KR20230078098A - Flooring material and method for preparing the same - Google Patents

Abstract

The flooring material according to one embodiment of the present invention includes a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer in a sequential stacked structure from bottom to top, and the printing layer is formed using a digital printing process. , The transparent layer may include a first transparent layer provided on the ink receiving layer; and a second transparent layer provided on the first transparent layer, wherein a glass transition temperature of the second transparent layer is higher than that of the first transparent layer.

Description

Flooring material and its manufacturing method {FLOORING MATERIAL AND METHOD FOR PREPARING THE SAME}

The present invention relates to a flooring material and a manufacturing method thereof.

Since polyvinyl chloride-based flooring materials are used in actual living spaces of humans, various functionalities and decorative properties are required. Recently, as living standards have increased and residential living environments have been improved, voices demanding various patterns and luxurious interiors are growing.

A commonly used polyvinyl chloride-based flooring material is composed of a base layer, a white layer, a printed layer, and a transparent layer, and in this case, the printed layer is generally printed by a gravure printing method to express the appearance. However, since the gravure printing is printed on a flat surface, it is difficult to obtain a three-dimensional product, and a plurality of gravure printing rolls suitable for each design are required to express various colors and images.

Therefore, the gravure printing method not only consumes a lot of production time and manpower for the printing roll, and requires a lot of production cost, but also takes a lot of time to color to match a certain color, so it does not respond quickly to customer needs. Problems also arose. As a result, there were limitations in printing specific mosaic designs or images, such as my own unique design or specific logo.

In addition, due to the change in viscosity of the gravure printing ink used, not only the color change between lots is severe, but it is difficult to print powder pigments with large particles. , there is a problem that occurs when printing is not partially performed due to clogging of the mesh of the gravure printing roll.

Due to these problems, it is not only impossible to produce various colors with the gravure printing method, but there is a limit to printing a unique pattern in the form of a mosaic, so it is difficult to produce a three-dimensional effect and various colors and patterns at the same time.

In addition, in the case of applying water-based ink as the gravure printing method, since the polyvinyl chloride resin is hydrophobic, there is a problem in that the printing layer and the transparent layer including the polyvinyl chloride resin may be separated from each other due to insufficient adhesive strength.

Republic of Korea Patent Publication No. 10-2003-0040694

The present invention is to provide a flooring material and a manufacturing method thereof. More specifically, the present invention is to provide a flooring material having improved peel strength of the transparent layer due to excellent adhesion between the printing layer and the transparent layer, and a manufacturing method thereof.

One embodiment of the present invention,

From the bottom to the top, a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer are sequentially formed in a laminated structure,

The printed layer is formed using a digital printing process,

The transparent layer may include a first transparent layer provided on the ink receiving layer; And a second transparent layer provided on the first transparent layer,

The glass transition temperature of the second transparent layer provides a flooring material that is higher than the glass transition temperature of the first transparent layer.

In addition, another embodiment of the present invention,

It is a method of manufacturing a flooring material formed in a sequential laminated structure of a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer from bottom to top,

After forming an ink receiving layer on the transfer film, forming a printing layer on the ink receiving layer by a digital printing process;

Forming a white layer on the base layer;

forming a printing layer and an ink receiving layer on the white layer by performing a transfer process while laminating the transfer film on which the printing layer is formed on the white layer; and

After peeling off the transfer film, forming a transparent layer on the ink receiving layer,

a first transparent layer provided on the ink receiving layer; And forming a structure of a second transparent layer provided on the first transparent layer,

The glass transition temperature of the second transparent layer provides a method for producing a flooring material that is higher than the glass transition temperature of the first transparent layer.

In the flooring material according to an exemplary embodiment of the present invention, a first transparent layer, which is a soft transparent layer, and a second transparent layer, which is a hard transparent layer, are simultaneously applied as transparent layers provided on a printing layer including an ink receiving layer, thereby preventing scratches by external force on the surface of the flooring material. sexuality can be improved. When a hard transparent layer is applied as a transparent layer provided in direct contact with the ink receiving layer, the transparent layer can be easily peeled off due to lack of adhesion between the ink receiving layer and the hard transparent layer. However, in the present invention, as a transparent layer provided in direct contact with the ink receiving layer By applying the soft transparent layer, there is a feature that can improve the adhesion between the printing layer including the ink receiving layer and the transparent layer.

In addition, the method for manufacturing a flooring material according to an exemplary embodiment of the present invention is characterized in that adhesion between the printed layer and the transparent layer can be improved by transferring the printed layer formed by the digital printing process to one surface of the white layer. Conventionally, a method of forming a printing layer by a gravure printing method and then transferring it to one side of a white layer was used, but the gravure printing method consumes a lot of time and manpower to produce a print roll, and there is a problem in that a lot of manufacturing cost is required. In addition, many repeating patterns are generated in the printed layer, and the design is inevitably monotonous. However, in the manufacturing method of the flooring material according to an exemplary embodiment of the present invention, the manufacturing process of the printing layer is relatively simple when compared to the gravure printing method by transferring the printing layer formed by the digital printing process to one side of the white layer. It has a feature that can increase the design autonomy of the printing layer.

