KR102069714B1 - Eco-friendly floor material - Google Patents

Abstract

Crystalline poly-extrusion molding a composition comprising a lactic acid resin, a car rendering or blow-molding (blow molding), and including a transparent layer formed by non-isothermal crystallization rate index (t _1/2) of the crystalline polylactic acid resin is from about 10 minutes to It is about 10 ³ minutes and provides an environmentally friendly flooring having a content of the crystalline polylactic acid resin from about 5% to about 65% by weight.

Description

Eco-Friendly Flooring {ECO-FRIENDLY FLOOR MATERIAL}

It relates to environmentally friendly flooring.

Flooring materials using petroleum resins such as polyvinyl chloride (PVC) are widely used as flooring materials in buildings such as houses, apartments, apartments, offices, and stores. Such a flooring material is manufactured by extrusion method, calendaring, etc. using resin, such as polyvinyl chloride (PVC). However, since the raw materials are all obtained from crude oil, which is a limited resource, it is expected that problems such as supply and demand of raw materials will occur in the future due to exhaustion of petroleum resources. In addition, the flooring material removed after use is disposed of by a landfill or incineration method, and the landfill method takes a long time to completely decompose the flooring material, and incineration method generates dioxin harmful to the human body. There is a problem in that a large amount of polluting material is released to pollute the environment causing secondary environmental pollution that damages the surrounding animals or plants.

Thus, although the flooring is manufactured using a polylactic acid resin, which is a biodegradable material, the processability is poor when forming by extrusion molding or calendering, and molding does not occur smoothly, and the material loss rate increases due to raw material sticking to the manufacturing apparatus. There is. In addition, there is a problem that the viscosity and elasticity of the flooring material is greatly changed by the heating in winter, so that the restoring force is lowered, and thus the floor partially recesses so that the floor cannot be maintained for a long time.

In one embodiment of the present invention while providing biodegradability provides an environmentally friendly flooring material that implements excellent processability, low material loss rate and excellent resilience.

In one embodiment of the present invention, the composition comprising a crystalline polylactic acid resin comprising a transparent layer formed by extrusion molding, calendering or blow molding (blow molding), the non-isothermal crystallization rate index of the crystalline polylactic acid resin (t _{1 / 2} ) is about 10 minutes to about 10 ³ minutes, the content of the crystalline polylactic acid resin to provide an environmentally friendly flooring material of 5% to 65% by weight.

The crystallization rate constant calculated according to the Abrami equation of the crystalline polylactic acid resin may be about 0.001 to about 3.12.

The rate of change of viscosity according to Formula 2 of the composition may be about 2% to about 20%:

[Calculation 2]

Viscosity change rate (ΔV,%) = (Vf-Vi) / Vi × 100

In the above formula, Vi is a viscosity at a time when the temperature is raised from a predetermined temperature and reaches about 160 ° C., and Vf is a viscosity at a time at which it is maintained at about 160 ° C. for about 10 minutes from the time when the temperature reaches about 160 ° C.

The tan δ measured at a temperature of about 80 ° C. to about 140 ° C. with respect to the transparent layer may be about 0.1 to about 1.0.

The weight ratio of L-lactic acid to D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin may be about 1: 0.01 to about 1: 0.12.

The content of D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin may be about 1% by weight to about 10% by weight.

The composition may or may not comprise an amorphous polylactic acid resin.

When the composition further comprises an amorphous polylactic acid resin, the weight ratio of the crystalline polylactic acid resin to the amorphous polylactic acid resin may be about 1:19 to less than about 100: 0.

When the molecular weight distribution of the crystalline polylactic acid resin is about 1.7 to about 2.2, and the composition further comprises an amorphous polylactic acid resin, the molecular weight distribution of the amorphous polylactic acid resin may be about 1.5 to about 2.1.

The weight average molecular weight of the crystalline polylactic acid resin is about 160,000 g / mol to about 250,000 g / mol, and when the composition further includes an amorphous polylactic acid resin, the weight average molecular weight of the amorphous polylactic acid resin is about 160,000 g / mol. To about 250,000 g / mol.

Melt index according to the conditions of ASTM D1238 of the transparent layer may be about 2g / 10 minutes to about 8g / 10 minutes.

The composition may further comprise at least one selected from the group consisting of plasticizers, melt strength enhancers, lubricants and other additives.

The amount of the plasticizer may be about 20 wt% or less.

The lower surface of the transparent layer may further include at least one selected from the group consisting of a printed layer, a chip inlay deucheung layer, a white layer, a dimensionally stable layer, a base layer, a balance layer and combinations thereof.

The eco-friendly flooring material is a transparent layer / printing layer or a chip inlay layer / white layer / base layer; Or a transparent layer / print layer or a chip inlay layer / white layer / dimension stabilization layer / base layer; Or a transparent layer / print layer or a chip inlay layer / white layer / base layer / balance layer; Or a laminate including a structure of a transparent layer / printed layer or a chip inlaid layer / white layer / dimension stabilization layer / base layer / balance layer.

At least one of the printed layer, the chip inlaid layer, the white layer, the dimensional stability layer, the base layer, and the balance layer may include the crystalline polylactic acid resin, the amorphous polylactic acid resin, or both.

The eco-friendly flooring provides an eco-friendly flooring that implements biodegradability while implementing excellent processability, low material loss rate, and excellent resilience.

1 is a schematic diagram showing a cross-section of an environmentally friendly flooring material according to an embodiment of the present invention.
2 is a schematic diagram schematically showing a cross section of the eco-friendly flooring material further comprising a print layer, a white layer, a dimensionally stable layer, a base layer, and a balance layer.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification. In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, for convenience of description, the thicknesses of some layers and regions are exaggerated.

Hereinafter, any configuration is formed on the "top (or bottom)" of the substrate or "top (or bottom)" of the substrate means that any configuration is formed in contact with the top (or bottom) of the substrate. However, it is not limited to including no other configuration between the substrate and any configuration formed on (or under) the substrate.

