KR100375876B1 - Polyolefin Type Resin Composition Used in Coating Cloth and Coating Film Comprising Such Resin Composition - Google Patents

Abstract

The present invention (i) alpha olefin is formed of one of hexene and metallocene, 0.1 to 30 parts by weight of ethylene-alpha-olefin copolymer resin having a melt index of 1.0 to 20.0, the density of 0.865 to 0.935; (ii) 0.1 to 30 parts by weight of low density polyethylene resin having a melt index of 1.5 to 20.0 and a density of 0.900 to 0.938; (iii) 0.1 to 39 parts by weight of ethylene vinyl acetate copolymer resin having 5 parts by weight or more of vinyl acetate, having a melt resin of 1,0 to 20.0 and a density of 0.910 to 0.940; And (iv) at least one selected from clay talc, talc, barium sulfate, alumina and zeolite, mixed with each other, and 0.1 to 30 parts by weight of an inorganic filler having a particle diameter of 0.5 to 30 μm. It provides a resin composition. The polyolefin-based resin composition was developed as an economical material that can replace PVC, which causes environmental pollution problems caused by dioxin, and in particular, the polyester coated fiber coated with the resin composition can be used as a bag fabric and various industrial coating materials. It can be effective.

Description

Polyolefin-based resin composition for fiber coating and coating film prepared using the same {Polyolefin Type Resin Composition Used in Coating Cloth and Coating Film Comprising Such Resin Composition}

The present invention is an extrusion-lamination, in order to develop a new economical coating material that does not generate fiber processing and environmental pollutants such as easy processing, adhesiveness, flexibility and elasticity for sewing and natural fibers and synthetic fibers used as the fabric of bags The present invention relates to a polyolefin-based resin composition which can be coated on fibers using extrusion-coating and other coating methods, a film made of the resin composition, and a method of coating the film on the fibers.

In the past, it was very common to use PVC resin for waterproof coating of synthetic fiber and natural fiber. In particular, when PVC resin was coated using polyester synthetic fiber and extrusion coating or knife coating method, the texture of the fiber was well expressed and it was spotlighted as a suitable and economical material. However, PVC resin coating products, which were used to impart waterproofing to synthetic fibers used as fabrics for bags, caused dioxin, which is very harmful to the human body when incinerated, causing environmental pollution problems. In view of this, as a substitute material, a coating product composed of a polyolefin-based resin composition, which is not harmful to the human body at all, is more economical, and has excellent chemical stability, waterproofness, and moldability.

However, although these products are economical and practical, they have been limited mainly to applications such as paper coating and plastic coating because they are too stiff and inflexible. In addition, since the polyolefin-based resin has a weak polarity due to its chemical structure, when coated on a substrate such as polyester fiber or metal, which is mainly used as a fabric of bags, adhesive strength is reduced, and therefore, extrusion coating is required at high temperature. Since the coating must be coated at a pressure of 150g / m ² or more, there is a problem that the hardness of the coating fabric itself becomes high and becomes very stiff. So in an effort to improve adhesion, Japan's JPKokai No. In 57-200438, examples of using a halogen-substituted polyolefin resin and an acrylic resin are known. In Japanese Patent Laid-Open No. 59-27968, digestion 62-149735, and Pyeong 4-132783, polyolefins and acrylic monomers substituted with chlorine are known. And copolymers of polyesters having a number average molecular weight of 500 to 3000 and an isocyanate compound are known. In Japanese Patent Laid-Open No. 59-27968, No. 62-149734 and No. 4-132783, chlorine is substituted. The use of a mixture of a polyolefin resin, an acrylic monomer and a chlorine-substituted polydiene and an isocyanate compound is known, but in the known data, about 35% by weight of chlorine atoms are contained, resulting in phase separation of the mixture. Uniform mixing becomes difficult, adhesion, chemical resistance, water resistance and weather resistance There is a problem in that the deterioration of the properties, such as the coating property due to phase separation, the chlorine-based element or isocyanate is contained, which generates harmful environmental pollutants.

In addition, when the polyolefin resin composition is coated on a fiber fabric, the coated fabric must be folded during sewing, but the workability is significantly reduced during sewing, particularly the properties of the coated fiber itself, that is, flexibility and softness. And elasticity were weak.

Under these circumstances, the present inventors have intensively researched to solve the above-mentioned conventional problems. As a result, in order to improve flexibility, softness and elasticity for smooth sewing processability, the present inventors have a low density and ethylene-alpha-olefin copolymer resin, which is a polyolefin resin.