1 is a diagram schematically showing a laminated structure of a flooring material according to an exemplary embodiment of the present invention.
2 is a diagram schematically showing a laminated structure of a flooring material according to an exemplary embodiment of the present invention.
3 is a view schematically showing a laminated structure of a flooring material according to the prior art.

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

In the present invention, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

In the present invention, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

As described above, when the printing layer of the polyvinyl chloride-based flooring material is manufactured by the gravure printing method of water-based ink, since the polyvinyl chloride resin is hydrophobic, the adhesion between the printing layer and the transparent layer containing the polyvinyl chloride resin is insufficient, so that each other There is a problem that can be peeled off. In addition, conventionally, since a soft transparent layer is applied as a single film as a transparent layer of a polyvinyl chloride-based flooring material, scratch resistance due to external force on the surface of the flooring material is weak.

Therefore, in the present invention, even when the printing layer is formed with water-based ink, the adhesion between the printing layer and the transparent layer is excellent, so that the peel strength of the transparent layer is improved, and the scratch resistance against external force is excellent. To provide a flooring material and a manufacturing method thereof do.

The flooring material according to one embodiment of the present invention includes a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer in a sequential stacked structure from bottom to top, and the printing layer is formed using a digital printing process. , The transparent layer may include a first transparent layer provided on the ink receiving layer; and a second transparent layer provided on the first transparent layer, wherein a glass transition temperature of the second transparent layer is higher than that of the first transparent layer.

Hereinafter, each layer constituting the flooring material of the present invention will be described in detail.

In one embodiment of the present invention, the base layer, the white layer and the transparent layer may each include a polyvinyl chloride resin. The base layer, the white layer, and the transparent layer may be prepared in a sheet form using an extruder using a composition for a base layer, a composition for a white layer, a composition for a transparent layer, or the like, or may be prepared in a sheet form using a calendering method.

In the present invention, the polyvinyl chloride resin may be, for example, a polymer of vinyl chloride having viscoelasticity suitable for calendering. The vinyl chloride polymer means a homopolymer, a copolymer containing 50% by weight or more of vinyl chloride, and the like.

In general, polyvinyl chloride resin has the characteristics of freely adjusting the flexibility from soft to hard depending on the type and amount of plasticizer added, as well as excellent water resistance, chemical resistance, electrical insulation, etc., and melts at 170 ° C. or higher. The degree of polymerization of the polyvinyl chloride resin may be 700 to 1,300, for example, 700 to 1,000. The degree of polymerization may be measured according to a method commonly used in the art.

base layer

In the present invention, the base layer may serve to impart volume and strength to the flooring material, and the base layer may be manufactured by molding a composition for the base layer.

The base layer includes a polyvinyl chloride resin, a filler and a plasticizer, and based on 100 parts by weight of the polyvinyl chloride resin, 300 parts by weight to 800 parts by weight of the filler; and 30 parts by weight to 60 parts by weight of a plasticizer. More preferably, the base layer includes 400 parts by weight to 700 parts by weight of a filler based on 100 parts by weight of the polyvinyl chloride resin; and 40 parts by weight to 50 parts by weight of a plasticizer.

The thickness of the base layer may be 1 mm to 7 mm, and may be 2 mm to 5 mm. When the thickness range of the base layer is satisfied, the effect of imparting volume and strength to the flooring material is excellent.

white layer

In the present invention, the white layer may serve to conceal the lower black base layer and improve the printing effect of the printing layer transferred to one surface of the white layer. The white layer may be prepared by molding the composition for the white layer.

The white layer includes a polyvinyl chloride resin, a filler, and a pigment, and based on 100 parts by weight of the polyvinyl chloride resin, 30 parts by weight to 50 parts by weight of the filler; and 5 parts by weight to 20 parts by weight of the pigment. More preferably, the white layer is based on 100 parts by weight of the polyvinyl chloride resin, 35 parts by weight to 45 parts by weight of the filler; and 10 parts by weight to 15 parts by weight of the pigment.

In addition, the white layer may further include a plasticizer. The amount of the plasticizer may be 15 parts by weight to 35 parts by weight or 20 parts by weight to 30 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

The white layer may have a thickness of 0.04 mm to 0.15 mm or 0.05 mm to 0.08 mm. When the thickness range of the white layer is satisfied, the effect of hiding the black lower base layer and the printing effect of the printing layer provided on the white layer are excellent. When the thickness of the white layer exceeds 0.15 mm, manufacturing cost may increase, and when the thickness of the white layer is less than 0.04 mm, the hiding power of the lower base layer and the sharpness of the printed layer may decrease.

transparent layer

In the present invention, the transparent layer can play a role of protecting the printing layer and the ink receiving layer, and can play a role of exhibiting excellent scratch resistance characteristics by further increasing the hardness while securing processability and thermal stability of the flooring material. can The transparent layer may be prepared by molding a composition for the transparent layer.

In the present invention, the transparent layer includes a first transparent layer provided on the ink receiving layer; and a second transparent layer provided on the first transparent layer, wherein a glass transition temperature of the second transparent layer is higher than that of the first transparent layer.