In one embodiment of the present invention, the composition comprising a crystalline polylactic acid resin comprising a transparent layer formed by extrusion molding, calendering or blow molding (blow molding), the non-isothermal crystallization rate index of the crystalline polylactic acid resin (t _{1 / 2} ) (non-isothermal crystallization half-life) is about 10 minutes to about 10 ³ minutes, and the content of the crystalline polylactic acid resin provides about 5% to about 65% by weight environmentally friendly flooring.

Polylactic acid resin is, for example, an eco-friendly resin produced by lactic fermentation of vegetable starch, but polylactic acid resin, which is generally used, is crystallized at a processing temperature range due to a slower crystallization rate than other types of resins used for flooring. The degree is low. Accordingly, the viscosity of the composition including the same can be easily changed in a relatively wide range, so the molding processability is very low, so that molding does not proceed smoothly to a specific shape, or the productivity is low due to high productivity loss due to sticking to a manufacturing apparatus. There is a problem.

In addition, even after the product molding of the polylactic acid resin is completely completed as the flooring material, the crystallization of the polylactic acid resin may not exist sufficiently so that the physical properties of the flooring material may be easily changed as the crystallization progresses further in the course of use. Since the heat resistance is low and the restoring power is low, the pressing phenomenon of the flooring material occurs easily at high temperatures such as the heating temperature in winter, and the durability is insufficient.

The polylactic acid resin may be formed by polycondensation of monomers including lactic acid, and may be formed by, for example, polycondensation of L-lactic acid and D-lactic acid, but is not limited thereto. .

Thus, in one embodiment, the content of the non-isothermal crystallization rate index (t _1/2) and at the same time about 10 minutes to form a lower level of from about 10 ^thirds of the crystalline polylactic acid resin to about 5 wt% By adjusting the level to about 65% by weight, the viscosity change rate of the composition including the crystalline polylactic acid resin may be implemented at an appropriately low level of about 2% to about 20%, as described below.

As a result, the crystallization of the crystalline polylactic acid resin proceeds at an appropriately high speed, and thus the molding loss is effectively reduced during extrusion, calendering, or blow molding of the composition containing the crystalline polylactic acid resin. And the productivity is increased, it is possible to realize the excellent workability and excellent economy.

At the same time, since the crystallization is sufficiently advanced in the finished product and the crystallization is no longer greatly progressed in the subsequent use process, the physical properties of the eco-friendly flooring material are maintained at a uniform level, and the heat resistance at high temperature increases and the resilience is increased. Pressing of the flooring does not occur easily, so that a flat floor shape is maintained for a long time, thereby achieving excellent uniformity and excellent durability of long-term excellent physical properties.

1 schematically shows a cross section of an eco-friendly flooring 100 according to one embodiment of the invention. The eco-friendly flooring material 100 includes a transparent layer 110 formed by extrusion molding, calendering or blow molding a composition including a crystalline polylactic acid resin, and the non-isothermal crystallization rate index of the crystalline polylactic acid resin ( t can be _{1/2) (non-isothermal} crystallization half-life) of about 10 minutes to about 10 minutes and ^3, the content of the crystalline polylactic acid resin, from about 5% to about 65% by weight.

The non-isothermal crystallization rate index (t _1/2) is then heated to the crystalline polylactic acid resin melt at a certain temperature of a temperature above the melting temperature and held for a certain time at the specified temperature, then the crystalline polyester wherein a specific temperature The crystallization degree corresponding to the fully crystallized state as a result of non-isothermal crystallization of the lactic acid resin while cooling to a specific temperature among the temperatures lower than the crystallization temperature at cooling rates such as about 2.5 ° C./min, about 5 ° C./min, and about 10 ° C./min. It may refer to 1/2, that is, the time taken to reach the degree of semicrystallization. Non-isothermal crystallization rate index (t _1/2) of the crystalline polylactic acid resin is specifically, can be measured under the conditions of a cooling rate of about 2.5 ℃ / min.

Specifically, in this specification, were measured by using a differential scanning calorimeter (Differential Scanning Calorimetry, DSC) of the non-isothermal crystallization rate index (t _1/2), for example, the crystalline polylactic acid resin, from about 10 ℃ / After heating to about 250 ° C at a heating rate of min for melting, the crystallized polylactic acid resin in the molten state is non-isothermally crystallized while cooling to about 0 ° C at a cooling rate of about 2.5 ° C / min. Although by definition a non-isothermal crystallization rate index (t _1/2), but is not limited to the above-described measurement method.

The crystalline polyester-isothermal crystallization rate index _{(t 1/2) (non} -isothermal crystallization half-life) of the lactic acid resin is from about 10 to about 10 minutes can be ³ minutes. By having a non-isothermal crystallization rate index within the above range, the crystallization rate of the crystalline polylactic acid resin is controlled at an appropriately high speed at a processing temperature, thereby effectively improving the molding processability during extrusion, calendering, or blow molding of the composition, thereby reducing the raw material loss rate. Reduction and increased productivity result in good processability and good economy.

In addition, the composition may include, for example, about 5% to about 65% by weight of the crystalline polylactic acid resin, specifically about 10% to about 50% by weight. As described above, the biodegradability can be sufficiently realized by including the content in the above range, and the crystallization rate of the crystalline polylactic acid resin is controlled at an appropriately high speed, so that crystallization is sufficiently progressed in the finished product, and thus crystallization is used in subsequent use. May not go any further. Accordingly, the physical properties of the eco-friendly flooring material is maintained at a uniform level, and also because the heat resistance at high temperature increases the restoring force is not easy to press the phenomenon of the flooring to maintain a flat floor shape for a long time excellent uniformity and Excellent durability can be achieved.

