was measured using a gloss meter.

C) Scratch resistance evaluation

Micro-scratch resistance was evaluated according to procedure B of EN 16094:2012. Specifically, the surface of the laminated film was rubbed 160 times with a medium fine hand pad (Scotch Brite SB7440). Thereafter, it was visually checked whether scratches and patterns caused by scratches on the rubbed surface were generated, and grades were given according to the following criteria:

Grade B1: No scratches at all;

Grade B2: less than 10 minor scratches confirmed;

B3 grade: 10 or more but less than 30 light scratches confirmed;

Grade B4: Numerous narrow and fine scratches were identified, and a lissajous figure due to scratches was partially confirmed;

Grade B5: A number of narrow and fine scratches were confirmed, and a lissajous figure due to scratches was confirmed in a mixed form.

D) Non-slip evaluation

A ramp test according to DIN 51130 was performed to measure the angle of inclination at which slipping occurred, and the measured inclination angle was classified according to the following criteria to determine the non-slip grade:

- R9: The angle of inclination at which slip occurs is 6° or more but less than 10°

- R10: The angle of inclination at which slip occurs is 10° or more but less than 19°

- R11: The angle of inclination at which slip occurs is 19° or more and less than 27°

- R12: The angle of inclination at which slip occurs is 27° or more but less than 35°

- R13: The angle of inclination at which slip occurs is 35° or more

E) Low-temperature breaking strength evaluation

In the specimens of Examples and Comparative Examples, 5 specimens with a width of 20 mm and a length of 100 mm are cut in the longitudinal and transverse directions, respectively, with the surface of the specimen facing outward and both ends in the longitudinal direction are overlapped, about 5 mm of one end was fixed to the clamp of the cold resistance test device. After that, the fixed test piece was immersed in a low temperature methanol water bath, and a falling body (weight: 2.5 kgf (≈24.5N)) was prepared at a position of about 50 mm above the test piece. The test piece was fixed and immersed, and when 5 minutes had elapsed, the falling object was dropped on the surface of the test piece, and the test piece from which the falling object fell was taken out of the water tank, and whether or not the surface was damaged, specifically, the occurrence of residuals, cracks, pinholes, etc. was visually confirmed. Here, the temperature of the methanol bath was adjusted to -30°C, -25°C and -20°C, respectively, and the temperature at which damage occurred on the surface of the specimen was measured as a result of low-temperature breaking strength.

Surface roughness (Rz) glossiness scratch resistance non-slip breaking temperature Example 1 22±0.5 μm 2.5±0.01 B3 R11 -25℃ Example 2 22±0.5 μm 4.0±0.01 B3 R11 -25℃ Example 3 25±0.5 μm 3.0±0.01 B3 R11 -25℃ Example 4 25±0.5 μm 5.0±0.01 B3 R11 -25℃ Comparative Example 1 12±0.5 μm 2.0±0.01 B4 R10 -25℃ Comparative Example 2 7±0.5 μm 4.0±0.1 B3 R9 -25℃ Comparative Example 3 3±0.5 μm 10.0±0.1 B3 R9 -25℃ Comparative Example 4 24±0.5 μm 0.9±0.05 B3 R11 -20℃

As shown in Table 6, it can be seen that the flooring material according to the present invention exhibits excellent surface properties by curing by irradiating a specific range of short-wavelength light under different conditions in stages.

Specifically, the flooring specimens of Examples 1 to 4 have a constant average roughness (Rz) of 21 to 26 μm, so even when a small amount of a matting agent is used, the glossiness in the gloss 60° condition is 5 or less, and the inclination angle is less than 19 It was found that no slippage occurred. In addition, it was confirmed that the flooring specimens had excellent micro-scratch resistance, so that the rate of occurrence of scratches on the surface was not high, and surface damage did not occur at a temperature of -25°C or higher when a falling object (2.5 kgf) was dropped.

