Patent Application
20130052900
The present invention relates to a recyclable, environmentally friendly coated yarn, a preparation method thereof, a fabric thereof, and a flame retardant coating composition used therefor.
A polyvinyl chloride (PVC) coated yarn is prepared by extrusion coating a PVC resin on a polyester yarn. Since a PVC yarn has excellent elasticity, anti-wrinkle property, resilience, antibiosis and coloring property, it has been widely used in the preparation of a blind, wall paper, a flooring material, household items, decorations, electronics, furniture, etc.
A PVC coated yarn is prepared by coating a PVC resin on a high-tenacity polyethylene terephthalate (PET) yarn at a coating rate of 300 to 1100 m/min in an extrusion coating machine to impart to the PET yarn such properties as flame retardancy, antibiosis, and others.
Korean Patent Laid-open Publication No. 2005-79896 discloses a method for preparing a fabric by coating a glass fiber or a polyester fiber with a coating composition comprising a PVC resin, a plasticizer and a flame retardant.
Although such a PVC coated yarn has excellent flame retardancy, antibiosis, tensile strength and elongation, it involves a problem that once defective products are produced during the extrusion coating, warping, or weaving process, they cannot be recycled but have to be disposed since the PVC coating layer is not readily removed from the polyester yarn. Moreover, when a PVC coated fiber is burned, chlorine release from PVC may react with the plasticizer, e.g., a phthalate-based compound, contained in the PVC coating layer, thereby generating toxic pollutants. Such an environmentally hazardous fiber product must be disfavored by consumers since it may threaten their health.
Therefore, there is a need for developing an environmentally friendly yarn having improved flame retardancy and antibiosis.
Accordingly, it is an object of the present invention to provide an environmentally friendly coated yarn having improved flame retardancy.
It is another object of the present invention to provide a method for preparing an environmentally friendly coated yarn.
It is a further object of the present invention to provide a coating composition used in the preparation of an environmentally friendly coated yarn.
It is a still further object of the present invention to provide a fabric woven from a coated yarn.
In accordance with one aspect of the present invention, there is provided a coated yarn composed of a core yarn comprising a first polyolefin resin and a coating layer covering the core yarn, wherein the coating layer comprises a second polyolefin resin and a flame retardant, and the first polyolefin resin and the second polyolefin resin are each independently selected from the group consisting of a polyethylene resin, a polyethylene copolymer resin, a polypropylene rein, a polypropylene copolymer resin and a blend resin thereof.
In accordance with another aspect of the present invention, there is provided a method for preparing a coated yarn, comprising the steps of: a) preparing a core yarn comprising a first polyolefin resin; b) preparing a coating composition comprising a second polyolefin resin and a flame retardant; and c) coating the core yarn with the coating composition to obtain the coated yarn, wherein the first polyolefin resin and the second polyolefin resin are each independently selected from the group consisting of a polyethylene resin, a polyethylene copolymer resin, a polypropylene resin, a polypropylene copolymer resin, and a blend resin thereof.
In accordance with a further aspect of the present invention, there is provided a coating composition for preparing a coated yarn, wherein the coating composition comprises a polymer selected from the group consisting of a polypropylene resin, a polypropylene copolymer resin, and a blend resin thereof; and a flame retardant selected from the group consisting of an organic phosphorus-based flame retardant, an inorganic flame retardant, and a mixture thereof.
In accordance with a still further aspect of the present invention, there is provided a fabric woven from the coated yarn.
Since both of the core yarn and the coating layer of the coated yarn according to the present invention are made of polyolefin resins, the coated yarn can readily be recycled and re-extruded to produce a coreless yarn useful as a flooring material or other industrial materials. Moreover, the inventive coated yarn solves the problem of poor flame retardancy of conventional non-PVC coated yarn so that a fabric woven made from the inventive coated yarn is useful in the preparation of a blind, a flooring material, wall paper, household items and other interior elements.
The above and other objects and features of the present invention will become apparent from the following description of the invention, when taken in conjunction with the accompanying drawing,
As shown in
The coated yarn can be recycled and re-extruded to produce a coreless yarn (30), which can be used in the preparation of a flooring material or other industrial materials.