Mainly made of polyethylene resin, and mixed with ethylene vinyl acetate resin, alpha-olefin copolymer resin and elastomer, it is possible to maintain the texture of economical and general fibers as it is, and to prepare a polyolefin resin composition for fiber coating having excellent sewing processability. It became.

In addition, eco-friendly polyolefin which reduces the cost of products by using a large amount of inorganic fillers, provides flexibility by solving stiffness, and reduces heat consumption by reducing the amount of heat consumed by the amount of inorganic fillers contained in incineration by fire. The resin composition was developed. In addition, when coating with fibers and extrusion coating and extrusion dry lamination method, while maintaining the texture of the fiber as it is, economical, sewing workability is advantageous. Also, it provides waterproof function and antistatic function to prevent dust or foreign matters from working on the finished product, and it is possible to prevent and prevent damage caused by fire by imparting flame retardant function, and to prevent finished product by providing anti-broking function. During the work, the fabric wound on the roll is released and used.Blocking that can occur during this process prevents the fabric from sticking to each other and causes trouble in the work, and also gives slip function to the surface of the coated fabric. The present invention was completed by allowing the user to feel a smooth texture.

After all, the main object of the present invention is to provide a fiber coating polyolefin resin composition for imparting a waterproof function, antistatic function, flame retardant function, anti-blocking function, slip function, adhesiveness, flexibility and elasticity to the fiber.

Another object of the present invention is to provide a film for coating prepared by melt mixing the polyolefin resin composition.

1 is a view showing a two-ply extrusion lamination apparatus for coating a polyolefin resin composition of the present invention on fibers.

2 is a schematic diagram coated on fibers using the polyolefin resin composition of the present invention.

3 is a view showing a three-ply extrusion lamination device for coating the polyolefin resin composition of the present invention on fibers.

* Description of the symbols for the main parts of the drawings *

1: polyester fiber feed roller (Unwinder) 2: adhesive Sarah and knife coater

3: dry chamber

4: (Extruded Resin Composition) Film Feeder (Unwinder) and Crimping Device

5: Coated Polyester Fiber Pressing Machine (Kinderder Roll) 6: Finished Winding Roller (Rewinder)

7: polyester fiber 8: adhesive

9: polyolefin film 10. Extrusion laminator.

11: T-die 12: matt embossing roller

13: Nylon Dafuda fiber feed roller (Unwinder) 14: Adhesive coating device

15: elastic rubber roller

16: 3 layer laminated product rewinder

Hereinafter, the present invention will be described in detail.

The present invention (i) 0.1 to 30 parts by weight of ethylene-alpha-olefin copolymer resin; (ii) 0.1 to 30 parts by weight of low density polyethylene resin; (iii) 0.1 to 39 parts by weight of general purpose resin; And (iv) 0.1 to 30 parts by weight of an inorganic filler.

In addition, the fiber comprising a step of melting and mixing the above-described polyolefin resin composition, the fiber coating film formed by melting and mixing the above-mentioned polyolefin resin composition to form a film, and coating the molded film and the fiber fabric It provides a method for producing a.

It is preferable to use the ethylene-alpha-olefin copolymer resin used by this invention whose density is 0.865-0.935. If the density is lower than 0.865, the flexibility of the film is increased, so it is suitable for coating with fibers, but it is not suitable because of poor extrusion processability, and if the density is higher than 0.935, the film is stiff, causing a bad texture. It is preferable to use a melt index of 1.0 to 20 or less. When the melt index is more than 20.0, the extrusion processability is excellent, but the compatibility is poor, and uniform dispersibility with other resins may be lowered. In particular, the physical properties such as flexibility and elasticity may be weakened, but the adhesion is very excellent. Since it is double-sided, it is more effective to use 0.1-30 weight part suitably.

Butene, hexene, octene or metallocene may be used as the alpha-olefin of the ethylene-alpha-olefin copolymer resin.

In addition, the low density polyethylene resin has a density of 0.900 to 0.938 and a melt index of 1.5 to 20, preferably 2.0 to 20 in consideration of compatibility with other resins, flexibility, elasticity, and adhesive strength after extrusion coating. effective. In particular, the low density polyethylene resin used for extrusion coating is used as an essential material because the higher the melt index, the better the adhesive strength and the better the extrudability, but the higher the blending amount of the low density polyethylene resin, the higher the processability of the film and The dispersibility of the fiber is improved, and the adhesion to the fiber is increased. However, the tensile strength, the actual rate and the tear strength are decreased, and the fiber fabric is stiff, which can cause fatal defects that cannot be used as the fiber. And since adhesive strength falls, it is preferable to use 0.1-30 weight part.

