KR20110052528A - Resin composition for flooring material - Google Patents

Abstract

PURPOSE: A resin composition for flooring materials is provided to ensure excellent melting efficiency, melting strength, viscosity, shock resistance, heat resistance, mechanical strength and processability even if polylactic acids obtained from raw materials extracted from recycling plant resources are used. CONSTITUTION: A resin composition for flooring materials comprises 100 parts by weight of polylactic acid, 5-60 parts by weight of plasticizer, 0.001-30 parts by weight of lubricant, and 1-60 parts by weight of a processing aid including a copolymer containing methyl methacrylate as a polymerization unit. The polylactic acid is a polymer including, as a polymerization unit, one or more selected from the group consisting of L-lactic acid, D-lactic acid, L,D-lactic acid, L-lactide D-lactide and L,D-lactide.

Description

Resin composition for flooring material

The present invention relates to a resin composition for flooring.

BACKGROUND ART The flooring manufactured by applying petroleum resin such as polyvinyl chloride (PVC) to a construction method such as calendering is widely used in buildings such as houses, apartments, apartments, offices, and stores.

By the way, since the polyvinyl chloride-based flooring material is manufactured from a fossil energy source that is not renewable, it is expected that the supply of raw materials and the continuous increase in price will occur due to resource depletion.

In addition, flooring made of fossil raw materials, such as polyvinyl chloride, emits a large amount of greenhouse gases (eg, CO _2, etc.) during the manufacturing process. In addition, the polyvinyl chloride flooring material contains a toxic plasticizer such as DOP (dioctyl phthalate), and releases harmful substances such as environmental hormones and toxic gases at incineration disposal or fire, and in a natural environment at landfill disposal. There is a problem that remains permanently, causing a large environmental burden.

Accordingly, a method of constructing a flooring material using polylactic acid, which is a biodegradable resin, is known.

However, since polylactic acid is inferior in physical properties such as impact resistance, melting efficiency, melt strength, and heat resistance, it is difficult to apply a calendering method, and thus it is mostly manufactured by a press or extrusion method. By the way, the flooring material produced by applying the polylactic acid to the press or extrusion method is disadvantageous in terms of reducing the production cost, such as physical properties, such as flexibility.

An object of this invention is to provide the resin composition for flooring materials, the flooring material manufactured using the same, and its manufacturing method.

The present invention includes a polymer comprising 100 parts by weight of polylactic acid (PLA), 5 parts by weight to 60 parts by weight of plasticizer, 0.001 parts by weight to 30 parts by weight of lubricant, and methyl methacrylate as polymerized units. It relates to a resin composition for flooring comprising 1 part by weight to 60 parts by weight of a processing aid.

The resin composition may be, in particular, a composition for calendering processing, that is, a composition that can be effectively applied to a calendering method in the manufacturing process of a flooring material.

Hereinafter, the said resin composition for flooring materials is demonstrated concretely.

The kind of the polylactic acid in the present invention is not particularly limited, and for example, a polylactic acid obtained by polymerizing a monomer mixture containing lactide or lactic acid may be used. Specifically, the polylactic acid, which comprises at least one selected from the group consisting of L-lactic acid, D-lactic acid, L, D-lactic acid, L-lactide, D-lactide and L, D-lactide as polymerized units Polymers can be used. The lactic acid or lactide may be prepared by fermenting starch extracted from corn, potato, or sweet potato, which are renewable plant resources. In the present invention, the polylactic acid, together with the above-described lactic acid or lactide, glycol compounds such as ethylene glycol or propylene glycol, if necessary; Dicarboxylic acids such as terephthalic acid or ethanedioic acid; Hydroxycarboxylic acids such as glycolic acid or 2-hydroxybenzoic acid; Alternatively, monomers such as lactones such as caprolactone or propiolactone may be further included as polymerized units. Such polylactic acid usually contains a repeating unit represented by the following formula (1).

[Formula 1]

Such polylactic acid has an environment-friendly property that hardly emits greenhouse gases and toxic substances during use or incineration, and can be easily biodegraded under natural environment even when disposed of landfill.

The polylactic acid may be generally classified into D-polylactic acid, L-polylactic acid, D, L-polylactic acid, or meso-polylactic acid, and the present invention is not limited thereto, and may be one or more of the above. The above polylactic acid can be used.

The resin composition for the flooring material also includes a plasticizer, and the plasticizer can impart excellent flexibility, impact resistance and melting efficiency to the composition or a molded article produced therefrom.

