KR20130051840A - Eco-friendly bio based pellet with plant biomass and method of the same - Google Patents

Abstract

PURPOSE: A manufacturing method of environment-friendly bio base pallet is provided to manufacture environment-friendly bio base pallets containing more plant body biomass. CONSTITUTION: A manufacturing method of environment-friendly bio base pallets comprises the following steps: (A) producing plant body powder by pulverizing a plant body into particles under 80-300 mesh; (B) removing moisture by heating and drying the plant body powder at 50-150 deg. C for 0.5-24 hours; (C) producing coated plant body powder by injecting wax into the plant body powder and mixing the plant body powder with the wax by 300-800 rpm for 10-30 minutes; (D) forming a mixture by injecting a plastic resin acting as a binder, organic acid and peroxide into the coated plant body powder and mixing; and (E) manufacturing a pellet by leading a plastic resin-biomass graft bond by injecting the mixture into an extruder, and releasing the material having the plastic resin-biomass graft bond through an outlet, then cutting after air-drying or die-face hot cutting the released strand while transferring through a conveyor belt. [Reference numerals] (AA) Plastic resin-Biomass graft bond mimetic diagram; (BB) Plastic resin bond structure; (CC) Peroxide: cut polymer, Organic acid graft bond on the cut side; (DD) Compatibility productivity improvement, physical property improvement effect; (EE) Plastic resin; (FF) Biomass(plant body, starch, and others); (GG) Organic acid; (HH) Starch; (II) Plant body; (JJ) Polymer

Description

Eco-friendly bio based pellet with plant biomass and method of the same}

The present invention relates to eco-friendly bio-based pellets using biomass and a method of manufacturing the same, and more particularly, waste materials using carbon neutral plant biomass, at the same time reducing the plastic properties, carbon dioxide reduction and decomposition effect It relates to an eco-friendly bio-based pellets and a method for manufacturing the same, which are processed to facilitate the production of injection molding, extrusion molding, vinyl film, industrial products, and the like.

With the increase in the use of various plastic products including films, the amount of plastic waste has increased exponentially in recent years. Plastic waste is generally disposed of by landfill, incineration or recycling.

However, in the case of landfill, the decomposition time of the landfilled plastic waste takes a very long time, which causes a shortage of landfill space and soil pollution. Incineration also contributes to global warming as well as air pollution due to the generation of toxic gases. In addition, recycling is not only difficult to collect and separate, but also increases the processing cost.

In recent years, plastic products have been developed to provide fast degradability. For example, there has been disclosed a disposable plastic container manufactured using a composition in which starch is added together with rice straw, rice hull, and sawdust grind to a synthetic resin. However, in the case of such a composition is effective in improving the degradability, when produced in the form of a film has a disadvantage in physical properties, in particular the initial elongation and tensile strength of the film produced.

      Bio-based plastics (in Japan, called biomass plastics) are plastics containing 25% or more of the so-called biomass derived from plants such as corn. There is an effect of suppressing the increase in the concentration of carbon dioxide in the water, it is possible to reduce the consumption of petroleum, a limited resource, and has been attracting attention recently because it is decomposed by microorganisms after disposal. Among them, plant biomass, which belongs to non-edible organic waste resources such as agricultural waste, industrial waste, and food factory by-products, which are difficult to use for food, is drawing attention as an environmentally friendly carbon neutral biomass material.

      Degradation involving bio-based plastics occurs in three stages. The first step is the step of microbial decomposition and oxidative decomposition of the biodegradable components, and the physical breakdown of the polymer occurs as the biomass components contained in the final product such as food containers are microbially degraded. As the first step proceeds, the surface area increases, the physical strength and the elongation decrease, and the polymer proceeds to a porous state. The second stage is a chemical decomposition (molecular weight reduction) step, and an automatic oxidation reaction is performed by carboxylic acids, ketones, aldehydes, and unsaturated fatty acids generated by natural decomposition, and the surface is gradually hydrophilic to promote thermochemical decomposition. Chemical decomposition occurs due to peroxides, organic acids and the like, and the molecular weight of the polymer decreases. The third stage is a microbial decomposition (final biodegradation) stage, in which the molecular weight is lowered and the plastic is made into a low molecular weight, changed into alcohol, aldehyde, fatty acid, etc., and then further decomposed into water, carbon dioxide and biomass.