According to one embodiment of the present invention, the glass transition temperature of the second transparent layer is higher than the glass transition temperature of the first transparent layer, so that the product can be prevented from being warped, and the product has scratch resistance against curling and daily scratches. can be improved, and it can be easily applied to calendering. Since flexibility, adhesion, adhesiveness, etc. can be improved only when the glass transition temperature of the transparent layer is low, in the present invention, in order to improve bonding strength between the transparent layer having different constituents and the ink receiving layer, a first transparent layer having a relatively low glass transition temperature is provided. It is provided so as to directly contact the ink receiving layer. In particular, in the case where the second transparent layer having a relatively high glass transition temperature is provided on the ink receiving layer, it is not preferable because the bonding strength between the ink receiving layer and the second transparent layer may be insufficient and the second transparent layer may be peeled off. That is, in the present invention, by simultaneously applying the first transparent layer and the second transparent layer having the above-described glass transition temperature characteristics, not only can the bonding strength between the ink receiving layer and the transparent layer be improved by the first transparent layer, but also the product by the second transparent layer. The scratch resistance of the surface can be improved.

The first transparent layer may include a polyvinyl chloride resin and a plasticizer, and the amount of the plasticizer may be 25 parts by weight to 50 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. In addition, the amount of the plasticizer in the first transparent layer may be 25 parts by weight to 40 parts by weight or 25 parts by weight to 35 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. When the content of the plasticizer is less than 25 parts by weight, bonding strength between the printing layer and the first transparent layer may be lowered, and when it exceeds 50 parts by weight, physical properties may be deteriorated due to migration of the plasticizer. In order to optimize the physical properties of the product, it is more preferable that the content of the plasticizer is 28 parts by weight to 32 parts by weight.

In addition, the second transparent layer may include a polyvinyl chloride resin and a plasticizer, and based on 100 parts by weight of the polyvinyl chloride resin, the content of the plasticizer may be 3 parts by weight to 15 parts by weight. In addition, the second transparent layer may have a plasticizer content of 3 parts by weight to 10 parts by weight or 4 parts by weight to 8 parts by weight based on 100 parts by weight of the polyvinyl chloride resin. When the content of the plasticizer is less than 3 parts by weight, bonding strength between the first transparent layer and the second transparent layer may be lowered, and when it exceeds 15 parts by weight, the effect of improving the scratch resistance of the surface of the transparent layer may be insignificant.

The glass transition temperature of the first transparent layer may be 15 °C to 30 °C, preferably 20 °C to 25 °C. In addition, the glass transition temperature of the second transparent layer may be 40 ℃ to 70 ℃, preferably 55 ℃ to 65 ℃. A difference in glass transition temperature between the first transparent layer and the second transparent layer may play an important role in implementing the present invention.

The glass transition temperature difference between the first transparent layer and the second transparent layer may be 10 °C to 50 °C, 15 °C to 45 °C, or 20 °C to 40 °C. When the above-described difference in glass transition temperature between the first transparent layer and the second transparent layer is satisfied, the first transparent layer having a relatively low glass transition temperature and having an elastic property and the second transparent layer having a relatively high glass transition temperature and having a hard property 2 Since it contains a transparent layer, the flooring material is flexible and can provide a structural balance and can be suitable for calendering. When the difference in glass transition temperature between the first transparent layer and the second transparent layer is less than 10° C., it is not preferable because the effects of improving scratch resistance and preventing warping of the product cannot be obtained at the same time.

The glass transition temperature may be measured by a method known in the art, and may be measured using, for example, a Differential Scanning Calorimetry (DSC) Ta Instrument Q10.

The thickness of the first transparent layer may be 3 to 10 times, and may be 4 to 7 times the thickness of the second transparent layer. When the above-described thickness ratio of the first transparent layer and the second transparent layer is satisfied, thick scratches can be prevented from occurring even with a force of up to 10 N that may occur during use with structural balance, which is preferable.

The total thickness of the first transparent layer and the second transparent layer may be 0.15 mm to 0.7 mm, preferably 0.4 mm to 0.6 mm. When the above-mentioned thickness of the transparent layer is satisfied, formability can be improved while maintaining excellent hardness, friction resistance and durability. When the thickness of the transparent layer is less than 0.15 mm, hardness, friction resistance, durability, etc. may be deteriorated, and when it exceeds 0.7 mm, difficulties in the process and structural balance deterioration (severe curling due to distortion) may occur, A problem of deterioration in formability may occur. The thickness of the first transparent layer may be 0.32 mm to 0.52 mm, and may be 0.35 mm to 0.45 mm. In addition, the thickness of the second transparent layer may be 0.05mm to 0.2mm, may be 0.07mm to 0.12mm.

In one embodiment of the present invention, the Shore D hardness of the first transparent layer may be 57 to 67, and may be 60 to 65. In addition, the Shore D hardness of the second transparent layer may be 70 to 85, or 75 to 80.

In the present invention, Shore hardness is measured using a hardness scale defined by Albert Ferdinand Shore, who developed a device for measuring Shore hardness in the 1920s. The two most common grades of shore hardness are the ASTM D2240 Type A and Type D grades. Grade A is for softer plastics, while Grade D is for harder ones. Shore hardness of the present invention was measured using a D grade.

