KR100948499B1 - Pellet composite containing ultra fine calcium carbonate and method for preparing the same - Google Patents

Abstract

The present invention relates to a masterbatch composition using ultra-fine calcium carbonate, the master batch using ultra-fine calcium carbonate, improved cost reduction, surface improvement, compatibility, properties increase properties by using the ultra-fine calcium carbonate, binder resin as the main raw material It relates to a composition. The composition of the present invention is excellent in compatibility with various polymer materials such as biodegradable resins, synthetic resins, there is an advantage that can be variously applied as a raw material of film and vinyl extrusion, sheet molding, vacuum molding, vacuum molding, injection molded products.

Ultra Fine Calcium Carbonate, Masterbatch, Incineration, Packaging Materials, Physical Properties Improvement, Compatibility, Polymer

Description

Master batch composition using ultra fine calcium carbonate and its manufacturing method {PELLET COMPOSITE CONTAINING ULTRA FINE CALCIUM CARBONATE AND METHOD FOR PREPARING THE SAME}

The present invention relates to a masterbatch composition having the properties of improving the properties of the packaging material, cost reduction, incineration, and productivity by using calcium carbonate as a main raw material. It relates to a masterbatch composition with improved properties. The composition based on the ultrafine calcium carbonate and the binder resin of the present invention has excellent compatibility with various polymer materials such as biodegradable resins and synthetic resins, and is a raw material for film and vinyl extrusion, sheet molding, vacuum molding, vacuum molding, and injection molded products. There is an advantage that can be applied to various.

       Synthetic resin polymer called plastic is the main material which occupies more than 80% by the volume ratio of our industry and life, and is obtained as the final product of petrochemical. More than 50% of plastics are consumed for short-term products, light packaging materials, and disposables, and environmental waste has become one of the biggest social issues in recent years. But plastics are the quintessence of petrochemical technology and, as mentioned earlier, they are positioned as the most important and most consumed materials of our time.

       Meanwhile, since 1995, the price of crude oil has risen sharply due to concerns about the depletion of petroleum resources, natural disasters and unrest in the international community. As a result, raw material prices of plastics have risen sharply, but final consumer prices have almost frozen. Due to the phenomenon, many domestic SMEs have lost their competitiveness and abolished their business, moved to foreign countries or went bankrupt. In addition, unlike the past periods of the first and second oil surges, the social response to the saving of national energy and all industrial goods derived from petroleum due to the rise in oil prices was too wasteful.

       In the present invention, by developing a masterbatch by concentrating natural inorganic materials such as ultra-micronized products, talc (talc powder), calcium carbonate and the like in the existing polymer, the developed masterbatch is film, sheet, vacuum forming, vacuum forming and It can be applied to general injection products. As a result, we strengthen our competitiveness in packaging films and shopping bags, and use them as extrusion raw materials for consumable plastic materials markets such as film makers, sheet makers, blow molding companies, and molding companies, such as injection products for packaging / transporting or consumable short-term products. It was confirmed that the utility is high.

        Plastic compounds using undifferentiated inorganic fillers have already been widely used to reinforce the mechanical and physical strength of injection molded plastic products and at the same time offer a price advantage, but these products are generally used only in very expensive or limited areas. For example, it is well known that the products that provide price competitiveness have had a significant decrease in mechanical and physical properties, resulting in a loss of merchandise or a substantial loss in the economic evaluation due to the specific gravity difference between the inorganic material and the polymer.

        The present inventors have decades of experience in the field, and have been trying to overcome these shortcomings. By applying the recent emerging nanotechnology to this, the economic loss due to the specific gravity difference of the product as well as the reinforcement of physical mechanical properties and Successfully developed a masterbatch to improve productivity and applied it to packaging materials such as film and sheet. As a result, it showed physical strength increase, surface improvement effect and cost reduction effect on existing products in terms of quality competitiveness. Indicated. Incidentally, the finished product using the present invention contains at least 20% to 40% of inorganic materials, and is expected to contribute greatly to the safety of incineration and the reduction of petroleum resources in the country.

          The demand for disposable products, including plastics, which is hygienic, convenient and inexpensive, is increasing due to the increase of income level and the spread of the atmosphere for convenience of living. In particular, fast food stores, convenience stores, department stores, marts, food packaging materials, various disposable products, packaging containers, vending machines, etc. are mostly used products made of plastic, which is a thermoplastic polymer.