The core yarn (10) may have a diameter of 30 to 1500 denier, more preferably 150 to 600 denier, and the coating layer (20) has a thickness of 120 to 1000 μm, more preferably 100 to 700 μm. The coated yarn may have a diameter of 300 to 4000 denier, more preferably 490 to 3200 denier.
The coating layer (20) is made from a coating composition comprising a polyolefin resin, a flame retardant and other additives, each of which is described in detail below.
The polyolefin resin used in the present invention may be a polyethylene (PE) resin, a polyethylene copolymer resin, a polypropylene (PP) resin, a polypropylene copolymer resin, or a blend resin thereof.
More specifically, the polyolefin resin may be a low-density polyethylene (LDPE) resin, a linear low-density polyethylene (LLDPE) resin, a high-density polyethylene (HDPE) resin, an ethylene-vinyl acetate (EVA) resin, a polypropylene resin, a polypropylene block copolymer resin, a polypropylene random copolymer resin, a polypropylene elastomer resin, or a blend resin thereof.
Examples of the PE resin may include PE resins commercially available from LG Chem, Ltd. such as LUTENE CC0550BK, LUTENE XL2700BK, LUTENE XL2808BK, LUTENE XL8080NT, LUTENE XL8080TR and LUTENE XL8080UC.
Examples of the LDPE resin may include LDPE resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as 512W, 531G, 530G, 431G and 432G; and those commercially available from Honam Petrochemical Corporation such as XJ700, XJ710, XJ800, XL610, XL505, XL600, XL700, XL710 and X8855.
Examples of the LLDPE resin may include LLDPE resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as 4141W, 4222F, 4220U, 4141C and 4220S; and those commercially available from Honam Petrochemical Corporation such as UF316, UF313, UF315, UF317 and UF414.
Examples of the HDPE resin may include HDPE resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as B230E, F120U, P110A, Y910A, B221B, F120A, F123A, B220A, B230A and P110PT12; and those commercially available from Honam Petrochemical Corporation such as CJ680, CJ681, 2200J, 2210J, 2600J, 3510J, 2700J, 3520J, 5220B, 5220BN, 6300BN, 8301B, 5200B, 5500B, 6010BP, 6200B, 4000B, 2600F, 5000S, 5000ST, 5100ST, 5500SF, 7000F, 7000FM, 7700F and 5305E.
Examples of the PP resin may include PP resins commercially available from LG Chem, Ltd. such as SEETEC H1500, SEETEC H1501, SEETEC M1315, SEETEC M1400, SEETEC M1425, SEETEC M1500, SEETEC M1600, SEETEC M1700, SEETEC R1560, SEETEC R1610, SEETEC R3400, SEETEC H5300, SEETEC H7411, SEETEC H7500, SEETEC H7511, SEETEC H7525, SEETEC H7600, SEETEC H7630, SEETEC H7700, SEETEC R3420, SEETEC R7700, SEETEC R3410, SEETEC R3450 and SEETEC T3410; homo-PP resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as HF400, HF409, HS120, HF429, HJ730L, HY301, HY311, HJ700, HS301, HY300, HJ400, HY110, HJ730, HI831 and HJ500; and homo-PP resins commercially available from Honam Petrochemical Corporation such as H1500, H140, H1501, H1600, J-150, J-160, J-170 and J-150HC.
Examples of the PP block copolymer resin may include PP block copolymer resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as BJ501, BI830, BJ100, B1300, B1530, BB110, BJ500, BJ730, BJ700, BJ520, BJ522, BJ600, BI518, BI970, BJ300, BJ800, I310, BI740, BI452, BI451 and BI750.