In one embodiment of the present invention, the peel strength of the transparent layer may be 4 kgf / 2 cm or more, may be 5 kgf / 2 cm or more, may be 6 kgf / 2 cm or more, and may be 15 kgf / 2 cm or less. The peel strength of the transparent layer may be the peel strength of the transparent layer with respect to the printing layer, or may be the peel strength of the transparent layer with respect to the ink receiving layer. When the peel strength of the transparent layer is less than 4 kgf/2 cm, the adhesive force between the printing layer/ink receiving layer and the transparent layer is insufficient and the transparent layer may be easily peeled off, thereby deteriorating practical usability. The peel strength may be measured according to the KS M 3802 standard. A more specific method for measuring the peel strength of the transparent layer was described in Examples to be described later.

balance layer

In one embodiment of the present invention, a balance layer may be further included under the base layer, and the balance layer may include a polyvinyl chloride resin.

The balance layer may be located at the lowermost part of the flooring material and serve to impart bending balance to the flooring material, and the balance layer may be manufactured by molding a composition for a balance layer.

The balance layer includes a polyvinyl chloride resin, a filler and a plasticizer, and based on 100 parts by weight of the polyvinyl chloride resin, 70 parts by weight to 130 parts by weight of the filler; and 10 parts by weight to 50 parts by weight of a plasticizer. More preferably, the balance layer includes 80 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the polyvinyl chloride resin; and 20 parts by weight to 40 parts by weight of a plasticizer.

The thickness of the balance layer may be 0.1 mm to 0.7 mm, and may be 0.15 mm to 0.5 mm. When the thickness range of the base layer is satisfied, the effect of imparting a bending balance to the flooring is excellent.

In the present application, the filler includes at least one selected from calcium carbonate, amorphous silica, talc, zeolite, magnesium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, aluminum oxide, kaolin, ATH (Alumina trihydrate), and talc. can do. More specifically, the inorganic filler may be calcium carbonate.

In the present invention, the plasticizer may include at least one selected from phthalate-based plasticizers, terephthalate-based plasticizers, benzoate-based plasticizers, citrate-based plasticizers, phosphate-based plasticizers and adipate-based plasticizers.

The phthalate-based plasticizer is selected from dioctyl phthalate, diethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, dinonyl phthalate and ditridecyl phthalate It may be one or more.

The terephthalate-based plasticizer may be dioctyl terephthalate.

The benzoate-based plasticizer is 2-(2-(2-phenylcarbonyloxyethoxy)ethoxy)ethyl benzoate, glyceryl tribenzoate, trimethylolpropane tribenzoate, isononyl benzoate, 1-methyl- 1 selected from 2-(2-phenylcarbonyloxypropoxy)ethyl benzoate, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, n-hexyl benzoate and trimethylol propanetribenzoate There may be more than one species.

The citrate-based plasticizer may be at least one selected from acetyl tributyl citrate and tributyl citrate.

The phosphate-based plasticizer may be at least one selected from tricresyl phosphate and tributyl phosphate.

The adipate-based plasticizer may be at least one selected from bis(2-ethylhexyl) adipate, dimethyl adipate, monomethyl adipate, dioctyl adipate, and diisononyl adipate.

In the present invention, the pigment may be at least one selected from titanium dioxide, carbon black, water-based epoxy, and alcohol-based compounds. More specifically, the pigment may be titanium dioxide in order to clearly show the pattern or pattern of the printed layer provided on the upper part of the white layer.

In one embodiment of the present invention, the balance layer, the base layer, the white layer, and the transparent layer each selectively contain one or more selected from antioxidants, lubricants, processing aids, stabilizers, flame retardants, matting agents, impact stabilizers, and flame retardants. It may further include, and the content is not particularly limited.

The antioxidant may be at least one selected from phenol-based, sulfur-based, and phosphorus-based antioxidants.

The lubricant may be used alone or in combination with stearic acid, which is a saturated higher fatty acid having 18 carbon atoms, or a higher fatty acid having more than 18 carbon atoms, which is an eco-friendly lubricant.

The processing aid may be an acrylic copolymer.

The stabilizer may be at least one selected from barium-zinc-based and calcium-zinc-based thermal stabilizers.

The flame retardant is included to implement flame retardancy, and may be at least one selected from antimony trioxide, phosphorus-based flame retardants, and melamine-based flame retardants, and more preferably, antimony trioxide may be used in consideration of compatibility and flame retardant auxiliary effect.

As the matting agent and the impact stabilizer, those known in the art may be used without limitation.

The flame retardant is a metal hydroxide including aluminum hydroxide and magnesium hydroxide; phosphorus-based flame retardants; And it may include at least one selected from ammonium pyrophosphate.

Printing layer and ink receiving layer

In one embodiment of the present invention, the printed layer may be formed using a digital printing process, and more specifically, the printed layer may be formed using a digital printing process and a transfer process. The contents of the digital printing process and the transfer process are described in detail in the description of the manufacturing method of the flooring material to be described later.