The crystallization rate index (t _1/2) of the crystalline polylactic acid resin by the US Abraham equation (Equation Avrami) crystallization rate constant (rystallization rate constant) is substituted by a calculation to be about 0.001 to about 3.12. By having a crystallization rate constant within the above range it is possible to reduce the rate of change of the viscosity of the composition to effectively improve the molding processability during extrusion, calendering or blow molding process, thereby increasing the processability of the composition to reduce the raw material loss rate Excellent economics can be achieved. Specifically, when the crystallization rate constant is greater than about 3.12, the phenomenon of sticking at the processing temperature during extrusion, calendering, or blow molding is increased, and the loss rate of the raw material is high. When the crystallization rate constant is less than about 0.001, the fluidity is too high at the processing temperature. Molding is difficult to shape.

The Abram equation can be defined as Formula 1 below:

[Calculation 1]

Log (-ln (1-X _t )) = logK _n + nlogt

In Formula 1, X _t is the volume fraction of the crystallized phase, n is the Abrami index, t is the crystallization rate index, and K _n is the crystallization rate constant. In other words, the crystallization rate constant may thus be calculated using the Abrami equation according to methods known in the art.

It provides an environmentally friendly flooring material having a viscosity change rate of about 2% to about 20% by the following formula 2 of the composition:

[Calculation 2]

Viscosity change rate (ΔV,%) = (Vf-Vi) / Vi × 100

In the above formula, Vi is a viscosity at a time when the temperature is raised from a predetermined temperature and reaches about 160 ° C., and Vf is a viscosity at a time at which it is maintained at about 160 ° C. for about 10 minutes from the time when the temperature reaches about 160 ° C. Specifically, Vi means a time point when the temperature of the composition is stably reached at about 160 ° C., and refers to a time point when the total temperature of the composition reaches about 160 ° C. and reaches a state having a uniform viscosity as a whole.

The temperature increase rate may be, for example, about 10 ° C / min to stably reach the temperature of the composition at about 160 ° C when measuring Vi, but may stably reach about 160 ° C depending on the specific components of the composition As long as it can be changed, it can change suitably and it is not specifically limited.

In addition, the rate of change of the viscosity of the composition may be, for example, about 2% to about 20%, specifically about 2% to about 15%. By having a viscosity change rate within the above range it is possible to maintain a more uniform viscosity at the processing temperature of extrusion molding, calendaring or blow molding to effectively improve the molding processability to increase the processability of the composition to reduce the raw material loss rate, thereby achieving excellent economic efficiency Can be.

Usually, the flooring material formed using the composition including the polylactic acid resin is low in heat resistance, and is inferior in durability due to a large change in physical properties at high temperature such as winter heating temperature, a decrease in resilience, and a crushing phenomenon easily occurring.

Thus, one embodiment in, the amount of non-isothermal crystallization rate index (t _1/2) and at the same time about 10 minutes to limit the suitably low level of about 10 ^thirds of the crystalline polylactic acid resin, about 5, as described above The tan δ measured at a temperature of about 80 ° C. to about 140 ° C. with respect to the transparent layer may be about 0.1 to about 1.0 by appropriately adjusting the level to a weight% to about 65% by weight. By maintaining the tanδ at a uniform level within a narrow range of about 0.1 to about 1.0 at a high temperature in the above range, the change in physical properties of the eco-friendly flooring material can be effectively suppressed and the crushing phenomenon can be improved, thereby increasing the resilience of the eco-friendly flooring material. By maintaining a flat bottom shape for a long time, excellent durability can be realized for a long time.

Specifically, the tan δ can be obtained from the result of viscoelasticity measured at a temperature of about −70 ° C. to about 150 ° C., a frequency of 1 Hz, and a heating rate of 3 ° C./min, and from about 80 ° C. to about 140 of the results of the viscoelasticity. The tan δ measured at a temperature of ° C. is narrow as described above, so that physical properties may be maintained at a uniform level. In addition, the tanδ obtained from the result of the viscoelasticity may have a maximum value of, for example, about 1.0 to about 2.5, and the maximum value may exist within a temperature range of about 50 ° C to about 80 ° C.

In addition, the melt index according to the conditions of ASTM D1238 of the transparent layer may be, for example, about 2g / 10 minutes to about 8g / 10 minutes, specifically, about 3g / 10 minutes to about 7g / 10 minutes Can be. By having a melt index within the above range, the molding of the flooring during extrusion, calendering or blow molding is more easily performed, thereby realizing excellent workability, and the molded eco-friendly flooring 100 may have excellent mechanical properties.

The weight ratio of L-lactic acid to D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin may be about 1: 0.01 to about 1: 0.12. By having a weight ratio within the range it is possible to more easily form a regular arrangement with a constant orientation in the process of crystallizing the crystalline polylactic acid resin, it is possible to control the crystallization rate of the crystalline polylactic acid resin to a low level, Accordingly, it is possible to further suppress the change in physical properties of the environmentally friendly flooring at a high temperature while further reducing the viscosity change rate of the composition.

The content of the D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin may be about 1% by weight to about 10% by weight. The D-lactic acid can be included in the weight range within the above range to control the crystallization rate of the crystalline polylactic acid resin to a low level, thereby further reducing the change in viscosity of the composition at a high temperature while further changing the physical properties of the environmentally friendly flooring material It can be suppressed.

In one embodiment, the composition may or may not further comprise an amorphous polylactic acid resin.

When the composition further comprises the amorphous polylactic acid resin, the weight ratio of the crystalline polylactic acid resin to the amorphous polylactic acid resin may be, for example, about 1:19 to less than about 100: greater than 0, specifically about And from greater than 1: 4 to less than about 100: zero.

As such, when the composition does not include the amorphous polylactic acid resin or includes the amorphous resin, the composition has a weight ratio in the above range, thereby suitably adjusting the viscosity change rate according to Formula 2 of the composition from about 2% to about 20%. It can be implemented at a low level, thereby maintaining the viscosity more uniformly at the processing temperature of extrusion, calendering, or blow molding, thereby effectively improving the molding processability, thereby increasing the processability of the composition and reducing the raw material loss rate, thereby providing excellent economy. Can be implemented.