     Various bacteria, bacteria, enzymes, etc. present in the soil act on the low molecular weight polymer and finally biodegrade in nature. When the molecular weight falls below 40,000, decomposition by the microorganisms proceeds actively without the action of additives or the like. In a real natural environment, the three decompositions proceed simultaneously and complementarily. Vise base pellets are needed to contribute to the decomposition of the first and second stages above.

     Biomass, a carbon-neutral plant, refers to plant resources, microbial metabolites, and seaweeds in which atmospheric carbon is fixed by photosynthesis. It is known to contribute to the prevention of global warming by not increasing the total amount of carbon dioxide on the planet. However, there is a disadvantage in that the flowability, productivity and physical properties deteriorate when molding the plant biomass into the finished polymer, so that the amount of adding the plant to the polymer is hardly exceeding 5%, which is an effective method for using the plant in large quantities. Development has been requested.

     Eco-friendly plastics such as biodegradable plastics and bio-based plastics that are known at present include biodegradable plastic molding compositions (Japanese Patent Application No. 10-226393), polyolefin- Resin composition for plant fiber-based molding (Patent Publication No. 96-8117), biodegradable resin composition for extrusion injection molding (patent registration 10-443275), and the like.

     However, when the modified starch is made, it has a disadvantage in that it is not practical due to its weak physical properties such as tensile and elongation, and in actual use, thermoplastic starch or starch fermentation and polymerization through plasticization reaction at high temperature and high pressure. PLA (Poly lactic acid) processing through the process is used in reality. In addition, the surface-treated resin composition for polyolefin-plant fiber-based molding has a disadvantage in that the process, cost and biodegradation rate is lowered. In the case of using biodegradable plastics such as aliphatic polyester, there are disadvantages in that it is difficult to apply to actual industrialization due to problems of deterioration of physical properties, strength of finished products, and problems due to biodegradation during distribution or product use due to premature degradation.

The first problem to be solved by the present invention is to disclose an eco-friendly bio-based pellet and a method of manufacturing the same using a carbon neutral plant biomass waste resources and at the same time have a plastic properties, carbon dioxide reduction and decomposition efficiency will be.

Another problem to be solved by the present invention is to disclose an eco-friendly bio-based pellets with increased use of plant biomass.

In order to achieve the above object, the present invention (A) a grinding step of grinding the plant to 80 ~ 300 mesh; (B) a drying step of heating and drying the ground plant powder at 50 to 150 to remove moisture; (C) a coating step in which the wax is added to the dried plant powder and stirred at a high speed at 300 to 800 rpm to coat the wax on the surface of the rice husk powder; (D) a mixing step of adding and mixing a plastic resin polymer, an organic acid, and a peroxide, which serve as a binder, to the wax-coated plant powder to form a mixture; (E) Injecting the mixture into a twin extruder so that the plastic resin-biomass graft coupling is performed, and discharges the material made of the plastic resin-biomass graft coupling through the discharge port, the discharged strand is conveyed The present invention provides a method for manufacturing eco-friendly bio-base pellets, including the step of preparing eco-friendly bio-based pellets by cutting or die-cutting hot-dip after blowing through the belt.

       In the step (D), the starch and starch plasticizer is further added before mixing the input, and the starch is preferably 5 to 50 parts by weight based on 100 parts by weight of the eco-friendly bio-based pellets.

      In the step (D), prior to mixing the charge is to add any one or more of a compatibilizer, a lubricant, an oxidizing agent and an inorganic filler, the addition amount is 0.5 g of the compatibilizer with respect to 100 parts by weight of eco-friendly bio-based pellets To 5 parts by weight, the lubricant is 0.5 to 5 parts by weight, the oxidizing agent is 0.2 to 6 parts by weight, the inorganic filler is preferably 10 to 65 parts by weight.

     The content of the peroxide is preferably 0.01 to 5.0 parts by weight based on 100 parts by weight of the plastic resin.

      Wherein the organic acid is at least one of citric acid, malic acid, maleic acid and acetic acid, and the content of the organic acid is at least one of an organic biomass bonding structure It is preferably 0.2 to 5 parts by weight based on 100 parts by weight of the base pellets.

      The compatibilizer is a substance which gives compatibility by removing the releasability between the non-polar synthetic resin and the polar herbal agricultural waste, wherein the compatibilizer content is 0.5 to 5 parts by weight based on 100 parts by weight of eco-friendly bio-based pellets. It is preferable.