          Recently, the overall domestic and international atmosphere has been actively researched on the use of plastic polymers and the development of alternative materials in accordance with the rise of international crude oil prices following the alarm on the finiteness of global petroleum resources, global warming, carbon dioxide reduction and environmental pollution. Apart from this, research is being actively conducted to improve the properties of polymers, such as plastics, and to reduce costs and to provide eco-friendliness.

Previously, developments using inorganic fillers such as calcium carbonate, clay, zeolite, loess, and talc have been made. However, in the case of the existing inorganic additives, it is difficult to industrialize a wide range of realistically because of using only in a specific field, high price, lowering of physical properties.

      Korean Patent Application No. 10-2005-0077246 relates to a nano calcium carbonate and vinyl chloride composite resin composition, which is an alternative to the use of expensive impact modifiers, and also has a low usage amount, which is less than 30% or more of incineration standards at home and abroad. . According to Korean Patent Registration No. 10-0656551, nano calcium carbonate was used in the tread rubber composition to improve wear resistance and rotational resistance characteristics. In addition, according to Korean Patent Registration No. 10-0827296, a waterproof coating using calcium carbonate was provided, and eco-friendliness was increased by substituting adhesive and flame retardant materials with eco-friendly raw materials. Compared with the above patents, the substitution rate of the petroleum-derived synthetic resin polymer is low, and it is used in a specific field, and thus, it is found that the present invention can be used as a raw material for a wide range of packaging materials.

The technical problem to be achieved by the present invention is excellent compatibility when applied to a variety of packaging polymers, to provide a master batch composition using ultra-fine calcium carbonate that can be expected to increase the properties of the finished product packaging material, surface improvement effect and cost reduction For the purpose. In addition, another object of the present invention is to use the existing equipment without modification when manufacturing the finished product packaging material using the masterbatch composition, easy to produce, excellent physical properties of the produced finished product packaging material can be expected to reduce costs It is intended to provide a masterbatch composition using ultrafine calcium carbonate and a preparation method thereof.

In order to achieve the above object, the masterbatch composition using the ultra fine calcium carbonate of the present invention is based on 100% by weight of the total composition (a) 5% to 70% by weight of ultra fine calcium carbonate, (b) fine calcium carbonate 10 Weight percent to 60 weight percent, (c) 1 to 20 weight percent talc, (d) 0.1 to 20 weight percent lubricant, and (e) 5 to 50 weight percent binder resin. .

        The object of the present invention is also achieved by a first method comprising the following steps.

        Ultra-calcium carbonate, fine calcium carbonate, talc, lubricant, binder resin in a dispersing kneader to remove moisture and kneading step 1;

        The dough is put into an extruder and a method for producing a masterbatch composition using ultra fine calcium carbonate by two steps of preparing pellets is provided.

        The object of the present invention is also achieved by a second method comprising the following steps.

        Ultra-calcium carbonate, fine calcium carbonate, talc is added to the mixer and the high-speed mixing and water removal step 1;

Adding a lubricant and a binder resin to the material of the step where moisture is removed, followed by high-speed mixing;

One or more kneading zones and one or more reverse screws are installed on the materials completed until the mixing process, and a vent hole capable of discharging moisture and volatile substances that may be generated during raw material processing ( Provided is a method for producing a masterbatch composition using ultra-fine calcium carbonate by three steps of producing a pellet type using a conventional biaxial extruder having one or more vent holes.

      The composition according to the present invention forms a bond with the monomer of the polymer material, the ultra-fine particles to fill the empty space between the polymer shows the physical properties such as strength and surface improvement effect.

      Calcium carbonate is used in industrial fields such as cement, rubber, plastics, paper, and the like, and generally, particles having a particle diameter of several tens to hundreds of micrometers are used. In addition, since calcium carbonate is hydrophilic, surface modification may be used by coating with fatty acid or wax when applied to a product vulnerable to moisture.

      The nano-grade ultra-fine calcium carbonate is used having a particle size of 50 to 900 nm, the amount may be 3 to 80% by weight, preferably 5 to 70% by weight based on the total weight of the composition. When it is used at 5 wt% or less, it is difficult to expect the effects of product compatibility, surface modification, and physical property increase when applied to the finished product packaging material, and when it is used at 70 wt% or more, productivity decreases, cost rises, material aggregation phenomenon. This will adversely affect the masterbatch properties. In the case of using such ultrafine calcium carbonate, the surface area is increased by the ultrafine particles and the proportion of ions placed on the surface is increased. Therefore, it plays a very large role in the physical properties of the polymer such as bonding strength, cohesion, and the like, a remarkable effect of physical properties improvement, surface modification, strength increase.