The type of plasticizer that can be used in the present invention is not particularly limited as long as it can perform the above-described functions, but it is preferable to use a plasticizer having environmentally friendly characteristics. Examples of such plasticizers include phthalate compounds, citric acid compounds (e.g. citric acid or citric acid esters), fatty acid esters, polyalkylene glycols (e.g. polyethylene glycol or polypropylene glycol). Glycerol esters, vegetable oils, modified vegetable oils, allyl phosphate esters, dialkyl ether diesters, tricarboxylic acid esters, epoxidized oils, epoxidized esters, polyesters, polyglycol diesters, allyl ether di One kind or a mixture of two or more kinds of esters, aliphatic diesters, alkyl ether monoesters and dicarboxylic acid esters may be used. Among them, citric acid compounds, fatty acid esters, polyalkylene glycols, glycerol esters, A kind of vegetable oil or modified vegetable oil Or a mixture of two or more may be used, but is not limited thereto.

In one aspect of the invention, the modified vegetable oil may be an epoxidized vegetable oil or other modified vegetable oils, for example, epoxidized soybean oil, specifically MSO (epoxidized methyl soyate), EPO (epoxidized linseed oil), It may be an epoxidized soy oil (ESO) or an epoxidized tall oil (ETO).

In the present invention, the environmentally friendly citric acid plasticizer is, for example, triethyl citrate (TEC, triethyl citrate), acetyl triethyl citrate (ATEC, acetyl triethyl citrate), tripropyl citrate (TPC, tripropyl citrate) , Acetyl tripropyl citrate (ATPC, acetyl tripropyl citrate), tributyl citrate (TBC, tributyl citrate), acetyl tributyl citrate (ATBC, acetyl tributyl citrate), trihexyl citrate (THC, trihexyl citrate), Acetyl trihexyl citrate (ATHC) or a blend of citrate and modified vegetable oils can be used, preferably, acetyl tributyl citrate, more preferably acetyl tributyl citrate Mixtures of vegetable oils can be used.

The resin composition of the present invention, the plasticizer as described above, 5 parts by weight to 60 parts by weight, preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of polylactic acid. More preferably 15 parts by weight to 40 parts by weight. If the content of the plasticizer is less than 5 parts by weight, there may be a slight improvement in physical properties due to the addition of the plasticizer. If the content of the plasticizer exceeds 60 parts by weight, the softening degree of the resin may be excessively increased, or the melt viscosity may be low, thereby making processing difficult.

The resin composition of this invention contains a lubricant further in addition to the component mentioned above. Lubricants improve the fluidity by lubricating the surface of metal fittings such as calender rollers during molding of the resin composition of the present invention, preventing adhesion between metal fittings and resins, improving slip properties, and controlling melt viscosity to form It is possible to maximize processability, in particular, calendering moldability.

The type of lubricant that can be used in the present invention is not particularly limited as long as it performs the above-mentioned action, for example, stearic acid, stearic acid metal salt (ex. Calcium salt, magnesium salt, or zinc salt). ; Synthetic waxes in ester or amide form; Hydrocarbons such as montan wax, paraffin wax or mineral oil; Or silicone compounds.

The resin composition of the present invention, the lubricant is based on 100 parts by weight of polylactic acid, 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, more preferably 1 to 10 parts by weight It may include. If the amount of the lubricant is less than 0.001 part by weight, the effect of improving the moldability due to the addition of the lubricant may be insignificant. If the amount of the lubricant is more than 30 parts by weight, the printability of the flooring material may be deteriorated due to a decrease in adhesive strength with ink, or a decrease in interlayer adhesion. There is a fear that plywood with other layers becomes difficult.

The resin composition for floor coverings of this invention contains a processing aid. The processing aid may improve melt efficiency, melt strength, viscosity characteristics, impact resistance, heat resistance, mechanical strength, and the like, so that the composition of the present invention has particularly suitable physical properties for calendering molding.

In the present invention, as the processing aid, a copolymer containing methyl methacrylate (MMA) as a polymer unit, preferably a ternary copolymer, is used. The term "three-way copolymer" means a three-component copolymer containing methyl methacrylate as a basic component and further including two monomers as polymerized units in addition to the above.

The copolymer may further include, as a component constituting the terpolymer, a monomer represented by the following formula (2) as a polymerized unit.

 [Formula 2]

In Formula 2, R represents hydrogen or an alkyl group, and R ₁ represents an alkyl group having 1 to 20 carbon atoms, except that R and R ₁ are methyl groups at the same time.