Examples of the PP random copolymer resin may include PP random copolymer resins commercially available from Samsung Total Petrochemicals Co., Ltd. such as RB200, RS401, RJ700, RJ560, RF401 and RF402; and those commercially available from Honam Petrochemical Corporation such as SEP-740, SEP-550, SB-530, B-220D, B-320, SEP-750, SFR-171H, FR-170, FR-160U, FR-160, FR-150H, Y-130, Y-120A, Y-120, SY-140, SY-130, H5300, SB-550A, SB-520, B-310, B-122, SB-520Y, SB-520Y, B-122, B-310, SB-520, SB-550A, H5300, SY-130, SY-140, Y-120, Y-120A, Y-130, FR-150H, FR-160, FR-160U, FR-170, SFR-171H, B-320, B-220D, SB-530, SEP-550, SEP-740, SEP-750, M9600, DL-670M, DL-270A, SFI-740P, SFI-151, FI-155S, SFI-740A, H4540, H4500, SFC-851, SFC-750R, SFC-750, FC-150U, FC-150B, SFC-650BT, SFC-550, H3401, H3400, SFO-130BA-1, SFO-130E, SFO-130A, 5500EF, PH-6000, 7000FT3, V-451, V-411, V-235, V-225, G-153, G-152, G-151, E-373D, E-362SH, E-362S, E-362J, RX-20000, RX-12000, RX-10000, B-352, B-162, HCA-352T, HCA-352S, AE-352S, A-354S, A-354, A-353, A-352 and A-351.
Examples of the PP elastomer resin may include a PP elastomer resins having an ethylene content of 10 to 30%, more specifically PP elastomer resins commercially available from Exxon Mobil Corporation such as Vistamaxx 3000, Vistamaxx 3020FL, 3980FL, Vistamaxx 6102, Vistamaxx 6102FL, Vistamaxx 6202, Vistamaxx 6202FL; those commercially available from Eastman Corporate such as Ecdel elastomer 9965, Ecdel elastomer 9966, Ecdel elastomer 9967, Neostar elastomer FN005, Neostar elastomer FN006 and Neostar elastomer FN007; and those commercially available from Kuraray Co., Ltd. such as SEP 1001, SEP 1020, SEPS 2002, SEPS 2004, SEPS 2005, SEPS 2006, SEPS 2007, SEPS 2063, SEPS 2104, SEEPS 4033, SEEPS 4044, SEEPS 4055, SEEPS 4077, SEEPS 4099, SEBS 8004, SEBS 8006, SEBS 8007, SEBS 8076 and SEBS 8104.
Examples of the EVA resin may include EVA copolymer resins commercially available from LG Chem, Ltd. such as LC100, LC170, LC180, LC370 and LC670.
The coating composition of the present invention may comprise a mixture of two or more polyolefin resins.
The coating composition preferably comprises the polyolefin resin in an amount of 30 to 90 wt %, more preferably 55 to 80 wt %, based on the weight of the coating composition.
Preferably, the polyolefin resin comprises a polypropylene resin, a polypropylene block copolymer resin, a polypropylene random copolymer resin, a polypropylene elastomer resin, an EVA resin or a blend resin thereof, more preferably, a polypropylene random copolymer resin, a polypropylene elastomer resin or an EVA resin.
Most preferably, the coating composition comprises a polypropylene random copolymer resin in an amount of 50 to 70 wt %, and a polypropylene elastomer resin or an EVA resin in an amount of 5 to 20 wt %, based on the weight of the coating composition.
The flame retardant used in present invention may be a halogen-, phosphorous- or nitrogen-based flame retardant, or an inorganic flame retardant such as a metal oxide and a metal hydroxide.
Examples of the halogen-based flame retardant may include decabromodiphenyl oxide (DBDPO), decabromodiphenyl ethane (DBDPE), hexabromocyclodecane (HBCD), 1,2,5,6,9,10-hexabromocyclododecane (HBCD), tetrabromobisphenol-A (TBBA), and tetrabromobisphenol-A bis(2,3-dibromopropyl ether) (BDDP).