     The micro-grade fine calcium carbonate can be used having a particle diameter of 3 to 100㎛, when using only ultra-fine calcium carbonate is agglomerated calcium carbonate by a strong self-cohesive force has a rather bad effect on the finished product packaging material. For example, disadvantages such as deterioration of surface condition, lowering of dimensional stability, lowering of elastic modulus of elasticity, lowering of physical properties such as strength and lowering of productivity are increased. The amount of fine calcium carbonate may be 5 to 70% by weight, preferably 10 to 60% by weight based on the total weight of the composition.

     The lubricant may be used alone or in combination with calcium stearate, zinc stearate, glycerin stearate, butyl stearate, solid paraffin, liquid paraffin, beeswax, drive wax, emulsion wax, candelilla wax, P. wax, P. wax. Its usage amount may be 0.2 to 20% by weight, preferably 0.5 to 15% by weight. Lubricants have a disadvantage in that the cost of materials increases when using behenic acid series with 22 carbon atoms, which have good lubrication effects. There is an advantage in In addition, when using a fatty acid-based lubricant, there is an advantage in showing the affinity to the inorganic material, such as filler, there is an advantage that the surface is modified by coating a hydrophilic inorganic material. Lubricants are additives that are used to literally reduce and smooth the friction between raw materials. Not all frictions are bad, but the heat of friction during mixing, melting, and processing of the raw materials causes the raw materials to be heated and decomposed more than necessary, carbonizing organic additives such as starch in the raw materials, and It is used to eliminate the occurrence of defects by pressing on the surface.

       The binder resin in the composition is low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile butadiene styrene ( ABS), polyhydroxybutyrate valerate (PHBV), polycaprolactone (PCL), polybutylene succinate (PBS), polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyalkanoate ( PHA), starch resin may be used alone or in combination, the amount of the starch resin may be 3 to 60% by weight, preferably 5 to 50% by weight. It is to play an important role in the formation of pellets, when it is added less than 5% by weight, it is difficult to form pellets by weakening the binding force, when using more than 50% by weight is no particular problem, but the unit price There are disadvantages to rise.

       The masterbatch composition according to the present invention is a melt extrusion molding process using a conventional single or twin extruder after mixing or making a lump dough using a conventional Henschel mixer, a super mixer or a dispersing kneader. It is used to make a pellet having a size of about 2-8mm. The conventional thermoplastic polymer resin and the additive composition required according to the use can be immediately mixed to form a product to be produced. Alternatively, the required thermoplastic polymer resin and the other components may be mixed in an appropriate ratio according to the use to prepare a compound beforehand to prepare a desired product. Packaging materials that can be manufactured can be manufactured in a variety of known forms such as films, vinyl, sheets, vacuum molded products, injection molded products. Such a masterbatch or compound for decomposition additives is suitably prepared to a degree that can be mixed and used in a ratio of about 3 to 75% by weight relative to the total weight of the conventional polymer resin, but the present invention is not limited thereto.

The masterbatch composition using ultra-fine calcium carbonate prepared according to the present invention is compatible with the polymer synthetic resin, no particular problem was found in producing the finished product packaging material, the product productivity is excellent and the product strength is increased. As the masterbatch composition of the present invention is applied to industrialization, the use of the synthetic resin polymers can be significantly reduced, thereby reducing the use of synthetic polymers, a global trend, and contributing to the reduction of petroleum resources. Apart from this, large-scale substitutes for synthetic resins derived from expensive petroleum resources, which continue to rise in price, are highly cost effective and highly applicable to the industry.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are intended to illustrate the invention and are not intended to limit the invention thereto.

<Example 1>

25 wt% of ultra fine calcium carbonate, 45 wt% of fine calcium carbonate, 3 wt% of talc, 1.7 wt% zinc stearate, 0.3 wt% of zinc wax, and 25 wt% of low density polystyrene were added to the dispersion kneader and the temperature was 140 degrees or higher. Knead until you get a paste. After cutting the dough in the paste state to a certain size, it was put into a single-axis extruder with a cylinder temperature of 130 degrees or more and face-cut with gala system to prepare a master batch pellet.

<Example 2>

 Ultrafine calcium carbonate 25% by weight, fine calcium carbonate 48% by weight, zinc stearate 1.7% pywax 0.3% by weight, low-density polyethylene 25% by weight was added to the mixer was mixed at high speed to remove moisture and mixed. The obtained mixture was prepared using a conventional biaxial extruder having two or more vent holes.

<Example 3>

40 wt% of the masterbatch composition prepared in Example 2, 10 wt% of regenerated resin, 4 wt% of high density polyethylene, and 3 wt% of linear low density polyethylene were mixed to prepare a film using a conventional film extruder.