The general purpose resin used in the present invention is characterized in that at least one selected from ethylene vinyl acetate copolymer resin, alpha-olefin copolymer resin and elastomer is selected and mixed.

The ethylene vinyl acetate copolymer resin has a vinyl acetate content of 5 or more, a density of 0.910 to 0.940, and a melt index of 1.0 to 20 is preferably used to improve coating property, adhesion, flexibility, and feel.

It is preferable to use an alpha-olefin copolymer resin having a density of 0.890 to 0.930 and a melt index of 0.9 to 4.5 to improve coating property, adhesion, flexibility and feel.

It is preferable to use an elastomer having a Shore Hardness 'A' of 95 or less and a specific gravity of 0.890 to 0.980 to improve coating property, adhesion, flexibility, and feel.

In addition, when the compounding amount of the ethylene vinyl acetate copolymer resin increases in the compounding of the general-purpose resin described above, it is possible to obtain a soft-textured product having elasticity and flexibility desired in the present invention, but the ethylene vinyl acetate copolymer resin If the content is increased more than necessary, the cost of the raw material is high, the problem of dispersion with other resins, and the extrusion workability is significantly reduced, it is preferable to use 0.1 to 39 parts by weight.

In the present invention, the alpha-olefin copolymer resin and the elastomer improve adhesive strength when coated by extrusion coating, extrusion lamination and other coating methods, and in particular, to maintain the texture of the synthetic fiber used in the present invention. However, if the usage is high, the elasticity and flexibility is high, but the effective material that can make the texture of the fiber, but there is a concern that the cost will be high. Particularly, the elastomer having excellent compatibility with the polyolefin resin may be made of polyolefin elastomer, polyurethane elastomer, polyester elastomer, polystyrene elastomer, rubber elastomer such as EPR or EPDM, and the like. To be used is very effective. It is more effective to use 1 to 40 parts by weight of the alpha-olefin-based copolymer resin and the elastomer, respectively.

The inorganic filler used in the present invention may be calcium carbonate, silica, clay talc, talc, barium sulfate, alumina, zeolite and the like, and in particular, calcium carbonate, barium sulfate and talc are preferably used. The inorganic filler can use both the thing surface-treated with stearic acid etc. by a well-known method, and the average particle diameter is 0.5-30 micrometers, Preferably it is 0.7-5.0 micrometers. It is preferable to use 0.1-30 weight part of inorganic fillers. At this time, if the amount falls below 0.1 parts by weight, bending strength, elasticity and flexibility are inferior, and when 30 parts by weight or more, the adhesive strength, tensile strength, elongation and tear strength rapidly decrease.

In addition, in the resin composition of the present invention, a known additive may be used in addition to the above-described ethylene-alpha-olefin copolymer resin, low density polyethylene resin, and general-purpose resin and inorganic filler. For example, 0.1-10 weight part of fatty acid ester type antistatic agent; 0.1 to 5 parts by weight of a silica based anti-broking agent; 0.1 to 10 parts by weight of bromine flame retardant; 0.1 to 5 parts by weight of an anti slip agent; Lubricants such as metal stearate, such as 0.1 to 10 parts by weight of zinc stearate and calcium stearate; 0.01 to 0.05 parts by weight of phenolic, phosphorus and thio antioxidants; 0.01 to 0.03 parts by weight of a polymer UV stabilizer, processing stabilizer and the like can be used.

Each of the polyolefin resin compositions is transferred to the hopper of the extruder through a hopper and a hopper loader capable of automatically supplying each resin composition, an automatic weighing apparatus, a mixer, and the like to be extruded. Alternatively, the respective compositions may be added to a tumbler or Henschel mixer, mixed, melted, processed using a twin screw extruder, a kneader or a Benbury mixer, or rolled into pelletized compounds. At this time, the processing temperature is in the range of 180 to 250 ° C, and the respective resins, inorganic fillers, processing aids and additives are melted and mixed in advance, and master-batched, and then the inorganic fillers are mixed to melt in the above-described method. Mixing is particularly good in dispersion and very effective for use in extrusion lamination, extrusion coating and dry lamination. On the other hand, the compound process may also cause a disadvantage of deterioration in physical properties, so only the inorganic filler can be master-beached and the remaining resins may be extrusion melted through dry blending to form a film.