In Formula 2, R is preferably hydrogen or a straight or branched chain alkyl group having 1 to 12 carbon atoms, more preferably hydrogen or a straight or branched chain alkyl group having 1 to 8 carbon atoms, more preferably hydrogen or 1 to 4 carbon atoms. It may be a linear or branched alkyl group of, specifically, may be hydrogen or methyl.

On the other hand, in Formula 2, R ₁ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, preferably a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, more preferably May be a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

In addition, the alkyl group is, for example, by a substituent known in the chemical art, including a halogen atom, hydroxy group, alkyl group, alkenyl group, alkynyl group, carboxyl group, epoxy group, thiol group, isocyanate group or alkoxy group It may be substituted or unsubstituted.

More specific examples of the monomer of Formula 2 include methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate or cyclohexyl (meth) acrylate, and the like, but are not limited thereto.

In the present invention, the copolymer may further include a monomer represented by the following Chemical Formula 3 or 4 as a polymerized unit.

(3)

[Formula 4]

In Formulas 3 and 4, R represents hydrogen or alkyl, A represents alkylene, n represents an integer of 1 to 5, R ₂ is an aryl group or -C (unsubstituted or substituted with an alkenyl group) = O) -OR ₃ , wherein R ₃ represents an aryl group or an arylalkyl group.

In Formulas 3 and 4, R is preferably hydrogen or a straight or branched chain alkyl group having 1 to 12 carbon atoms, more preferably hydrogen or a straight or branched chain alkyl group having 1 to 8 carbon atoms, still more preferably hydrogen or 1 carbon atom. It may be a straight or branched chain alkyl group of 4 to 4, specifically, may be hydrogen or methyl.

Meanwhile, in Formulas 3 and 4, A is a linear, branched or cyclic alkylene group having 1 to 14 carbon atoms, preferably linear, branched or cyclic alkylene having 1 to 10 carbon atoms, and more Preferably, it may be a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms.

In addition, in Formula 4, the aryl group of R _{1 may be} an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and specifically, may be a phenyl group. In addition, examples of the alkenyl group which may be substituted with the aryl group represented by Chemical Formula 4 include a vinyl group, but are not limited thereto.

In addition, in Formula 4, the aryl group of R _{3 may be} an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, preferably a phenyl group, and an arylalkyl group may be an arylalkyl group having 7 to 30 carbon atoms, Preferably it may be an arylalkyl group having 8 to 13 carbon atoms, specifically benzyl group.

In addition, n in Chemical Formula 3 may be preferably 1 to 3, more preferably 1 to 2.

In addition, the alkyl group, alkylene group, aryl group or arylalkyl group in the above, for example, containing a halogen atom, hydroxy group, alkyl group, alkenyl group, alkynyl group, carboxyl group, epoxy group, thiol group, isocyanate group or alkoxy group It may be substituted or unsubstituted by a substituent known in the chemical art.

Specific examples of the monomer represented by the formula (3) or (4) include phenyl (meth) acrylate, benzyl (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (Meth) acrylate, divinyl benzene, ethylene glycol di (meth) acrylate or diethylene glycol di (meth) acrylate, and the like, but are not limited thereto.

On the other hand, in the present invention, when the terpolymer is a methyl methacrylate and a monomer of the formula (2) as a polymer unit, the copolymer, 60 parts by weight to 86 parts by weight of methyl methacrylate, preferably 75 parts by weight Parts to 85 parts by weight; And 14 parts by weight to 40 parts by weight, preferably 15 parts by weight to 25 parts by weight, of the monomer of Formula 2 as a polymerization unit.

In addition, when the copolymer comprises methyl methacrylate, a monomer of formula (2) and a monomer of formula (3) or (4), the copolymer is 60 parts by weight to 86 parts by weight of methyl methacrylate, preferably 75 parts by weight. Parts to 85 parts by weight; 14 to 39.9 parts by weight, preferably 15 to 25 parts by weight of the monomer of Formula 2; And 0.0001 parts by weight to 0.1 parts by weight, preferably 0.001 parts by weight to 0.5 parts by weight, of the monomer of Formula 3 or 4 as polymerized units.

If the content of methyl (meth) acrylate contained in the copolymer is less than 60 parts by weight, the compatibility with polylactic acid may be poor, and workability may deteriorate. If it exceeds 86 parts by weight, initial dispersibility at the time of processing There is a risk that the foaming nonuniformity or the like may be caused to decrease.