The printing layer includes water-based ink, and as long as the water-based ink is used to form the printing layer of the flooring material, any water-based ink applied in the art may be used.

The thickness of the printing layer may be 0.1 μm to 5 μm, and may be 1 μm to 3 μm. When the thickness range of the printing layer is satisfied, various appearance and design effects can be imparted to the flooring material.

The ink receiving layer may serve to maximize printability of the print layer and increase durability.

The ink receiving layer may include an acrylic resin; metal salts; and organic or inorganic particles.

The acrylic resin may be applied as a binder resin of the ink receiving layer. The acrylic resin is methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, cyclohexyl acrylate, methyl methacrylate, hexyl methacrylate, acrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, At least one selected from hydroxypropyl acrylate and hydroxypropyl methacrylate may be included.

The metal salt may serve to improve printability of the print layer. The metal salt may be nitrate, sulfate, or chloride including one or more selected from Zn, Cu, Fe, Mn, Li, Ag, Mg, and Ca.

The organic or inorganic particles may serve to improve durability of the ink receiving layer. The organic and inorganic particles include calcium carbonate, kaolin, silica, alumina, TiO ₂ , Ca(OH) ₂ , CaO, Al(OH) ₃ and Al ₂ O ₃ It may include one or more selected from among.

The ink receiving layer may include 10 parts by weight to 30 parts by weight of a metal salt based on 100 parts by weight of an acrylic resin; and 10 to 30 parts by weight of organic particles or inorganic particles.

The ink receiving layer may have a thickness of 2 μm to 5 μm. When the thickness range of the ink receiving layer is satisfied, printability of the printing layer may be maximized and durability may be increased.

surface protective layer

In one embodiment of the present invention, a surface protection layer may be further included on the transparent layer. The surface protection layer may be a bead-containing photocuring layer. By applying a bead-containing photo-curing layer as the surface protective layer, it is possible to improve stain resistance, scratch resistance, and scratch resistance against small scratches.

The bead-containing photocurable layer is prepared by applying and curing a bead-containing photocurable composition, and the bead-containing photocurable composition may include photocurable urethane (meth)acrylate, beads, and a photocuring agent.

The photocurable urethane (meth)acrylate may be included in 45 wt% to 85 wt% or 50 wt% to 80 wt% of the total composition. When the content of the photocurable urethane (meth)acrylate is less than 45% by weight, difficulties may occur in the photocuring process, and the surface protective layer may be formed thin, making it difficult to sufficiently improve scratch resistance. In addition, when the content of the photocurable urethane (meth)acrylate exceeds 85% by weight, the applicability may deteriorate and the appearance may deteriorate, and the surface protective layer may be formed excessively thick, resulting in problems in moldability.

The photocurable urethane (meth)acrylate may include a photocurable functional group in its main chain or side chain. The photocurable functional group included in the photocurable urethane (meth)acrylate may include at least one selected from an acrylate group, a methacrylate group, and a combination thereof. As the photocurable (meth)acrylate, it is preferable to use an ultraviolet curable urethane (meth)acrylate having a (meth)acrylate functional group of 5 or more, preferably 6 to 9.

As the photocurable urethane (meth)acrylate, a commercially available material may be used as long as it conforms to the definition of the present invention.

The photocurable urethane (meth)acrylate has a weight average molecular weight of 1,000 g/mol to 250,000 g/mol, preferably 10,000 g/mol to 230,000 g/mol, more preferably 50,000 g/mol to 200,000 g/mol which can be used If the above-mentioned range is satisfied, proper coatability, toughness and scratch resistance can be maintained, and reactivity and surface hardness can be easily secured.

In the present invention, the weight average molecular weight can be measured by a method commonly used in the art, for example, using THF (tetrahydrofuran) as an eluent and standard through GPC (Gel Permeation Chromatography, waters breeze) It can be measured as a relative value for a standard polystyrene (PS) sample.

The beads may include at least one type of beads selected from metal oxide beads, glass beads, and acrylic beads, and it is preferable to use alumina beads in consideration of construction convenience. Based on 100 parts by weight of the urethane (meth)acrylate, the beads may be included in 3 parts by weight to 45 parts by weight, 5 parts by weight to 33 parts by weight, 5 parts by weight to 25 parts by weight, or 10 parts by weight to 25 parts by weight can When the above range is satisfied, scratch resistance against small scratches may be improved.

It is preferable to use two types of beads having different average particle diameters as the beads can more effectively improve scratch resistance against small scratches. At this time, as an appropriate average particle diameter, it is recommended to use at least one bead of 3 μm to 8 μm, or 4 μm to 6 μm and a bead of 9 μm to 40 μm, or 9 μm to 25 μm in combination to prevent small scratches. It is preferable because it does not adversely affect scratch resistance improvement and UV light irradiation.

The average particle diameter can be measured by a method known in the art, and for example, it can be measured using a dynamic light scattering method.

The photocuring agent may be a compound commonly used in the art, for example, the photocuring agent is at least one selected from alpha-hydroxy ketones, alpha amino ketones, acetophenones, and benzophenones. Of 0.1% to 15% by weight or 0.1% to 10% by weight may be included.