Examples of the phosphorous-based flame retardant may include melamine phosphate (MP), melamine polyphosphate (MPP), ammonium phosphate, ammonium polyphosphate (APP), red phosphorus, tris(2-chloroethyl)phosphate (TCEP), tris(1-chloro-2-propyl)phosphate (TCPP), isopropylphenyl diphenyl phosphate (IPPP), triphenyl phosphate (TPP), triethyl phosphate (TEP), resorcinol diphosphate (RDP), tricresyl phosphate (TCP), dimethyl methyl phosphonate, diethyl ethyl phosphonate, dimethyl propyl phosphonate, diethyl N,N-bis(2-hydroxyethyl)aminomethyl phosphonate, phosphonic acid, methyl(5-methyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl) methyl ester P,P′-dioxide, phosphonic acid, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), poly(1,3-phenylenemethylphosphonate), hexaphenoxytricyclophosphazene, phosphophenanthrene, and a commercial phosphorous-based flame retardant available from Clariant Corporation such as Exolite OP 930, Exolite OP 1230, Exolite OP 550, Exolite OP 560, Exolite OP 1312, Exolite OP 935, Exolite OP 1314 and Exolite OP 1240.
Examples of the nitrogen-based flame retardant may include melamine phosphate (MP), nitrilo tris(methylphosphoneamide acid), and melamine cyanurate.
Examples of the inorganic flame retardant may include magnesium dihydroxide (MDH), aluminum trihydroxide (ATH), zinc borate, graphite, and antimony trioxide.
The present invention may use one or more flame retardants listed above.
In order to improve the environmentally friendly property as well as the flame retardancy, the flame retardant may preferably be a phosphorus-based flame retardant or an inorganic flame retardant.
For example, the flame retardant may preferably be melamine phosphate, melamine polyphosphate, ammonium phosphate, isopropylphenyl diphenyl phosphate (IPPP), triphenyl phosphate (TPP), triethyl phosphate (TEP), resorcinol diphosphate (RDP), tricresyl phosphate (TCP), magnesium dihydroxide (MDH), aluminum trihydroxide, zinc borate (ATH) and antimony trioxide.
These non halogen-based flame retardants can be recycled and reduce toxic pollutants when burned.
Preferably, the coating composition comprises the flame retardant in an amount of 5 to 60 wt % based on the weight of the coating composition. When the content falls within the above range, the limited oxygen index (LOI) can be more improved and deterioration of the coating property resulting from excess use of the flame retardant can be prevented.
More preferably, the coating composition comprises the flame retardant in an amount of 15 to 50 wt %, most preferably 20 to 40 wt %, based on the weight of the coating composition. When the content falls within the above range, the coating property, the processability, the elongation and the flame retardancy of the coating composition can be further improved.
The coating composition of the present invention may further comprise other additives such as lubricants, UV stabilizers, antimicrobials, an anti-drip burn agent and other functional fillers in order to enhance the properties thereof.
The coating composition may comprise the additives in an amount of 0.01 to 10 wt % based on the weight of the coating composition.
Preferably, the coating composition may comprise a lubricant, e.g., a stearate lubricant, in an amount of 0.01 to 3 wt % based on the weight of the coating composition in order to improve its miscibility and dispersibility.
The coating composition may comprise an anti-drip burn agent, e.g., fluorine-based anti-drip burn agent, in an amount of 0.01 to 2 wt % based on the weight of the coating composition in order to improve the flame retardancy so that it prevents flames from spreading on fires.
The UV stabilizer may preferably be a benzophenone-based compound or titanium oxide. The other functional fillers may be calcium carbonate, talc-based compound, silica, glass fiber, etc.
The core yarn of the inventive coated yarn preferably has a diameter of 30 to 1500 denier and a tensile strength of at least 0.5 g/denier, more preferably, at least 3 g/denier.
The core yarn comprises a polyolefin resin, which may be selected from those employed in the coating composition as listed above. The polyolefin resin of the core yarn may be the same as or different from the polyolefin resin of the coating layer.
In order to prepare a final fabric product from the coated yarn, the coated yarn is subjected to warping, weaving, inspection, tenter and packaging processes, which requires suitable properties of the coating composition or the coated yarn.
The coating composition of the present invention preferably has a hardness according to ASTM D2240 of 40 to 70 (Shore D). When the hardness falls within the above range, the coating composition can be prevented from scattering dust during a following weaving process.