In this regard, the cast extrusion coating machine used for the injection molding into the film or the sheet with the polyolefin resin composition described above has a screw diameter of 115 mm, an L / D of 32: 1, a compression ratio of 3.6: 1, and a die width of 1800 mm. , The motor capacity of the extruder was molded by the melt extrusion method through a 150 hp cast extruder.

When the resin composition thus prepared is extruded by a single screw extruder and cast on a casting roll through a tee die (2), the polyester (1) to be coated or the nylon thick fiber (4) are cast together with the resin composition to be extruded. It can be laminated and cooled while completing the finished product. At this time, a die used is a T-DIE, a fish-tail die, or a coat hanger die. And when the surface treatment of the corona treatment or plasma treatment on both sides of the adhesive surface of the extruded resin composition and the fiber to be coated will have a more excellent adhesion.

And the adhesive force can be further increased by coating the adhesive of the urethane or polyester-based before the coating of the fiber to be coated. Corrosion treatment of the surface of the casting roll used for coating gives the coated film surface an embossing effect such as matte effect and texture of the fiber, thus completing the function as coated fiber, and additionally, polyester Primary coating of fibers, adhesives, and flexible films, followed by pressing with a calender roll composed of elastic rubber rolls and steel rolls to give greater adhesion and flexibility to the polyester coated fibers. It is possible to complete the product with a very smooth and balanced base frame in the finished product.

Hereinafter, the present invention will be described in more detail with reference to Examples.

These examples are intended to illustrate the present invention in detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

In an embodiment of the present invention, the ethylene-alpha-olefin copolymer resin having a density of 0.918 and a melt index of 2.0 (SK stock: LE350V); Low density polyethylene resins having a density of 0.910 and a melt index of 12; Ethylene vinyl acetate copolymer resin having a vinyl acetate VA content of 15% and a melt index of 10; an alpha-olefin copolymer resin having a density of 0.89 and a melt index of 3.6; Polyurethane-based elastomers having a specific gravity of 0.90 and a Showa hardness of 85; Calcium carbonate with an average particle diameter of 3.0 mu m and surface treatment with stearic acid; Iganox 1010 (Songwon Industrial Products; Korea), a waste antioxidant; Igafos 168, a phosphorus antioxidant (Songwon Industrial Products: Korea); Calcium stearate; Zinc stearate; Glycerin monostearate antistatic agents; And silica antiblocking agents were used.

Example 1 5 parts by weight of ethylene-alpha-olefin copolymer resin, 15 parts by weight of low density polyethylene resin, 15 parts by weight of ethylene vinyl acetate copolymer resin, 25 parts by weight of calcium carbonate as inorganic filler and 0.03 parts by weight of phenolic antioxidant Knox 1010 (Songwon Industrial Products; Korea), 0.03 parts by weight of Igaphos 168 (Songwon Industrial Products: Korea), an antioxidant of 0.03 parts by weight, 0.03 parts by weight of calcium stearate, 0.03 parts by weight of zinc stearate, and 0.1 parts by weight of glycerin monostearate An antistatic agent and 0.03 parts by weight of silica blocking agent were added to a Henschel mixer, mixed at 60 ° C. for 30 minutes, and melt-extruded at 210 ° C. using a twin screw extruder to prepare pellets.

The polyolefin coated with the adhesive was first molded into a film using a pellet-shaped resin composition prepared by using a single screw extruder having a screw diameter of 115 mm and a casting coating equipment having a T-Die 11 width of 2,000 mm. The polyester fibers were coated. At this time, the cylinder temperature of the extruder is 300 ℃, the temperature of the Ti-die was extruded under the conditions of 310 ~ 320 ℃, the matte embossing roll 12 of the casting roll and the matte embossing roll (Back Up Roll) The temperature of 12) was 30 degreeC, and the polyester fiber was coated. And the product was completed by heating and pressurizing in the calendar roll 15 which consists of an elastic plastic roll and a steel roll secondary.

Example 2 The same composition, method and coating conditions as in Example 1 were used except that 5 parts by weight of ethylene-alpha-olefin copolymer resin, 15 parts by weight of low density polyethylene resin and 15 parts by weight of alpha-olefin copolymer resin were used.

Example 3 The same composition, method and coating conditions as in Example 1 were used except that 5 parts by weight of ethylene-alpha-olefin copolymer resin, 15 parts by weight of low density polyethylene resin and 15 parts by weight of polyurethane were used.

Example 4 The same composition, method and coating conditions as in Example 1 were used except that 5 parts by weight of ethylene-alpha-olefin copolymer resin and 20 parts by weight of low density polyethylene resin were used.