As the photocuring agent, a commercially available material may be used as long as it conforms to the definition of the present invention.

The bead-containing photocurable composition may further include at least one selected from a light stabilizer, a wetting agent, an antifoaming agent, and a thickening agent.

The bead-containing photocurable composition may have a viscosity of 300 cP to 1,500 cP and 500 cP to 1,000 cP measured at 25 °C. At this time, diacrylate and triacrylate may be included as monomers to control the viscosity, and an appropriate amount may be used within a range known in the art.

In the present invention, the viscosity may be the intrinsic viscosity (η) of the filtrate obtained after dissolving the sample in methylene chloride, measured at 20° C. using an Uberode-type viscous tube.

The bead-containing photocurable composition is cured through photocuring, and the thickness of the bead-containing photocurable layer including the photocured cured material may be 1 μm to 50 μm or 10 μm to 30 μm. When the thickness range of the bead-containing photocuring layer is satisfied, moldability can be improved while maintaining excellent hardness, friction resistance and durability. When the thickness of the bead-containing photocuring layer is less than 1 μm, hardness, friction resistance, durability, etc. may be deteriorated, and when it exceeds 50 μm, difficulties may occur in the process and formability may deteriorate. there is.

A laminated structure of a flooring material according to an exemplary embodiment of the present invention is schematically shown in FIGS. 1 and 2 below, and a laminated structure of a flooring material according to the prior art is schematically shown in FIG. 3 below.

As shown in FIG. 3, the conventional flooring material includes a laminated structure of a base layer 20, a white layer 30, a printing layer 40, and a transparent layer 90, and a soft transparent layer is used as the transparent layer 90 as a single layer. Since it is applied as a film, there is a problem in that scratch resistance due to external force on the surface of the flooring material is weak. In addition, in the conventional flooring material, even when a hard transparent layer is applied as a single film as the transparent layer 90, the adhesive strength between the print layer 40 and the transparent layer 90 is insufficient, so that the transparent layer 90 can be easily peeled off. there is

As shown in FIG. 1, the flooring material according to an exemplary embodiment of the present invention includes, from bottom to top, a base layer 20, a white layer 30, a printing layer 40, an ink receiving layer 50, and a first transparent layer ( 60) and the second transparent layer 70 in a sequentially stacked structure. In addition, as shown in FIG. 2 below, the flooring material according to one embodiment of the present invention may further include a balance layer 10 under the base layer 20, and on the second transparent layer 70 A surface protection layer 80 provided may be further included. At this time, the second transparent layer 70 may serve as a hard transparent layer, and the first transparent layer 60 is provided between the second transparent layer 70 and the printed layer 50 to serve as a soft transparent layer. can be done Therefore, in the flooring material according to an exemplary embodiment of the present invention, the first transparent layer, which is a soft transparent layer, and the second transparent layer, which is a hard transparent layer, are simultaneously applied as transparent layers provided on the ink receiving layer, so that adhesion between the printing layer including the ink receiving layer and the transparent layer is increased. In addition, it is possible to improve scratch resistance by external force on the surface of the flooring material.

Manufacturing method of flooring

A method for manufacturing a flooring material according to an exemplary embodiment of the present invention is a method for manufacturing a flooring material formed in a sequentially laminated structure of a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer from bottom to top, and on a transfer film. After forming the ink receiving layer, forming a printing layer on the ink receiving layer by a digital printing process; Forming a white layer on the base layer; forming a printing layer and an ink receiving layer on the white layer by performing a transfer process while laminating the transfer film on which the printing layer is formed on the white layer; and forming a transparent layer on the ink receiving layer after peeling off the transfer film, wherein the transparent layer is provided on the ink receiving layer as a first transparent layer; and forming a structure of a second transparent layer provided on the first transparent layer, wherein a glass transition temperature of the second transparent layer is higher than that of the first transparent layer.

A method for manufacturing a flooring material according to an exemplary embodiment of the present invention includes forming an ink receiving layer on a transfer film and then forming a printing layer on the ink receiving layer through a digital printing process.

The transfer film serves as a base film for forming a print layer in a digital printing process using water-based ink, and a transfer film known in the art may be used. For example, the transfer film may be a polyethylene terephthalate film or a paper film, and more preferably a polyethylene terephthalate film, but is not limited thereto.

The ink receiving layer may include the aforementioned acrylic resin; metal salts; And it can be formed by gravure printing a composition containing organic particles or inorganic particles on a transfer film.

The digital printing process may be performed by setting a desired pattern using a scan or graphic program on a digital computer, and printing the set pattern on the ink receiving layer by an inkjet method using water-based ink.

As described above, when the printing layer of the polyvinyl chloride-based flooring material is manufactured by the gravure printing method of water-based ink, since the polyvinyl chloride resin is hydrophobic, the adhesion between the printing layer and the transparent layer containing the polyvinyl chloride resin is insufficient, so that each other There is a problem that can be peeled off. In addition, the printing layer by the conventional gravure printing method not only cannot produce various colors, but also has limitations in printing a unique mosaic pattern, making it difficult to produce a three-dimensional effect and various colors and patterns at the same time. However, in the present invention, by forming the printed layer by a digital printing process using water-based ink, not only can the adhesion between the printed layer including the ink receiving layer and the transparent layer including polyvinyl chloride resin be improved, but also various colors are displayed on the printed layer. and patterns can be produced.