<Example 4>

40 wt% of the masterbatch composition prepared in Example 1, 10 wt% of regenerated resin, and 50 wt% of polypropylene were mixed to prepare a sheet in a conventional sheet extruder.

<Example 5>

Using the sheet prepared in Example 4, a vacuum molded article was manufactured using a conventional vacuum molding machine.

<Example 6>

40 wt% of the masterbatch composition prepared in Example 1, 10 wt% of regenerated resin, and 50 wt% of polypropylene were mixed to prepare an injection molded article in a conventional injection molding machine.

<Comparative Example 1>

Example of the Invention In order to carry out comparative experiments on films of the most difficult packaging materials with low physical properties such as strength, the masterbatch of the present invention was replaced with a conventional calcium carbonate masterbatch purchased commercially. Then, a commercially available calcium carbonate masterbatch 40% by weight, recycled resin 10% by weight, high density polyethylene 47% by weight, linear low density polyethylene 3% by weight was mixed to prepare a film using the same film extruder as in Example 3.

<Comparative Example 2>

 A film was prepared using the same film extruder as in Example 3 by mixing 87% by weight of high density polyethylene, 10% by weight of regenerated resin, and 3% by weight of linear low density polyethylene.

Experimental Example 1

The mechanical property test of the film prepared according to Example 3 and Comparative Example 1 was measured using a universal testing machine (product of Instron Co., Ltd.), and the average value except the highest and minimum values was measured 10 times for each measurement item. Was taken. The results are shown in Table 1 below.

(Table 1) Mechanical property test results

division Tensile Strength (N / ㎠) Tear strength (㎏ / ㎠) Elongation (%) Example 3 Width 1,578 135 669 Length 1,904 148 614 Comparative Example 1 Width 881 21 237 Length 952 35 238 Comparative Example 2 Width 1,601 130 721 Length 1,839 138 715

As can be seen in Table 1, the packaging film according to the composition according to the present invention has similar properties to general vinyl (Comparative Example 2), such as tensile strength, tear strength and elongation, the existing calcium carbonate masterbatch It can be seen that it is remarkably superior compared to the product using (Comparative Example 1). In addition, in the case of Comparative Example 2 there was a disadvantage that the film production is very difficult, such as bursting without forming a film rod.

Claims (5)

5.0 to 70 wt% of ultrafine calcium carbonate having a particle size of 50 to 900 nm, 10 to 60 wt% of fine calcium carbonate having a particle size of 3 to 100 μm, talc 1 to 20 wt%, lubricant 0.1 to 20 wt%, binder resin 5 To 50% by weight of a masterbatch composition using ultrafine calcium carbonate, characterized in that it is manufactured in pellet form using a conventional single screw, twin screw extruder. The method of claim 1, wherein the lubricant component is calcium stearate, zinc stearate, glycerin stearate, butyl stearate, solid paraffin, liquid paraffin, beeswax, drive wax, emulsifying wax, candelilla wax, pi wax, pipi Masterbatch composition using ultrafine calcium carbonate, characterized in that one or two or more selected from waxes The method of claim 1, wherein the binder resin is low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS), acrylonitrile Butadiene styrene (ABS), polyhydroxybutyrate valerate (PHBV), polycaprolactone (PCL), polybutylene succinate (PBS), polyhydroxybutyrate (PHB), polyhydroxyalkanoate (PHA), Masterbatch composition using ultrafine calcium carbonate, characterized in that one or two or more selected from the starch resin 1 step of removing water and kneading by adding ultra fine calcium carbonate having a particle size of 50 to 900 nm, fine calcium carbonate having a particle size of 3 to 100 μm, talc, a lubricant, and a binder resin to a dispersion kneader; Method of producing a master batch composition using ultra-fine calcium carbonate, characterized in that it comprises the step of putting the dough into the extruder and producing pellets in a conventional manner. Ultra-calcium carbonate having a particle size of 50 to 900 nm, fine calcium carbonate having a particle size of 3 to 100 μm, and talc are added to a mixer, followed by high speed mixing and water removal; Adding a lubricant and a binder resin to the material of the step where moisture is removed, followed by high speed mixing; One or more kneading zones and one or more reverse screws are installed on the materials completed until the mixing process, and a vent hole capable of discharging moisture and volatile substances that may be generated during raw material processing ( Method for producing a masterbatch composition using ultra-fine calcium carbonate, characterized in that it comprises three steps of producing a pellet type using a conventional biaxial extruder having one or more vent holes)