When the molecular weight distribution of the crystalline polylactic acid resin is about 1.7 to about 2.2, and the composition further comprises an amorphous polylactic acid resin, the molecular weight distribution of the amorphous polylactic acid resin may be about 1.5 to about 2.1. By having a molecular weight distribution in the above range by appropriately adjusting the melt viscosity and melt strength during extrusion, calendaring or blow molding of the composition including the same, it is possible to easily form the environmentally friendly flooring material and implement the required mechanical properties.

The molecular weight distribution may be defined as a value representing a distribution of molecular weights and a weight average molecular weight divided by a number average molecular weight. When the molecular weight distribution is smaller than the above range, deformation of the environmentally friendly flooring easily occurs and durability is lowered, and when larger than the above range, molding processability of the composition is significantly reduced.

In one embodiment, the weight average molecular weight of the crystalline polylactic acid resin is about 160,000g / mol to about 250,000g / mol, the weight average molecular weight of the amorphous polylactic acid resin when the composition further comprises an amorphous polylactic acid resin About 160,000 g / mol to about 250,000 g / mol. By having a weight average molecular weight within the above range, as described above, the viscosity change rate of the composition can be implemented at a low level to further improve molding processability and at the same time effectively change the physical properties of the eco-friendly flooring material at high temperatures. In addition, the resistance to surface friction and moisture is improved to achieve excellent wear resistance and hydrolysis resistance.

The number average molecular weight of the crystalline polylactic acid resin is about 80,000 g / mol to about 120,000 g / mol, and when the composition further includes an amorphous polylactic acid resin, the number average molecular weight of the amorphous polylactic acid resin is about 90,000 g / mol. To about 130,000 g / mol. By having a number average molecular weight within the above range to form a molecular weight distribution at the level within each of the above ranges together with the weight average molecular weight within the above range to appropriately control the melt viscosity and melt strength of the composition to facilitate the molding of environmentally friendly flooring and the required mechanical properties Can be implemented.

The composition may further comprise at least one selected from the group consisting of plasticizers, melt strength enhancers, lubricants and other additives.

As the plasticizer, for example, a benzoate-based, citrate-based, phosphate-based plasticizer or the like can be used to achieve environmental friendliness. In addition, the plasticizer may include about 20% by weight or less. As described above, the composition may not include the plasticizer by improving moldability, or may contain a content of less than about 20% by weight, thereby effectively suppressing the bleeding phenomenon of the plasticizer and simultaneously It is possible to easily implement the desired physical properties by maintaining a good level of compatibility with the components.

As the melt strength enhancer, for example, an acrylic copolymer may be used, and the acrylic copolymer is about 0.1 to about 20 weights based on 100 parts by weight of the total polylactic acid resin in which the crystalline polylactic acid resin and the amorphous polylactic acid resin are combined. It may be included in a negative ratio to improve melt strength or heat resistance to enable calendering and pressing.

The lubricant includes about 0.01 parts by weight to about 10 parts by weight with respect to 100 parts by weight of the total polylactic acid resin combined with the crystalline polylactic acid resin and the amorphous polylactic acid resin, and the resin is calendered during processing such as calendering and pressing. It can effectively prevent sticking to rolls or presses. The type of the lubricant is not particularly limited, but may be environmentally friendly including environmentally friendly higher fatty acids, and specifically, stearic acid, which is a saturated higher fatty acid having 18 carbon atoms, may be used.

The transparent layer 110 may be formed from the composition, and may be finally formed into a film or sheet shape using, for example, extrusion molding, calendaring, or blow molding.

In addition, the transparent layer 110 may have a thickness of about 0.05mm to about 1.0mm, and having a thickness within the above range to be laminated on the lower side as described below without excessively increasing the thickness of the eco-friendly flooring 100 The pattern or pattern of the printed layer or the chip inlay layer can be sufficiently protected.

On the lower surface of the transparent layer 110 may further include at least one selected from the group consisting of a printing layer, a chip inlay deucheung layer, a white layer, the dimensional stability layer 140, a base layer, a balance layer and combinations thereof.

For example, the eco-friendly flooring may be a transparent layer / printed layer or a chip inlay layer / white layer / base layer sequentially; Or a transparent layer / print layer or a chip inlay layer / white layer / dimension stabilization layer / base layer; Or a transparent layer / print layer or a chip inlay layer / white layer / base layer / balance layer; Or it may be a laminate including a structure of a transparent layer / printed layer or a chip inlay deucheung / white layer / dimensionally stable layer / base layer / balance layer, but is not limited thereto. In addition, a surface treatment layer may be further included on an upper surface of the transparent layer.

2, the surface treatment layer 170, the transparent layer 110, the print layer 120, the white layer 130, the dimensionally stable layer 140, the base layer 150, and the balance layer 160 are sequentially stacked. Schematically shows a cross-section of an environmentally friendly flooring 100 '. The printed layer 120 may be replaced with the chip inlaid layer according to the purpose and function of the invention.

Hereinafter, each layer constituting the eco-friendly flooring 100 'will be described. At least one of the printed layer 120, the chip inlaid layer, the white layer 130, the dimensional stability layer 140, the base layer 150 and the balance layer 160 is the crystalline polylactic acid resin, The amorphous polylactic acid resin or both may be included, and accordingly, excellent affinity, excellent processability, low material loss rate, and excellent restoring force may be simultaneously implemented.

In addition, each of the layers may further include at least one selected from the group consisting of a melt strength enhancer, a lubricant and other additives, the content can be appropriately adjusted according to the properties and functions of the respective layers, it is particularly limited no.