From these results, when the composition is cured by irradiating a specific range of short-wavelength light in stages under different conditions during light curing, the curing rate of the composition is improved, as well as by inducing a wrinkled fine curved structure on the surface of a certain size and frequency It can be seen that not only the glossiness of the coating layer can be reduced, but also scratch resistance and non-slip properties are improved at the same time.

100: light curing device
110: light irradiation room
111: first light irradiator (UV irradiator)
112: second light irradiator (UV irradiator)
113: third light irradiator (UV irradiator)
120: irradiated light
130: conveyor belt
140: gas diaphragm
150: Psalm
200: cross-sectional structure of the flooring
210: coating layer
220: base layer
211: dendrite

Claims (15)

a foam layer, a base layer, and a coating layer of an acrylic resin composition;
The coating layer may include a first wrinkle having a first directionality; and a surface structure comprising a second pleat branching from the first pleat and having a second directionality,
The second directionality is a flooring material having an angle of 50 to 140° with respect to the first directionality.
According to claim 1,
The average thickness of the first wrinkle is 10 μm to 100 μm,
The average thickness of the second wrinkle is 1 μm to 50 μm,
The first wrinkle and the second wrinkle are flooring materials that satisfy Equation 1:
[Equation 1] 0.9 ≤ T _1st /T _2nd ≤ 3
In Equation 1, T _1st is the thickness of the first wrinkle, and T _2nd is the thickness of the second wrinkle.
According to claim 1,
The second pleats are branched from 2 to 20 per unit length (0.5 mm) of the first pleats.
According to claim 1,
The average length of the first wrinkle is 200 μm to 5,000 μm,
The average length of the second corrugation is 50㎛ to 1,000㎛ flooring.
According to claim 1,
The surface roughness (Rz) of the coating layer is an average of 10㎛ to 30㎛ flooring.
According to claim 1,
The flooring material is grade B2 or lower when micro-scratch resistance is evaluated according to procedure B of EN 16094.
According to claim 1,
A flooring material having a surface gloss of 1 to 6 under conditions of 60° gloss.
According to claim 1,
The coating layer is a flooring material having an inclination angle rating of R10 or more at which slipping occurs during a ramp test according to DIN 51130.
According to claim 1,
The average thickness of the coating layer is 5㎛ to 30㎛ flooring.
A first light irradiation step of activating the composition by irradiating the acrylic resin composition with light having a wavelength of less than 300 nm under an inert gas condition;
A second light irradiation step of primary light curing of the composition by irradiating the activated composition with light having a wavelength of 200 nm to 400 nm under air conditions; and
The method for producing a flooring material according to claim 1, comprising a third light irradiation step of irradiating the light of a wavelength of 200 nm to 400 nm under an inert gas condition to the primary cured composition to secondary light curing the composition.
11. The method of claim 10,
The light irradiation amount of the first light irradiation step is 25 mJ/cm 2 to 75 mJ/cm 2 A method of manufacturing a flooring material.
11. The method of claim 10,
The first light irradiation step and the third light irradiation step, oxygen (O ₂ ) The concentration of 10 ppm to 30,000 ppm nitrogen (N ₂ ) Method of manufacturing flooring, characterized in that it is performed under conditions.
11. The method of claim 10,
The acrylic resin composition,
100 parts by weight of urethane acrylic oligomer;
10 to 40 parts by weight of an oligomer containing a silicon-containing functional group;
20 to 60 parts by weight of an acrylic monomer having a reactive functional group; and
A method for producing a flooring material comprising 40 to 80 parts by weight of a polyfunctional acrylic monomer containing two or more polymerizable functional groups.
11. The method of claim 10,
The acrylic resin composition is a method of manufacturing a flooring material further comprising one or more fillers selected from the group consisting of silica, alumina, glass beads, and organic beads.
15. The method of claim 14,
The average diameter of the filler is 1 ㎛ to 30 ㎛ method of manufacturing a flooring material.

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