     The glidants may be used without limitation in general, and any one of zinc stearate and calcium stearate may be used. The inorganic filler is preferably one or more of calcium carbonate, clay, talc, loess, talc, kaolin. It is preferable that the amount used is 0.5 parts by weight in 0.5 parts by weight of lubricant, 0.2 to 6 parts by weight of oxidant, and 10 to 65 parts by weight of inorganic filler based on 100 parts by weight of eco-friendly bio-based pellets.

      The starch plasticizer is any one or more of glycerin and sorbitol, the content of the starch plasticizer is preferably 10 to 30 parts by weight based on 100 parts by weight of the starch based on the starch content.

      The content of the plant powder is 10 to 50 parts by weight based on 100 parts by weight of the bio-based pellets, the content of the plant and starch is increased as the content of the plastic resin increases, the content of the peroxide of the plastic resin The content is increased with increasing content, and the content of the organic acid is preferably increased with increasing content of the sum of the contents of the plant and the starch.

     The binder plastic resin is a linear low density polyethylene (LLDPE), low density polyethylene (LDPE, Low density polyethylene), high density polyethylene (HDPE, High density polyethylene), polypropylene (PP, Polypropylene), polystyrene (PS, Polystylene), vinyl acetate (PVAc, Poly vinyl acetate), polyamide (PA, Pply amide), polycarbonate (PC, Poly carbonate) and acrylonitrile butadiene styrene (ABS) is preferably at least one Do.

      The plastic resin preferably has a melt index of 3.0 or more.

      Preferably, the coating step of step (C) and the step (D) are performed at the same time.

      In order to achieve the other object of the present invention, it provides an environmentally friendly bio-base pellets produced by the above-described manufacturing method.

Utilizing the present invention, it is possible to produce environmentally friendly bio-based pellets with an increased content of plant biomass.

1 is an exemplary flow chart of a method for producing an environmentally-friendly bio-based pellet of the present invention.
2 is a schematic diagram in which a plastic resin-biomass graft bonding structure is produced.
3 is a SEM photograph of a pellet fragment in which the graft bonding structure is not produced and a SEM photograph of the pellet fragment in which the graft bonding structure is produced.
4 is a schematic diagram of the reaction point of the plastic resin-biomass graft bond.

Hereinafter, it demonstrates in detail, referring drawings.

1 is an exemplary flow chart of a method for producing environmentally friendly bio-based pellets using the plant biomass of the present invention.

The manufacturing method of the eco-friendly bio-base pellet of the present invention is largely divided into five steps. Step A is a step of producing a plant powder by grinding the plant biomass. The plant is pulverized into fine powder so as to be about 80 to 300 mesh. If it is less than 80 mesh, the particle size is so large that the productivity is poor due to poor flowability during pellet production, the surface is rough, and the quality of the final product, such as film, is deteriorated, and the strength and elongation of the product is deteriorated. If the particle size is very small, the product quality is excellent, but the grinding process time is too long, which lowers the overall productivity and the price competitiveness due to the cost increase.

Plant biomass used in the present invention is a bran (or shell) of grains including corn, oats, rice, wheat, barley, etc., oxime, soybean meal, tofu meal, coffee foil and straw It means a combination containing by-products or mixtures thereof except grains or seeds obtained from herbal farm products such as grains including corn, barley, wheat, rapeseed, sunflower, etc.

      Subsequently, in step B, the plant powder is coated with wax to produce a coated plant powder. In the coating step, the plant powder is heated and dried at 50 to 150 degrees to remove moisture, and the wax is added to the heat-dried plant powder and stirred to produce a coated plant powder. Drying is carried out for 0.5 hours to 24 hours with heating and stirring at 50 to 150 degrees using a conventional drying apparatus to dry to 10% or less moisture content. If the drying temperature is less than 50 degrees, there is a problem that the drying is not sufficient, or the drying time takes a long time, and if the drying temperature is higher than 150 degrees, there is a problem that the plant biomass or the like becomes more likely to be carbonized, thereby deteriorating the quality of the product.

If the drying time is less than 0.5 hours, there is a problem that the product quality is bad due to moisture problems when producing the product by applying the finished product is not enough, and if more than 24 hours there is a problem that only energy is wasted without additional drying effect.