The surface treatment layer 170 is the print layer 120 or the chip for the purpose of improving the surface quality such as scratch resistance or abrasion resistance of the eco-friendly flooring material 100 ', and to improve the pollution resistance to facilitate cleaning It may be formed on the laid layer. The surface treatment layer 170 is, for example, a UV curable composition known in the art, such as a urethane acrylate-based UV curable composition is applied on the printed layer 120 or the chip inlay layer, and irradiated with ultraviolet rays It can be formed by curing, but is not limited thereto.

As described above, the transparent layer 110 is formed on the printed layer 120 or the chip inlaid layer and serves to protect a pattern, a pattern, and the like formed on the printed layer 120 or the chip inlaid layer.

The print layer 120 may be formed by applying a pattern to various surfaces such as transfer printing, gravure printing, screen printing, offset printing, rotary printing, or flexographic printing on the surface of the white layer 130 stacked below. have.

The chip inlaid layer may be formed by including separate chips such as chips or fragrance chips made of polylactic acid resin, or the chip inlaid layer does not include a separate chip, but may include wood powder or the like in the form of a chip. Thus, when viewed from the surface of the eco-friendly flooring 100 'may be a form that looks like a chip embedded, but is not limited thereto.

The white layer 130 is a layer having a white color, and the printed layer 120 or the chip inlaid layer stacked on top of the printed layer 120 or the chip inlaid layer so that the pattern or pattern of the printed layer 120 is clearly displayed. It is possible to implement excellent durability by improving the adhesion between the dimensionally stable layer 140 stacked on the bottom.

The dimensionally stable layer 140, the dimensionally stable layer 140 further comprises a glass fiber, the mass per unit area of the glass fiber contained in the dimensionally stable layer 140 is about 30g / mm ² To about 150 g / mm ² . By having a mass per unit area within the above range it is possible to implement excellent durability by reducing the dimensional strain even under high temperature and high humidity conditions while maintaining excellent dimensional stability while maintaining a high level of adhesion with other layers laminated on the top and bottom. That is, the dimensionally stable layer 140 may have a structure in which glass fibers are impregnated with a binder resin, and for example, glass may be formed in at least one selected from the group consisting of acrylic resins, melamine resins, polylactic acid resins, and combinations thereof. The structure may be impregnated with fibers, but is not limited thereto.

The base layer 150 serves as the most basic layer of the eco-friendly flooring material 100 ′ and supports the transparent layer 110, the printing layer 120, the chip inlay layer, etc., and absorbs the impact of the upper or lower portion. can do.

The balance layer 160 is a portion that is bonded to the bottom surface during construction, protects the back surface opposite to the environment-friendly flooring 100 'surface, and serves to prevent the moisture of the floor.

At least one of the white layer 130, the chip inlaid layer, the base layer 150, and the balance layer 160 may include TiO ₂ , CaCO ₃ , wood flour, mica, glass fiber, It may further include at least one selected from the group consisting of starch, natural fiber, rice hull, rosin, talc and combinations thereof.

The eco-friendly flooring 100 'may be, for example, manufactured in the form of a film or sheet using extrusion molding, calendering or blow molding, and then using the plywood process known in the art. It can be formed by applying heat and pressure, but is not limited thereto.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Hereinafter, examples and comparative examples of the present invention are described. Such following examples are only examples of the present invention, and the present invention is not limited to the following examples.

( Example )

Example 1 (transparent layer: containing crystalline polylactic acid resin as binder resin)

(Transparent layer preparation)

65% by weight of crystalline polylactic acid resin (Nature Works, 4032D) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 200,000 g / mol, 20% by weight of benzoate plasticizer, and 10% by weight of acrylic copolymer And a composition containing 0.1% by weight of stearic acid as a higher fatty acid was kneaded at 160 ° C. with a half-barrier mixer, followed by primary and secondary mixing using a two-volume roll at 160 ° C., and then the prepared raw material was heated at a temperature of 170 ° C. It calendered and prepared the transparent layer as a film of thickness 0.5mm.

(Print layer and white layer preparation)

100 parts by weight of polylactic acid resin (Nature Works, 4032D), 12 parts by weight of benzoate plasticizer, 10 parts by weight of acrylic copolymer, 1 part by weight of stearic acid, 50 parts by weight of calcium carbonate, and 20 parts by weight of titanium dioxide were used. By calendering under the same conditions as in the preparation of the transparent layer, a white sheet was prepared as a white sheet having a thickness of 0.2 mm, and the printed layer was formed by applying a pattern to the surface of the white layer through a gravure printing or a transfer printing method. It was.

(Base layer preparation)

Preparation of the transparent layer using a composition of 100 parts by weight of polylactic acid resin (Nature Works, 4032D), 15 parts by weight of a benzoate plasticizer, 10 parts by weight of an acrylic copolymer, 2 parts by weight of stearic acid, and 500 parts by weight of calcium carbonate A calendering process was carried out under the same conditions as in the procedure to prepare a base layer as a sheet having a thickness of 2 mm.

(Balanced floor preparation)

Preparation of the transparent layer using a composition of 100 parts by weight of polylactic acid resin (Nature Works, 4032D), 15 parts by weight of a benzoate plasticizer, 10 parts by weight of an acrylic copolymer, 1 part by weight of stearic acid, and 150 parts by weight of calcium carbonate The calendering process was carried out on the same conditions as the above to prepare a balance layer as a sheet having a thickness of 1.2 mm.

The prepared transparent layer, the printed layer laminated white layer, base layer and the balance layer laminated in the structure of the transparent layer / printing layer / white layer / base layer / balance layer and then plywood by applying heat and pressure using a press device for eco-friendly flooring Was prepared.