Comparative Example 1: The same method and coating conditions as in Example 1 were used except that only 5 parts by weight of ethylene-alpha-olefin copolymer resin and 15 parts by weight of polyethylene resin were added.

Comparative Example 2: The same method and coating conditions as those of Comparative Example 1 were used except that only the low density polyethylene resin was used and the inorganic filler calcium carbonate was used.

Comparative Example 3: The same method and coating conditions as those of Comparative Example 1 were used except that only ethylene-alpha-oleicene copolymer resin and low density polyethylene resin were used.

The amounts of the compositions added in Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1 below.

Mechanical properties such as tensile strength, elongation rate, puncture strength, tear strength, bursting strength, electrostatic dissipation, hydrostatic head and flammability of the polyester coated fiber prepared in the above and Examples and Comparative Examples are as follows. It carried out in the same way.

(1) Tensile strength (unit: lbs) was measured by Grip-Method of ASTM5034 method.

(2) Elongation (%) was measured according to ASTM D5034.

At this time, the tensile strength of (1) and the elongation of (2) were C.R.E Type Test Machine, Test Speed was 300mm / min, Temperature was 20 ± 2 ℃ and Humidity was 65 ± 2%.

(3) Puncture resistance (Puncture Resistance, Unit: lbs) was measured by ASTM D4833.

(4) Tear Strength (unit: lbs) was measured by Traperzoid-Method in ASTM D5733.

(5) Bursting Strength (unit: lbs) was measured using BallBursting Method of ASTM D3787.

(6) Electrostatic Decay (unit: sec) was measured by KSK0555 method.

(7) Hydrostatic head (unit: cm) was measured by AATCC 127 method.

(8) Flammability was measured by 16CFR1610 method.

As can be seen in Table 2, when a film made of a polyolefin-based composition containing a polyolefin-based resin and a calcium carbonate inorganic filler according to the present invention is coated on a polyester fiber, the tensile strength, elongation, and hole of the polyester fiber It has excellent mechanical properties such as toughness, tear strength, bursting strength, electrostatic dissipation, hydrostatic head and flammability, and particularly excellent flexibility, elasticity and adhesion, as well as excellent texture of coated products. Can be.

FIG. 1 is a diagram showing a two-ply extrusion lamination apparatus for coating a polyolefin resin composition of the present invention on a fiber, and FIG. 2 shows a schematic diagram coated on a fiber using the polyolefin resin composition of the present invention. In addition, Figure 3 shows a three-ply extrusion lamination device for coating the polyolefin resin composition of the present invention on the fiber.

As described and demonstrated in detail above, the coating of the polyolefin-based resin composition according to the present invention on the fiber can not only maintain the flexibility of the fiber, elasticity, easy processability during sewing and the original texture of the fiber, but also due to the current dioxin It has been developed as an economical material that can replace the PVC causing environmental pollution problems, in particular, the polyester coated fiber coated with the present resin composition can be used as the fabric of bags and various industrial coating materials.

Claims (17)

(i) alpha olefin is formed of one of hexene and metallocene, 0.1 to 30 parts by weight of ethylene-alpha-olefin copolymer resin having a melt index of 1.0 to 20.0 and a density of 0.865 to 0.935; (ii) 0.1 to 30 parts by weight of low density polyethylene resin having a melt index of 1.5 to 20.0 and a density of 0.900 to 0.938; (iii) 0.1 to 39 parts by weight of ethylene vinyl acetate copolymer resin having 5 parts by weight or more of vinyl acetate, having a melt resin of 1,0 to 20.0 and a density of 0.910 to 0.940; And (iv) polyolefin resin for fiber coating comprising 0.1 to 30 parts by weight of inorganic filler having a particle diameter of 0.5 to 30 μm, formed by selecting and mixing one or more of clay talc, talc, barium sulfate, alumina, and zeolite. Composition. delete delete delete delete delete delete delete delete delete According to claim 1, 0.1 to 10 parts by weight of fatty acid ester antistatic agent; 0.1 to 5 parts by weight of a silica antiblocking agent; 0.1 to 10 parts by weight of bromine flame retardant; 0.1 to 5 parts by weight of an anti slip agent; 0.1 to 10 parts by weight of lubricant; 0.01 to 0.05 parts by weight of antioxidant; And 0.01 to 0.03 parts by weight of a polymer UV stabilizer, the polyolefin resin composition for fiber coating, characterized in that it further comprises at least one. The film for fiber coating formed by melting, mixing, and extruding the polyolefin resin composition of Claim 1 or 11. delete delete delete delete delete