On the other hand, when the copolymer contains a monomer of the formula (3) or 4, if the content is less than 0.0001 parts by weight, there is a fear that the foaming improvement effect, etc. due to the molecular weight decrease of the terpolymer is insignificant, if it exceeds 0.1 parts by weight There exists a possibility that processing efficiency and foam workability may fall.

In the present invention, the processing aid may have a weight average molecular weight (Mw) of 500,000 to 8 million, preferably 1 million to 5 million. If the weight average molecular weight of the processing aid is less than 500,000, there may be a slight improvement in physical properties due to the processing aid, if more than 8 million, there is a fear that the workability improvement effect due to a decrease in melting efficiency, etc ..

In the present invention, a method for preparing such a processing aid is not particularly limited. For example, solution polymerization, photopolymerization, bulk polymerization, suspension polymerization or emulsion polymerization using the above-described monomer mixture may be performed. emulsion polymerization), but in order to maximize performance as a processing aid, it is preferable to manufacture by applying an emulsion polymerization method. That is, in the present invention, the processing aid may be an emulsion polymer containing an emulsion polymer including methyl methacrylate as a polymerization unit.

In the present invention, when the emulsion polymerization method is applied to provide a processing aid, the processing aid may include a first step of applying a monomer mixture including methyl methacrylate to emulsion polymerization to prepare a polymer; And adding a second monomer in the presence of the polymer prepared in the first step, and preparing a polymer by emulsion polymerization, wherein each step is known in the art. It may also be carried out using a common emulsifier, a polymerization initiator or a redox catalyst.

On the other hand, the type or ratio of the monomer in the monomer mixture of the first step or the type and ratio of the monomer introduced in the second step is not particularly limited and may be selected according to the type of the desired processing aid.

For example, when preparing a copolymer comprising methyl methacrylate, a monomer of formula (2) and a monomer of formula (3) or (4) as a processing aid in the present invention, for the monomer mixture of the first step, methyl methacryl 69.9 parts by weight to 95 parts by weight; And 4 to 30 parts by weight of monomer of Formula 2 and / or 0.0001 to 0.1 parts by weight of monomer of Formula 3 or 4. In addition, the monomer introduced in the second step is 54.9 parts by weight to 70 parts by weight of methyl methacrylate; And 29 parts by weight to 45 parts by weight of monomer of Formula 2 and / or 0.0001 parts by weight to 0.1 parts by weight of monomer of Formula 3 or 4, and the final emulsion polymer is copolymer 25 prepared in the first step. The polymerization conditions are preferably controlled to include but are not limited to from 35 parts by weight to 65 parts by weight and 65 parts by weight to 75 parts by weight of the polymer prepared in the second step.

In the present invention, when the processing aid is an emulsion polymer, the polymer preferably has a relative viscosity (η _Rel ) at room temperature of 4.0 to 12.0. When the said viscosity is less than 4.0, there exists a possibility that foamability and stability of a foaming cell may fall, and when it exceeds 12.0, there exists a possibility that processing characteristics may fall.

Examples of such emulsion polymers that can be used in the present invention include, but are not limited to, PA series available from LG Chem.

In the present invention, the processing aid, 1 part by weight to 60 parts by weight, preferably 2 parts by weight to 40 parts by weight, more preferably 5 parts by weight to 30 parts by weight with respect to 100 parts by weight of polylactic acid. If the content of the processing aid is less than 1 part by weight, the effect of improving the physical properties by the processing aid may be insignificant. If it exceeds 60 parts by weight, the workability may be deteriorated due to a decrease in melting efficiency.

The resin composition of the present invention may further include a filler. The filler as described above may be added for the purpose of increasing strength, improving workability, providing stability, and reducing raw material costs, depending on the use of the molded article of the resin composition of the present invention.

The specific kind of filler that can be used in the present invention is not particularly limited, and inorganic fillers such as calcium carbonate, talc, ocher, silica or alumina; Or a mixture of one or more kinds of organic fillers such as wood fillers (ex. Wood flour, wood chips), cork, kenyaf or pulp. In the present invention, in particular, a mixture of an organic filler and an inorganic filler, preferably a mixed filler of calcium carbonate and wood powder, may be used. If necessary, a lightweight inorganic type such as perlite may be used for the purpose of lightening the product and reducing raw material costs. Light weight organic fillers, such as a filler and an aerosol, can be used further. The filler as described above is excellent in compatibility with the polylactic acid and can be uniformly dispersed in the resin composition. In addition, since the filler is particularly excellent in affinity with the plasticizer and can suppress elution of the plasticizer, the content of the plasticizer in the composition can be set relatively high and a product having excellent flexibility can be produced. There is an advantage.