Example 2 (transparent layer: includes both crystalline polylactic acid resin and amorphous polylactic acid resin)

55% by weight of crystalline polylactic acid resin (Nature Works, 4032D) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 200,000 g / mol, and an amorphous polylactic acid resin having a weight average molecular weight of 180,000 g / mol ( Nature Works, 6302D) 10% by weight, benzoate-based plasticizer 20% by weight, acrylic copolymer 10% by weight, and a higher fatty acid, the composition containing 0.1% by weight of stearic acid was kneaded at 160 ℃ with a half-barrier mixer and then First and second mixing using two rolls, and then the prepared raw material was calendered at a temperature of 170 ℃ to prepare a transparent layer as a film having a thickness of 0.5 mm and the same conditions and methods as in Example 1 As an environmentally friendly flooring material having a laminated structure of a transparent layer / printing layer / white layer / base layer / balance layer was prepared.

Example 3 (transparent layer: content ratio of crystalline polylactic acid resin and amorphous polylactic acid resin is different from Example 2)

35% by weight of crystalline polylactic acid resin (Nateure Works, 4032D) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 200,000 g / mol, and an amorphous polylactic acid resin having a weight average molecular weight of 180,000 g / mol. (Nateure Works, 6302D) A composition comprising 30% by weight, 15% by weight of benzoate plasticizer, 10% by weight of acrylic copolymer, and 0.1% by weight of stearic acid as a higher fatty acid was kneaded at 160 ° C. with a half-barrier mixer, and then 160 ° C. The first and second mixing was carried out using two rolls of, and then the prepared raw materials were calendered at a temperature of 170 ° C., and the same conditions as in Example 1 were prepared except that a transparent layer was prepared as a film having a thickness of 0.5 mm. An environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balance layer was manufactured by the method.

Example 4 (transparent layer: content ratio of crystalline polylactic acid resin and amorphous polylactic acid resin is different from Examples 2 and 3)

6% by weight of crystalline polylactic acid resin (Nateure Works, 4032D) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 200,000 g / mol, and an amorphous polylactic acid resin having a weight average molecular weight of 180,000 g / mol. (Nateure Works, 6302D) 54% by weight, benzoate-based plasticizer 20% by weight, acrylic copolymer 15% by weight, and a higher fatty acid composition containing 1% by weight of stearic acid kneaded in a semi-barrier mixer at 160 ℃ and then 160 ℃ The first and second mixing was carried out using two rolls of, and then the prepared raw materials were calendered at a temperature of 170 ° C., and the same conditions as in Example 1 were prepared except that a transparent layer was prepared as a film having a thickness of 0.5 mm. An environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balance layer was manufactured by the method.

Comparative Example 1 (When the crystallization rate of the crystalline polylactic acid resin is different compared to Example 1)

65 wt% of crystalline polylactic acid resin (Nature Works, 2500HP) having a ratio of L-lactic acid to D-lactic acid at 1: 0.009 and a weight average molecular weight of 200,000 g / mol, 20 wt% of a benzoate plasticizer, and 10 wt% of an acrylic copolymer And a composition comprising 0.1 wt% of stearic acid as a higher fatty acid was kneaded at 180 ° C. with a half-barrier mixer, and then mixed first and second using a two-bone roll at 180 ° C., and then the prepared raw material was heated at a temperature of 200 ° C. An environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balanced layer was manufactured under the same conditions and methods as in Example 1 except that a transparent layer was prepared as a film having a thickness of 0.5 mm by calendering. It was.

Comparative Example 2 (when the weight ratio of crystalline polylactic acid resin to amorphous polylactic acid resin is different)

2% by weight of crystalline polylactic acid resin (Nature Works, 4032D) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 200,000 g / mol, and an amorphous polylactic acid resin having a weight average molecular weight of 180,000 g / mol ( Nature Works, 6302D) A composition comprising 58% by weight, 20% by weight benzoate plasticizer, 10% by weight acrylic copolymer, and 0.1% by weight stearic acid as a higher fatty acid was kneaded at 180 ° C. with a half-barrier mixer and then The same conditions and methods as those in Example 1 were carried out using two rolls, followed by primary and secondary mixing, followed by calendering the prepared raw material at a temperature of 200 ° C. to prepare a transparent layer as a film having a thickness of 0.5 mm. As an environmentally friendly flooring material having a laminated structure of a transparent layer / printing layer / white layer / base layer / balance layer was prepared.

Comparative Example 3 (Transparent layer: When only amorphous polylactic acid resin was included as binder resin)

A composition comprising 65 wt% of an amorphous polylactic acid resin (Hisun, PLA 101L) having a weight average molecular weight of 190,000 g / mol, 20 wt% of a benzoate plasticizer, 15 wt% of an acrylic copolymer, and 0.1 wt% of stearic acid as a higher fatty acid. The mixture was kneaded at 140 ° C. with a half-barrier mixer, followed by primary and secondary mixing using two rolls of 140 ° C., and then the prepared raw materials were calendered at a temperature of 150 ° C. to form a transparent layer as a 0.5 mm thick film. Except for the preparation, an environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balance layer was prepared under the same conditions and methods as in Example 1.

Comparative Example 4 (when the weight average molecular weight of the crystalline polylactic acid resin is large)

65% by weight of crystalline polylactic acid resin (Purac, custom-made) having a ratio of L-lactic acid to D-lactic acid at 1: 0.015 and a weight average molecular weight of 260,000 g / mol, 20% by weight of benzoate plasticizer, and 10% by weight of acrylic copolymer And a composition containing 0.1% by weight of stearic acid as a higher fatty acid was kneaded at 200 ° C. with a half-barrier mixer, followed by primary and secondary mixing using a two-volume roll at 200 ° C., and then the prepared raw material was heated at a temperature of 210 ° C. An environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balanced layer was manufactured under the same conditions and methods as in Example 1 except that a transparent layer was prepared as a film having a thickness of 0.5 mm by calendering. It was.