The inventive coating composition preferably has a moisture content of 0.2% or less under 80% R.H.; a tensile strength according to ASTM D638 of 200 to 600 kgf/cm2, more preferably 400 to 600 kgf/cm2; an elongation according to ASTM D638 of 300 to 1000%, more preferably 500 to 600 kgf/cm2; a limited oxygen index according to ISO 5659-2 of at least 25%, more preferably at least 30%; a UV light fastness according to ISO 105 B02:2000 of grade 6 to 8; a thermal stability of 100 to 120 min when measured at least 180° C.; and a smoke density according to ISO 5659-2 of at most 200 ds, more preferably at most 100ds.
Further, the coated yarn of the present invention preferably has a tensile strength according to ASTM D2256/D2256M of at least 3 g/denier; and an elongation according to ASTM D2256/D2256M of 5 to 1000%, more preferably 100 to 800%. When the tensile strength and the elongation fall within the above ranges, the coated yarn is more suitable for industrial uses.
Further, the fabric of the present invention preferably has a light fastness according to ISO 105 B02:2000 of grade 7 to 8; a limited oxygen index according to ISO 5659-2 of at least 27%; and a smoke density according to ISO 5659-2 of at most 200 ds.
As stated above, the inventive coated yarn composed of a polyolefin core yarn and a polyolefin coating layer so that the coated yarn can be recycled and re-extruded to produce a coreless yarn. A coreless yarn means a yarn composed of a coating composition only, without a core yarn (see
Especially, the recycling can be conducted with any defective products of the coated yarn such as a defective compound, a defective coated yarn and a defective fabric, which have been generated during the processes of extrusion, coating, warping, weaving, inspection, tenter and packaging.
Further, compared with a halogen-based coated yarn such as a PVC coated yarn, the polyolefin coated yarn of the present invention can eliminate or curtail such harmful materials as phthalate plasticizers and dioxin, toxic gases such as chlorine gas, and other harmful elements causing industrial pollution. Accordingly, the coated yarn of the present invention can be applied for an interior material such as a blind, a flooring material, wall paper, an exterior material for display cupboard and awning, an interior/exterior material for vehicles, and other fiber products with improved properties in terms of flame retardancy as well as environmentally friendly property.
Hereinafter, embodiments of the preparation methods of the coating composition, the coated yarn and the fabric of the present invention are described.
In order to prepare a coating composition, one or more feedstock polymer resins, e.g., a polyethylene resin, a polyethylene copolymer resin, a polypropylene resin, a polypropylene copolymer resin, or a blend resin thereof, are added to a mixer in an amount of 20 to 90 wt % based on the total weight of the coating composition and then mixed at room temperature for 1 to 10 min.
A flame retardant is added to the resins in an amount of 5 to 60 wt % based on the total weight of the coating composition and then admixed for 3 to 10 min so as to raise the limited oxygen index of the final fabric product up to 25% or more.
Further, such functional additives as lubricants, pigments, UV stabilizers, antimicrobials and other fillers may be added to the resulting mixture in order to improve its properties. The functional additives may be added during extrusion compounding in the form of a master batch. If the amount of the additives is less than 5 wt % of the total weight of the coating composition, the additives can be added during the mixing process of the feedstock polymer resins.
After the admixing process is completed, the coating composition is subjected to an extrusion compounding process.
The extrusion compounding is preferably conducted with a twin-screw compounding extruder in order to disperse the coating composition sufficiently. Preferably, an extruder having a temperature range of 100 to 220° C. equipped with a cylinder having a length of at least 1 m is used.
The coating composition is introduced into the extruder through a hopper and extruded at a temperature of 100 to 220° C.
As stated above, such additives as lubricants, pigments, UV stabilizers, antimicrobials and other fillers may be added to the extruder in the form of a master batch, or may be added to the coating composition in step a) stated above. Since flame retardants are sensitive to moisture and gases, an extruder equipped with a gas venting system is preferred for an environmentally friendly process.
For the core yarn, a polyolefin yarn, e.g., having a diameter of 30 to 1500 denier and a tensile strength of at least 3 g/denier, is prepared.
The polyolefin yarn is introduced to an extrusion coating machine in the warp or weft direction. While the polyolefin yarn passes through the die nozzle of the extruder, the coating composition prepared in step b) is coated on the polyolefin yarn in a thickness of 300 to 350 μm, followed by winding thereof.