The content of the filler in the resin composition of the present invention may vary depending on the application, for example, 1,200 parts by weight or less, preferably 300 parts by weight to 1,000 parts by weight, more preferably based on 100 parts by weight of polylactic acid. Preferably it can be adjusted within the range of 500 parts by weight to 800 parts by weight. In the present invention, when the amount of the filler is too low, there is a possibility that the workability, the raw material cost reduction, the seating property and the strength increase effect may be insignificant. On the contrary, when the amount of the filler is excessively large, the bonding strength of other components such as resin is lowered, resulting in workability, for example, calendering workability. There is a risk of deterioration.

However, the content of the filler is only one example of the present invention. For example, when the resin composition for floor coverings of this invention is applied to the use which requires transparency like the surface layer of a decotile, the said filler may not be added to a resin composition. That is, in the present invention, in consideration of the application to which the sheet made of the resin composition (hereinafter referred to as a "polylactic acid sheet"), the desired strength, the seating property, or the raw material cost reduction effect, etc. The content of can be changed as appropriate.

In addition to the above components, the resin composition of the present invention may further include one or more additives such as, for example, antioxidants, UV stabilizers, foaming agents, crosslinking agents, or pigments, depending on the application applied.

The present invention also relates to a flooring comprising a sheet-like molded body of the resin composition for flooring according to the present invention.

The flooring material of this invention may be comprised including one or more sheet-like molded object of the resin composition for floor materials mentioned above, Preferably a calendering molded object. In the present invention, the term " sheet-shaped molded body " means a film- or sheet-shaped molded product produced by applying the resin composition of the present invention to various methods such as calendering, extrusion or pressing, and preferably a calendering method. In the present invention, the range of the sheet-shaped molded body includes a sheet or a film-shaped foam and a non-foamed body, and in some cases, may also include a molded body in which appropriate embossing is performed on all or part thereof. In addition, in this invention, the term "calendering molded object" means the sheet-like molded object manufactured by processing the resin composition of this invention by the calendering method.

Such a sheet-shaped molded article of the present invention is, for example, each layer (ex. Transparent layer, printed layer, interlayer layer, marble layer, base layer, elastic) constituting the existing polyvinyl chloride (PVC) -based flooring It may be applied to the flooring as one or more layers of the foam layer or easy layer, or optionally included as all the layers constituting the flooring.

In some cases, the flooring material of the present invention may further include a fiber layer or a fiber reinforced polymer layer (FRP), and in this case, the sheet-like molded body may be formed on the fiber layer or the fiber reinforced resin layer. It may be formed.

The fiber layer or the fiber-reinforced resin layer (hereinafter, sometimes referred to as "dimension stabilization layer") included in the flooring material may serve to secure dimensional stability.

The kind of the fibrous layer which can be used in the present invention is not particularly limited, and for example, glass fiber, carbon fiber, polyester fiber, polyamide fiber, polyurethane fiber, acrylic fiber, polyolefin fiber or cellulose fiber It may be a woven or nonwoven fabric including the above, and preferably, may be a woven or nonwoven fabric of glass fiber, but is not limited thereto. In the above, the woven fabric can be produced through a conventional weaving process using the fibers described above, and in the case of a nonwoven fabric, for example, by adding a water-soluble binder such as pulp and polyvinyl alcohol (PVA) to the fibers described above The sol can be prepared by applying to a conventional papermaking process.

In the present invention, the dimensionally stable layer may be a fiber reinforced resin layer. The term "fiber-reinforced resin layer" used in the present invention means a composite layer prepared by impregnating the above woven or nonwoven fabric with a resin, and curing or semi-curing the resin. In this case, the resin component impregnated in a woven or nonwoven fabric may be, for example, one or more types of polylactic acid, acrylic resin, polyvinyl chloride, urethane resin, melamine resin, phenol resin, epoxy resin, and polyester resin.

The flooring material of the present invention may include a sheet-like molded body formed on the above dimensional stability layer. In the present invention, the expressions "B formed on A", "B formed on the upper or lower portion of A", and "B formed on one surface of A" and the like, the surface of A when B is directly attached to the surface of A In the case where B is attached to the medium through an adhesive or an adhesive, and a separate layer between A and B is directly or interposed through the pressure-sensitive adhesive or adhesive may be used.

In the present invention, the sheet-like molded body is formed on one side or both sides of the fibrous layer or the fiber reinforced resin layer, for example, to constitute a surface layer or a back layer, or in some cases, a multilayer to constitute the surface layer or the back layer. It may be present in one or more layers of the structure.