Comparative Example 5 (When the weight average molecular weight of the crystalline polylactic acid resin is small)

65% by weight of crystalline polylactic acid resin (Hisun, PLA 210L) having a ratio of L-lactic acid to D-lactic acid 1: 0.13 and a weight average molecular weight of 130,000 g / mol, 20% by weight of benzoate plasticizer, 10% by weight of acrylic copolymer And a composition containing 0.1% by weight of stearic acid as a higher fatty acid was kneaded at 160 ° C. with a half-barrier mixer, followed by primary and secondary mixing using a two-volume roll at 160 ° C., and then the prepared raw material was heated at a temperature of 170 ° C. An environmentally friendly flooring material having a laminated structure of a transparent layer / printed layer / white layer / base layer / balanced layer was manufactured under the same conditions and methods as in Example 1 except that a transparent layer was prepared as a film having a thickness of 0.5 mm by calendering. It was.

( Experimental Example )

The viscoelasticity and melt index of each of the transparent layers of Examples 1-3 and Comparative Examples 1-5 were measured, and the viscosity change rate of the composition used to form each of the transparent layers was measured and described in Table 1 below. In addition, by measuring the crystallization rate of the crystalline polylactic acid resin included in the composition, by measuring the weight average molecular weight and the number average molecular weight of each of the crystalline polylactic acid resin or amorphous polylactic acid resin contained in the composition, by calculating the molecular weight distribution, It is listed in Table 2 below.

Experimental Example  One: Viscoelastic

Measuring method: Each of the films as the transparent layer was prepared with a sample of width 5.3mm and length 18mm, and they were prepared at -70 ° C to 150 ° C using DMA (TA, DMA Q800). Measured in the range. Frequency 1Hz, temperature rise rate 3 ℃ / min, amplitude gamma of 15㎛, Air atmosphere.

Experimental Example  2: resilience

Measuring method: Maintain 15 hours at 80 ℃ under a load of 60kg / m ² to the upper surface of each of the environmentally friendly flooring material, and then remove the load and leave for 1 hour and then visually observed the upper surface The restoring force was measured.

When the upper surface of the eco-friendly flooring is restored and returned to a flat floor state is displayed as "○", the case that the pressing phenomenon is rarely represented as "△", the case that the pressing phenomenon occurs because it is not restored ".

Experimental Example  3: viscosity change rate

Measurement method: Measured using a rheometer (manufactured by Anton Paar).

Specifically, each composition was put in the rheometer set to 80 ℃, after adjusting the gap between the Plate-Plate was heated at a temperature increase rate of 5 ℃ / min to measure the viscosity, Vi at the time point reached 160 ℃, After measuring the viscosity, Vf at the point of time maintained at 160 ° C for 10 minutes from the time of reaching 160 ° C, the viscosity change rate was calculated according to Formula 2 described above in one embodiment.

Experimental Example  4: Non-isothermal  Crystallization rate and crystallization rate constant

Measuring method: Measured using a differential scanning calorimeter (DSC, Discovery).

Specifically, the temperature was raised from room temperature to 250 ° C. at a temperature increase rate of 10 ° C./min, and then maintained at 250 ° C. for 5 minutes, followed by non-isothermal crystallization while cooling to 0 ° C. at a cooling rate of 2.5 ° C./min. Therefore, when the crystallinity degree finally reached is 1, the time taken to reach the point of crystallinity degree 0.5 was defined as the crystallization rate index. The crystallization rate constant k was calculated by substituting the non-isothermal crystallization rate index into the Abrami equation according to Formula 1 described above.

Experimental Example  5: weight average molecular weight ( Mw ), Number average  Molecular Weight( Mn ) And molecular weight distribution

Measuring method: Each polylactic acid resin was dissolved in Chloroform at a concentration of 0.25% by weight, and gel permeation chromatography (manufacturer: Agilent 1200, column: PLgel 10 μm Mixed-B * 2ea, PLgel 10 μm Guard * 1ea, Detector: RID).

Flow rate: 1.0 mL, solvent: chloroform, standard: polystyrene.

Subsequently, the measured weight average molecular weight (Mw) was divided by the measured number average molecular weight (Mn) to calculate the molecular weight distribution (Mw / Mn).

Experimental Example  6: melt index ( melt index )

Measurement method: measured using a weight of 2.16 kg at a temperature of 190 ° C. according to the conditions of ASTM D1238, the above measurements were repeated 10 times to evaluate the average of these as the melt index.

Dynamic viscoelasticity (tanδ) Viscosity Change Rate (%) Melt Index (g / 10min) dynamic stability Example 1 0.1-0.3
3 3 ○ Example 2 0.1-0.4 4 3 ○ Example 3 0.2-0.6 8 4
○ Example 4 0.35-1.0 20 6
△ Comparative Example 1 0.01 ~ 0.2 0 0
Ⅹ Comparative Example 2 0.4-1.1 22 7
Ⅹ Comparative Example 3 0.4-1.5 25 7 Ⅹ Comparative Example 4 0.05-0.25 0 0 Ⅹ Comparative Example 5 0.3 ~ 1.1 25 15 Ⅹ

Crystallization rate index (t _1/2)
(minute) Crystallization rate constant (K) Molecular weight distribution Weight average molecular weight
(g / mol) Number average molecular weight
(g / mol) Example 1 20 2 1.9 c-PLA: 200,000 c-PLA: 100,000 Example 2 20 2 c-PLA: 1.9,
a-PLA: 1.85 c-PLA: 200,000
a-PLA: 200,000 c-PLA: 100,000
a-PLA: 110,000 Example 3 20 2 c-PLA: 1.9,
a-PLA: 1.85 c-PLA: 200,000
a-PLA: 200,000 c-PLA: 100,000
a-PLA: 110,000 Example 4 20 2 c-PLA: 1.9,
a-PLA: 1.85 c-PLA: 200,000
a-PLA: 200,000 c-PLA: 100,000
a-PLA: 110,000 Comparative Example 1 9 3.12 2.0 c-PLA: 200,000 c-PLA: 110,000 Comparative Example 2 9 3.12 c-PLA: 2.0,
a-PLA: 2.0 c-PLA: 200,000
a-PLA: 190,000 c-PLA: 110,000
a-PLA: 90,000 Comparative Example 3 Not measurable Not measurable 2.0 a-PLA: 190,000 a-PLA: 90,000 Comparative Example 4 8 3.5 2.2 c-PLA: 260,000 c-PLA: 150,000 Comparative Example 5 1.005Ⅹ10 ³ 2.72 1.75 c-PLA: 130,000 c-PLA: 80,000

Eco-friendly flooring according to the embodiment 1-4 is characterized in that the non-isothermal crystallization rate index, the crystallization rate constant, the melt index, the viscosity change rate and the degree of change of viscoelasticity are all appropriate processability such as short-barrib release property, moldability; And use properties such as workability, structural balance, and restoring force.