Preferably, the extrusion coating process is conducted with a single-screw extrusion coating machine at a coating temperature of 100 to 220° C., more preferably 130 to 190° C. The coating temperature may be adjusted in light of the melting temperature of the polyolefin yarn. The higher the coating temperature is, the more frequently yarn breakage occurs. The coating rate is preferably 300 to 1200 m/min.
The coated yarn obtained in step c) is further subjected to the processes of warping, weaving and tenter to obtain a fabric.
The warping process means a process wherein a warp yarn is taken up around a beam of the warping machine at a specific number, length and interval, in light of the length, width and density of a desired fabric.
After the warping process, the warp yarns are weaved with coated yarns serving as weft yarns. The weaving process means a process wherein the warp and weft yarns are interlaced with each other perpendicularly to form a fabric. The fabric may be weaved to have a design or pattern thereon.
Finally, the fabric is subjected to a tenter process, wherein the fabric is stretched with a tenter machine and then the temperature is raised to a range from 120 to 250° C., while both of the longitudinal ends of the fabric are fixed by pins or clips, so that the fabric has a uniform width without shrinkage.
The following Examples are intended to further illustrate the present invention without limiting its scope.
Polymers and additives were mixed together, and the mixture thus obtained was subjected to a compounding process at a temperature of 190 to 230° C. in a twin extruder and then dried at 100° C. for 12 hours to obtain a coating composition.
The polymers and additives used in each of the examples and the contents thereof are as follows:
The coating composition obtained in Example 1 was introduced into a single-screw extrusion coating machine through a hopper.
The coating composition was coated onto a polypropylene yarn (300 denier, Dong Sun Synthetic Fiber Co., Ltd.), which passed through the nozzle in a single-extrusion coating machine, in an average coating thickness of 400 μm and at a rate of 600 m/min at 160° C. to thereby produce a coated yarn.
The coated yarn obtained in Example 2 was taken up as a warp yarn, and then the coated yarn was subjected to warping and weaving processes so that a fabric in the form of a net with a width of 1.6 m was prepared. Then, the net was subjected to a tenter process at 170° C. to produce a final fabric.
The properties of the coating composition, the coated yarn and the final fabric obtained from the Examples 1 to 3 were evaluated as follows.
The hardness of the coating compositions was measured according to ASTM D2240 (Shore D).
The tensile strength of the coating compositions was measured according to ASTM D638.
The limited oxygen index of the coating compositions was measured according to ASTM D2863 (flame mode), which was conducted by passing a mixture of oxygen and nitrogen over a burning specimen, and reducing the oxygen level until a critical level is reached.
The elongation of the coating compositions was measured according to ASTM D638.
A sample was prepared into a 5 cm×10 cm×0.5 cm specimen and placed in a oven at 180° C. Then, the change in the color of the sample was observed at an interval of 10 min for 90 min by using a color-difference meter.
As shown in Table 1, the coated yarns of the present invention exhibited good properties in terms of hardness, tensile strength and elongation. Further, the LOIs were sufficient to exhibit good flame retardancy and the thermal stabilities were enough to certify the color fastness suitable for exterior materials.
The tensile strength of the coated yarns was measured according to ASTM D2256/D2256M.
The elongation of the coated yarns was measured according to ASTM D2256/D2256M.
As shown in Table 2, the tensile strength and the elongation of the coated yarns of the present invention are suitable for weaving.
The color fastness to light of the fabrics was measured according to ISO 105 B02: 2000.
The limited oxygen index of the fabrics was measured according to ISO 5659-2 (flame mode).
The smoke density of the fabrics was measured according to ISO 5659-2.
As shown in Table 3, the fabric according to the present invention had a color fastnesses of the highest grade 8, which is suitable for exterior materials. Further, the LOIs were sufficient to exhibit good flame retardancy, and the smoke densities complied with the domestic and foreign standards for flame retardants, e.g., Korean or Australian standards.
While the invention has been described with respect to the above specific embodiments, it should be recognized that various modifications and changes may be made to the invention by those skilled in the art which also fall within the scope of the invention as defined by the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2011-0085269 | Aug 2011 | KR | national |