In the present invention, for example, the surface layer may include one or more selected from the group consisting of a transparent layer and a print layer, the back layer is one or more selected from the group consisting of a marble layer, a base layer, an elastic foam layer and an easy layer. It may include.

Sheet-like molded article of the present invention is a transparent layer as described above; Printed layer; Marble layer, base layer; One or more of the elastic foam layer and the easy layer may be included in the flooring material. In this case, the content of the processing aid, the plasticizer, or the filler, which is contained in the resin composition which is the raw material of the sheet-like molded body, may be appropriately selected in consideration of the application purpose. Can be.

The flooring material of the present invention may be present in various forms by adopting the configuration as described above, for example, as shown in Figure 1, the flooring material 1 of the present invention, the fiber layer or fiber reinforced resin layer 11 A surface layer including a transparent layer 22 and a printing layer 21 is formed on the upper side, and an interlayer layer 31, a base layer or an elastic foam layer 32, and an easy layer 33 are formed on the lower side. The back layer may be formed.

In addition, the flooring material 2 of the present invention, as shown in the accompanying Figure 2, the surface layer including the transparent layer 22 and the printed layer 21 is formed on the top of the fibrous layer or the fiber-reinforced resin layer 11 It may have a configuration in which the elastic layer 34 is formed at the bottom.

In addition, the flooring according to the present invention may include a surface treatment layer 41 on top of the flooring disclosed in FIGS. 1 and 2, as shown in FIGS. 3 and 4.

In the present invention, the surface treatment layer 41 is to improve scratch resistance and abrasion resistance of the flooring material, for example, using a conventional means such as UV curable paint (ex. Urethane acrylate UV curable paint). Can be formed.

The flooring material 5 of the present invention also has a surface layer including a transparent layer 22 and a printing layer 21 formed on the top of the fiber layer or the fiber reinforced resin layer 11, as shown in FIG. The back layer including the base layer or the elastic foam layer 32 and the easy layer 33 may be formed.

The flooring material 6 of the present invention may also have a structure in which the transparent layer 22, the print layer 21, the base layer 32, and the easy layer 33 are sequentially formed as shown in FIG. The flooring material of the present invention may also have a form in which a surface treatment layer is formed on the marble layer or the base layer.

7 and 8 are cross-sectional views of the floorings 8 and 9 according to another aspect of the present invention, respectively, in which the surface treatment layer 41 is formed on the top of the floorings shown in FIGS. to be. The surface treatment layer 41 may be formed in the same manner as described above with reference to FIGS. 3 and 4.

The present invention also relates to a method for producing a flooring material comprising the step of producing a sheet-like molded body by processing the resin composition for flooring according to the present invention described above by a calendering method.

The resin composition for flooring of the present invention may be applied to various methods known in the art, such as injection molding, extrusion molding, press molding, or calendar molding, but may be preferably applied particularly to calendar molding as described above. . In the case of calendering molding, as compared with other manufacturing methods, it is possible to freely control the content of components such as plasticizers and fillers, so that the flooring or floor having excellent flexibility, impact resistance, mechanical strength, processability, seating property and melting efficiency Finishing materials can be provided, and raw material costs can be further reduced.

In the present invention, a method for producing a sheet-shaped molded article by applying a calendering method is not particularly limited, and for example, mixing each of the raw materials to produce a resin composition; A kneading step of uniformly gelling the mixed raw materials by heating and pressing under appropriate conditions; And it may be produced through the step of calendering molding to the final sheet shape.

The mixing and kneading step of the raw material, for example, may be performed using a liquid or powder raw material using a super mixer, an extruder, a kneader, two or three rolls and the like. In addition, in this step, for more efficient mixing, the blended raw material is kneaded at a predetermined temperature (ex. 120 ° C to 200 ° C) using a banbury mixer or the like, and the kneaded raw material is also subjected to a predetermined temperature (ex. The mixing and kneading process may be repeated in multiple stages, such as in the manner of primary and secondary mixing using two rolls or the like at 120 ° C. to 200 ° C.). At this time, the kind of the raw material constituting the resin composition, its blending ratio, and the like are not particularly limited, and are within the above ranges in consideration of the use (ex. Interlayer, transparent layer, foam layer, etc.) to which the sheet-shaped molded article is to be applied. Can be appropriately selected.

On the other hand, the method of manufacturing the sheet-shaped molded article by applying the mixed raw materials as described above to the calendering method is also not particularly limited, and can be manufactured using, for example, a conventional apparatus such as an inverted L four-roll roll calender. .