In addition, since the printing layer by the conventional gravure printing method is formed by printing on the transfer film, it does not include an ink receiving layer as in the present invention.

A release coating layer may be further provided between the transfer film and the ink receiving layer. The release coating layer is provided so that the transfer film can be more easily removed after transferring the printing layer and the ink receiving layer on the white layer. For the release coating layer, information known in the art may be applied, and for example, the release coating layer may include a silicone resin, but is not limited thereto.

A method for manufacturing a flooring material according to an exemplary embodiment of the present invention includes forming a white layer on the base layer. In addition, a step of forming a balance layer on a surface opposite to the surface on which the white layer of the base layer is formed may be further included.

In the method for manufacturing a flooring material according to an exemplary embodiment of the present invention, a transfer process is performed while laminating a transfer film having the printed layer formed on the white layer to form a printed layer and an ink receiving layer on the white layer. include The transfer process may use a method known in the art, and is not particularly limited.

The method for manufacturing a flooring material according to an exemplary embodiment of the present invention includes forming a transparent layer on the printing layer after peeling the transfer film. The peeling method of the transfer film is not particularly limited, and a method known in the art may be used.

A method for manufacturing a flooring material according to an exemplary embodiment of the present invention includes a first transparent layer provided on the ink receiving layer; and forming a structure of a second transparent layer provided on the first transparent layer, wherein a glass transition temperature of the second transparent layer is higher than that of the first transparent layer.

In the method for manufacturing a flooring material according to an exemplary embodiment of the present invention, since the contents of the first transparent layer and the second transparent layer are the same as those described above, a detailed description thereof will be omitted.

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention is not construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

<Example>

<Example 1> Performed as a process of pressing at 135 ° C. during the transfer process of the printed layer

1) Manufacture of a transfer film having an ink receiving layer and a printing layer formed thereon

A release coating layer was formed on the polyethylene terephthalate film using a silicone resin. A composition for an ink receiving layer was gravure-printed on the release coating layer to form an ink receiving layer having a thickness of 3 μm.

At this time, the composition for the ink-receiving layer includes an acrylic resin, a metal salt, and inorganic particles, and the acrylic resin includes butyl acrylate, methyl methacrylate, hydroxyethyl acrylate, and a phthalate-based plasticizer and emulsifier (BriteCoat 2730, VAE emulsion). ) was used as an acrylic emulsion polymerized through emulsion polymerization. In addition, based on 100 parts by weight of the acrylic resin, 20 parts by weight of MgCl ₂ was applied as the metal salt, and 30 parts by weight of silica was applied as the inorganic particles.

A printed layer having a thickness of 2 μm was formed on the ink receiving layer by digital printing using an inkjet method using water-based ink.

2) Manufacture of flooring materials

After preparing a composition containing the components of Table 1 below, calendering the composition to form a balance layer (thickness: 0.3 mm), a base layer (thickness: 3 mm), a white layer (thickness: 0.07 mm), a first transparent layer (0.45 mm), and a first transparent layer (0.45 mm). 2 transparent layers (0.07 mm) were prepared respectively.

The transfer process was performed while sequentially stacking the balance layer, the base layer, and the white layer from the bottom to the top, and stacking the transfer film on which the ink receiving layer and the printing layer were formed on the white layer.

After peeling off the transfer film, the first transparent layer and the second transparent layer were sequentially laminated on the ink receiving layer to prepare a flooring material.

[Table 1]

<Example 2 and Comparative Examples 1 to 4>

Except for changing the method of forming the first transparent layer, the second transparent layer, or the printing layer as shown in Table 2 below, the same procedure as in Example 1 was performed.

[Table 2]

Digital: After forming a printed layer by digital printing using an inkjet method using water-based ink, the transfer process is performed on the white layer

Gravure: A gravure printing process using water-based ink, which performs a transfer process on a white layer after forming a printed layer

<Experiment> Evaluation of scratch resistance and peel strength of transparent layer

The scratch resistance and peel strength of the transparent layer of the flooring prepared in Examples and Comparative Examples were evaluated and shown in Table 3 below.

<Scratch resistance evaluation method>

It was measured with an Ericsson tester based on EN 482-2 standards. More specifically, a test was conducted to measure scratch resistance based on a load value at which scratches occurred by placing a tip on the surface of a sample (10 cm × 10 cm) and applying a load (local force).

A Ball-Pen Tip with a diameter of 0.5 mm was used, and if scratches occurred by more than 50% by visual inspection, it was regarded as a failure point, and the load at this time was marked.

<Peel strength evaluation method>

The sample was cut into a width of 20 mm and a length of 150 mm, put in water at 80° C. for 1 hour, and then dried at room temperature for 3 hours to evaluate peel strength.