On the other hand, the environmentally friendly flooring material according to Comparative Examples 1 and 4 has a small non-isothermal crystallization rate index, the melt index and the viscosity change rate are 0, so that blending does not occur at a processing temperature of about 160 ° C., which is performed at a higher temperature. In addition, workability and workability were inferior, and the use properties such as workability, structural balance, and restoring force were inferior. In addition, the eco-friendly flooring material according to Comparative Example 2 is inferior in workability and workability because the crystallization rate index is small, and the content of amorphous polylactic acid resin is high, so that the degree of change in the viscoelasticity, the viscosity change rate, and the melt index are large, the workability Physical properties such as structural balance and restoring force were also inferior. In addition, the environmentally friendly flooring material according to Comparative Example 3 can not measure the crystallization rate index, the crystallization rate constant, the degree of change in the viscoelasticity, the viscosity change rate and the melt index is too large, easily at a processing temperature of about 160 ℃ Workability such as meltability, moldability, and mold release; And use properties such as workability, structural balance, and restoring force. In addition, in Comparative Example 5, the crystallization rate index, the degree of change of the viscoelasticity, the viscosity change rate, and the melt index were remarkably large, resulting in inferior processability and inferior use properties such as workability, structural balance, and restoring force.

100, 100 ': eco-friendly flooring
110: transparent layer 120: printed layer 130: white layer 140: dimensionally stable layer
150: base layer 160: balance layer 170: surface treatment layer

Claims (16)

A transparent layer formed by extrusion molding, calendering or blow molding a composition comprising a crystalline polylactic acid resin,
The isothermal crystallization rate index (t _1/2 ) of the crystalline polylactic acid resin is 10 minutes to 10 ³ minutes,
The content of the crystalline polylactic acid resin is 5% by weight to 65% by weight,
The molecular weight distribution of the crystalline polylactic acid resin is 1.7 to 2.2,
When the composition further comprises an amorphous polylactic acid resin, the molecular weight distribution of the amorphous polylactic acid resin is 1.5 to 2.1
Eco-Friendly Flooring.
The method of claim 1,
The crystallization rate constant calculated according to the Abrami equation of the crystalline polylactic acid resin (rystallization rate constant) is 0.001 to 3.12
Eco-Friendly Flooring.
The method of claim 1,
Viscosity change rate according to the following formula 2 of the composition is 2% to 20%
Eco-friendly flooring:
[Calculation 2]
Viscosity change rate (ΔV,%) = (Vf-Vi) / Vi × 100
In the above formula, Vi is the viscosity at the time of heating up from a predetermined temperature to reach 160 ° C, and Vf is the viscosity at the time of holding at 160 ° C for 10 minutes from the time of reaching 160 ° C.
The method of claim 1,
Tan δ is 0.1 to 1.0 measured at a temperature of 80 ℃ to 140 ℃ for the transparent layer
Eco-Friendly Flooring.
The method of claim 1,
The weight ratio of L-lactic acid to D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin is 1: 0.01 to 1: 0.12.
Eco-Friendly Flooring.
The method of claim 1,
The content of D-lactic acid in the total polymerizable compounds constituting the crystalline polylactic acid resin is 1 wt% to 10 wt%
Eco-Friendly Flooring.
The method of claim 1,
When the composition further comprises the amorphous polylactic acid resin, the weight ratio of the crystalline polylactic acid resin to the amorphous polylactic acid resin is from 1:19 to less than 100: greater than 0.
Eco-Friendly Flooring.
delete The method of claim 1,
The weight average molecular weight of the crystalline polylactic acid resin is 160,000g / mol to 250,000g / mol,
When the composition further comprises the amorphous polylactic acid resin, the weight average molecular weight of the amorphous polylactic acid resin is 160,000g / mol to 250,000g / mol
Eco-Friendly Flooring.
The method of claim 1,
Melt index of the transparent layer according to the conditions of ASTM D1238 is 2g / 10 minutes to 8g / 10 minutes
Eco-Friendly Flooring.
The method of claim 1,
The composition further comprises at least one selected from the group consisting of plasticizers, melt strength enhancers, lubricants and other additives, the content of the plasticizer is 20% by weight or less
Eco-Friendly Flooring.
The method of claim 1,
On the lower surface of the transparent layer further comprises at least one selected from the group consisting of a printed layer, a chip inlaid layer, a white layer, a dimensionally stable layer, a base layer, a balance layer and combinations thereof
Eco-Friendly Flooring.
The method of claim 12,
Transparent layer / print layer or chip inlay layer / white layer / base layer; Or a transparent layer / print layer or a chip inlay layer / white layer / dimension stabilization layer / base layer; Or a transparent layer / print layer or a chip inlay layer / white layer / base layer / balance layer; Or a transparent layer / printing layer or a chip inlay layer / white layer / dimension stabilization layer / base layer / balance layer.
Eco-Friendly Flooring.

The method of claim 12,
At least one of the printed layer, the chip inlaid layer, the white layer, the dimensional stability layer, the base layer, and the balance layer includes the crystalline polylactic acid resin, the amorphous polylactic acid resin, or both
Eco-Friendly Flooring.
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