In addition, the above-described calendering processing conditions may be selected in consideration of the composition of the resin composition and the like, and may be controlled within a range of processing temperatures of, for example, 120 ° C to 200 ° C, preferably 130 ° C to 190 ° C. Can be. In processing the sheet, if the processing temperature is too low, the softening degree of the resin may be insufficient and the moldability may be deteriorated. If too high, the viscosity may be excessively lowered and the moldability may be deteriorated. In consideration of the composition and the like, it is preferable to appropriately control the processing temperature.

In the present invention, the polylactic acid-based sheet is manufactured by the above-described calendering process, and if necessary, laminating one or more polylactic acid-based sheets or polylactic acid-based sheets and dimensionally stable layers (fiber layers or fiber-reinforced resin layers). The process may be further carried out to produce flooring. In the present invention, in addition to the above-described process, if necessary, a process for producing a decorative layer through a known printing method such as digital photorealistic printing, gravure printing, screen printing, offset printing, rotary printing or flexographic printing, Foaming the prepared sheet-like molded article under appropriate conditions; Forming an embossed pattern on the sheet-like molded body; Alternatively, a process of forming a surface treatment layer using a UV curable paint or the like may be further performed.

In the present invention, flooring is constructed using polylactic acid, which can be produced from raw materials extracted from renewable plant resources. Accordingly, in the present invention, it is possible to solve the problem of supply and demand of raw materials due to exhaustion of fossil energy resources. In addition, the flooring material of the present invention does not discharge toxic substances at the time of manufacture, use, disposal or fire, and can be easily disposed. In addition, the present invention can provide a flooring material having excellent melt efficiency, melt strength, viscosity characteristics, tensile strength, flexural strength, impact strength, dimensional stability, and abrasion resistance, and in particular, a resin composition which can be effectively applied to a calendering method. can do.

1 to 8 are cross-sectional views showing various examples of the flooring material of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples according to the present invention and comparative examples not according to the present invention, but the scope of the present invention is not limited to the following examples.

Example 1.

Processing aid, which is an emulsion polymer containing 25 parts by weight of acetyltributyl citrate (ATBC) as an environmentally friendly plasticizer, and a polymer having methyl methacrylate as a polymerization unit in 100 parts by weight of polylactic acid (PLA) (weight average molecular weight: about 750 10 parts by weight of PA 828, LG Chem (manufactured by LG Chem), 600 parts by weight of calcium carbonate as filler, 2 parts by weight of stearic acid as lubricant, and 3 parts by weight of other additives are uniformly mixed to obtain a resin composition. Prepared. Specifically, each of the above components is first kneaded using an extruder, kneaded at about 150 ° C. to 160 ° C. with a short-barrier mixer, and then, first and secondly, using two rolls having a temperature of about 140 ° C. to 160 ° C. Tea was mixed. Thereafter, the prepared raw material was calendered at a temperature of about 140 ° C. to 160 ° C. to prepare a sheet-like molded body.

Comparative Example 1.

Resin composition in the same manner as in Example 1, except that ternary copolymers of ethylene, propylene and maleic anhydride (CAS # 31069-12-2, AC 950, Honeywell specialty Chemical Co.) were used as processing aids. Was prepared. Thereafter, the composition was applied to the calendering process in the same manner as in Example 1, but smooth processing was not performed due to low melt strength or the like. In addition, as shown below, it was confirmed that physical properties such as tensile strength, flexural strength, impact strength, dimensional stability, and abrasion resistance of the formed molded article were also significantly reduced.

For the molded articles prepared in Examples and Comparative Examples, tensile strength, flexural strength, impact strength, dimensional stability and wear resistance were measured according to standard specifications, and the results are summarized in Table 1 below.

Example 1 Comparative Example 1 How to measure Remarks The tensile strength
(kg / cm ² ) 1 time 58.81 24.60 ISO9001
-
Episode 2 69.70 30.28 Flexural strength
(kg / mm ² ) 1 time 0.637 0.312 ISO9001
-
Episode 2 0.929 0.456 Impact strength
(J / m) 1 time 18.696 8.218 ISO9001
-
Episode 2 23.040 9.878 Dimensional stability
(%) 1 time -0.05 -1.62 KS M 3802
-
Episode 2 -0.07 -2.02 Abrasion Resistance (g) 1.32 3.86 KS M3802 H-22
1,000
1,000 g

As can be seen from the results of Table 1 above, in the case of Example 1 using the processing aid according to the present invention, tensile strength and bending superior to 2 times or more as compared to Comparative Example 1 using the conventional general-purpose processing aid It showed strength, impact strength and abrasion resistance, and showed excellent effects from 28 to 32 times in terms of dimensional stability.