Both ends of the sample were clamped in a tensile tester (AMATEK LLOYD INSTRUMET), and peel strength was evaluated at a speed of 200 mm/min. At this time, a 5 kN load cell was applied as the load cell used, and the peel strength value was obtained by obtaining the average value of the 50 mm section of the peel load, and three samples were taken from the center and both edges of one tile and the average value was obtained.

[Table 3]

As a result, the flooring material according to an exemplary embodiment of the present invention simultaneously applies the first transparent layer, which is a soft transparent layer, and the second transparent layer, which is a hard transparent layer, as transparent layers provided on the printing layer including the ink receiving layer, thereby increasing the surface area of the flooring material. Scratch resistance by external force can be improved. When a hard transparent layer is applied as a transparent layer provided in direct contact with the ink receiving layer, the transparent layer can be easily peeled off due to lack of adhesion between the ink receiving layer and the hard transparent layer. However, in the present invention, as a transparent layer provided in direct contact with the ink receiving layer By applying the soft transparent layer, adhesion between the printing layer including the ink receiving layer and the transparent layer can be improved.

In addition, in order to simultaneously improve scratch resistance and peel strength of the flooring material, the first transparent layer preferably has a plasticizer content of 25 to 50 parts by weight based on 100 parts by weight of the polyvinyl chloride resin.

10: balance layer
20: base layer
30: white layer
40: printing layer
50: ink receiving layer
60: first transparent layer
70: second transparent layer
80: surface protective layer
90: transparent layer

Claims (15)

From the bottom to the top, a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer are sequentially formed in a laminated structure,
The printed layer is formed using a digital printing process,
The transparent layer may include a first transparent layer provided on the ink receiving layer; And a second transparent layer provided on the first transparent layer,
Flooring wherein the glass transition temperature of the second transparent layer is higher than the glass transition temperature of the first transparent layer. The method according to claim 1, wherein the printing layer comprises a water-based ink,
The ink receiving layer may include an acrylic resin; metal salts; and organic or inorganic particles. The method according to claim 2, wherein the metal salt is a nitrate, sulfate, or chloride containing one or more selected from Zn, Cu, Fe, Mn, Li, Ag, Mg, and Ca. flooring. The method according to claim 2, wherein the organic particles and inorganic particles are calcium carbonate (Calcium Carbonate), kaolin (Kaoline), silica (Silica), alumina (Alumina), TiO ₂ , Ca(OH) ₂ , CaO, Al(OH) ₃ And Al ₂ O ₃ A flooring material comprising at least one selected from the group consisting of: The method according to claim 2, wherein the ink receiving layer is based on 100 parts by weight of the acrylic resin, 10 parts by weight to 30 parts by weight of a metal salt; and 10 parts by weight to 30 parts by weight of organic particles or inorganic particles. The flooring material of claim 1, wherein the thickness of the first transparent layer is 3 to 10 times greater than the thickness of the second transparent layer. The flooring material according to claim 1, wherein the glass transition temperature of the first transparent layer is 15 °C to 30 °C, and the glass transition temperature of the second transparent layer is 40 °C to 70 °C. The method according to claim 1, wherein the first transparent layer comprises a polyvinyl chloride resin and a plasticizer,
Based on 100 parts by weight of the polyvinyl chloride resin, the content of the plasticizer is 25 parts by weight to 50 parts by weight. The method according to claim 1, wherein the second transparent layer comprises a polyvinyl chloride resin and a plasticizer,
Based on 100 parts by weight of the polyvinyl chloride resin, the content of the plasticizer is 3 parts by weight to 15 parts by weight of the flooring material. The flooring material according to claim 1, wherein each of the base layer and the white layer comprises a polyvinyl chloride resin. The method according to claim 1, further comprising a balance layer under the base layer,
The balance layer is a flooring material comprising a polyvinyl chloride resin. It is a method of manufacturing a flooring material formed in a sequential laminated structure of a base layer, a white layer, a printing layer, an ink receiving layer, and a transparent layer from bottom to top,
After forming an ink receiving layer on the transfer film, forming a printing layer on the ink receiving layer by a digital printing process;
Forming a white layer on the base layer;
forming a printing layer and an ink receiving layer on the white layer by performing a transfer process while laminating the transfer film on which the printing layer is formed on the white layer; and
After peeling off the transfer film, forming a transparent layer on the ink receiving layer,
a first transparent layer provided on the ink receiving layer; And forming a structure of a second transparent layer provided on the first transparent layer,
Method for producing a flooring material in which the glass transition temperature of the second transparent layer is higher than the glass transition temperature of the first transparent layer. 13. The method of claim 12, wherein the printing layer comprises an aqueous ink,
The ink receiving layer may include an acrylic resin; metal salts; And a method for producing a flooring material comprising organic or inorganic particles. The method according to claim 12, wherein the first transparent layer comprises a polyvinyl chloride resin and a plasticizer,
Based on 100 parts by weight of the polyvinyl chloride resin, the content of the plasticizer is 25 parts by weight to 50 parts by weight. The method according to claim 12, wherein the second transparent layer comprises a polyvinyl chloride resin and a plasticizer,
Based on 100 parts by weight of the polyvinyl chloride resin, the content of the plasticizer is 3 parts by weight to 15 parts by weight.

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