1, 2, 3, 4, 5, 6, 8, 9: Flooring
11: dimensionally stable layer 21: printing layer
22: transparent layer 31: interlayer
32: elastic foam layer or base layer 33: easy layer
34: elastic layer 41: surface treatment layer

Claims (19)

100 parts by weight of polylactic acid; 5 to 60 parts by weight of plasticizer; A resin composition for flooring, comprising from 1 part by weight to 60 parts by weight of a processing aid comprising 0.001 part by weight to 30 parts by weight of a lubricant and a copolymer comprising methyl methacrylate as a polymerization unit. The polymerized unit of claim 1, wherein the polylactic acid comprises at least one polymerized unit selected from the group consisting of L-lactic acid, D-lactic acid, L, D-lactic acid, L-lactide, D-lactide and L, D-lactide The resin composition for flooring which is a polymer containing. The plasticizer according to claim 1, wherein the plasticizer is a phthalate compound, citric acid compound, fatty acid ester, polyalkylene glycol, glycerol ester, vegetable oil, modified vegetable oil, allyl phosphate ester, dialkyl ether diester, tricarboxylic acid ester, epoxidized oil Resin composition for flooring, which is at least one selected from the group consisting of epoxidized esters, polyesters, polyglycol diesters, allyl ether diesters, aliphatic diesters, alkylether monoesters and dicarboxylic acid esters. The resin composition for flooring according to claim 1, wherein the lubricant is stearic acid, a stearic acid metal salt, a synthetic wax, a hydrocarbon, or a silicone compound. The resin composition for flooring according to claim 1, wherein the processing aid comprises a ternary copolymer containing methyl methacrylate as the polymerized unit. The resin composition for flooring according to claim 1, wherein the copolymer further comprises a monomer represented by the following Chemical Formula 2 as a polymerization unit:
(2)

In Formula 2, R represents hydrogen or an alkyl group, and R ₁ represents an alkyl group having 1 to 20 carbon atoms, except that R and R ₁ are methyl groups at the same time. The monomer represented by the formula (2) is methyl acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, The resin composition for flooring materials which is 2-ethylhexyl (meth) acrylate or cyclohexyl (meth) acrylate. The resin composition for flooring according to claim 1, wherein the copolymer further comprises a monomer represented by the following Chemical Formula 3 or 4 in a polymerized unit:
(3)

[Chemical Formula 4]

In Formulas 3 and 4, R represents hydrogen or alkyl, A represents alkylene, n represents an integer of 1 to 5, R ₂ is an aryl group or -C (unsubstituted or substituted with an alkenyl group) = O) -OR ₃ , wherein R ₃ represents an aryl group or an arylalkyl group. 9. A compound according to claim 8, wherein R is hydrogen or methyl, A is straight or branched chain alkylene having 1 to 6 carbon atoms, R ₂ is a phenyl group unsubstituted or substituted with a vinyl group, or -C (= 0) -OR ₃ In the above, R ₃ is a resin composition for flooring is an aryl group having 6 to 12 carbon atoms or an arylalkyl group having 8 to 14 carbon atoms. The resin composition for flooring according to claim 1, wherein the processing aid has a weight average molecular weight of 500,000 to 8 million. The resin composition for flooring materials of Claim 1 containing an emulsion polymer containing methyl methacrylate as a polymerization unit. The resin composition for flooring materials of Claim 11 whose processing aid is a relative viscosity of 4.0-12.0. The resin composition for floor coverings of Claim 1 which further contains 1,200 weight part or less of fillers with respect to 100 weight part of polylactic acid. The resin composition for flooring according to claim 13, wherein the filler is a mixed filler of an organic filler and an inorganic filler. Flooring containing the sheet-like molded object of the resin composition of Claim 1. The flooring material according to claim 15, wherein the sheet-like molded body is a calendering molded body. 16. The flooring according to claim 15, further comprising a fibrous layer or a fiber reinforced resin layer, wherein said sheet-like molded body is formed on said fibrous layer or fiber reinforced resin layer. A method for producing a flooring material comprising the step of processing the resin composition according to claim 1 by a calendering method to produce a sheet-like molded body. 19. The method of claim 18, wherein the calendering method is carried out at 120 ° C to 200 ° C.

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