     In step C, the wax is added to the dried plant powder and stirred at 300 to 800 rpm to coat the surface of the plant powder. The added wax is dissolved by self heating (self heating) and coated on the surface of the plant powder. The coated plant powder is prevented from reabsorbing moisture. Wax has the advantage of low molecular weight and low melting point can also perform the function as a lubricant aid when preparing the additive using an extruder, and also has the advantage of being biodegradable into a low molecular weight material.

Waxes may be used paraffin wax, liquid paraffin wax, beeswax, drive wax, emulsion wax, candelilla wax, PE wax, PP wax and the like. The amount of wax to be added is suitably 1 to 20 parts by weight based on 100 parts by weight of the plant. When using less than 1 part by weight of coating function and lubricant additives are weak, when using more than 20 parts by weight, such as debris occurs in the die, the cost increases. If a lot of wax is used, the coating for water resistance is excellent. However, it is recommended to use 1 to 5 parts by weight based on 100 parts by weight of eco-friendly bio-based pellets because debris is generated in production equipment dies in injection, extrusion, and film production. Even better.

In the coating step, the wax is added and then stirred at high speed at 300 to 800 rpm. Thus, the wax naturally dissolves by self-heating due to the high speed stirring and is coated on the surface of the plant powder. The coating time is not specified, the coating is finished in the point that the coated plant powder becomes a certain lump form, generally 10 to 30 minutes is a little lump form to complete the coating.

Subsequently, in step D, a plastic resin polymer, an organic acid, and a peroxide, which serve as a binder, are added to the coated plant powder to form a mixture. Peroxides chemically cut the polymer chains of plastic resins. Organic acids function as intermediates for binding plants such as oxpe to the end of the cut plastic resin polymer. 2 shows this schematic diagram. Peroxides and organic acids allow the plastic resin-plant graft bond structure shown in FIG. 2 to be produced. The organic acid binds to the polymer terminal group cut by the peroxide. The peroxide is azo-bis-isobutylnitrile, tributyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-tributyl peroxide, 2,5 dimethyl-2,5 di (thibutylper Oxy) hexane (2,5-Dimethyl-2,5-di (t-butyl peroxy) hexane), 1,3-bis (thi-butylperoxy-isopropyl) benzene (1,3-Bis (t-buthyl peroxy-isoproply) benzene), but dicumyl oxide, benzoyl peroxide, di-triple butyl peroxide were good, and the graft-bonding structure of plant powder and plastic polymer of dicumyl oxide was the most effective. Preferably, the productivity of finished products such as injection molded products was the best.

The peroxide chemically cuts the polymer chain of the plastic resin. The content of the peroxide may be 0.01 to 5 parts by weight based on 100 parts by weight of the plastic resin based on the plastic resin. However, if it is 0.01 parts by weight or less, there is a problem in that it is difficult to expect the graft bond function with the polymer due to the generation of the resin polymer end groups by cutting the polymer chain, thereby reducing the plant powder content of the final product, and natural decomposition and oxidation of the plastic resin There is a problem that the effect is reduced, resulting in a longer period of final natural degradation. On the other hand, if you use more than 5 parts by weight, the cost increases a lot, there is a problem that the economy is insufficient. Preferably, 0.01 part by weight or more and less than 1.0 part by weight with respect to 100 parts by weight of the eco-friendly bio-based pellets may be used.

The organic acid serves as an intermediate and an oxidizing agent for binding the plant biomass to the polymer terminal group cut by the peroxide. 2 shows this schematic diagram. The peroxide and the organic acid produce the plastic resin-biomass graft bond structure shown in FIG. 2. 3 is a SEM photograph of a pellet fragment in which the graft bonding structure is not produced and a SEM photograph of the pellet fragment in which the graft bonding structure is produced. As can be seen in Figure 3, the plastic resin-biomass graft bonding structure is produced is more entangled than it does not have a feature that the surface of the product when forming the finished product is excellent. The organic acid is preferably at least one selected from citric acid, malic acid, maleic acid, and acetic acid, and the content of the organic acid is 100 parts by weight of the eco-friendly biobased pellet. It is good to use 0.2 weight part or more and less than 5 weight part with respect to it. When the content of the organic acid is less than 0.2 parts by weight, the oxidative decomposition function of the plastic resin is weakened, and when it exceeds 5 parts by weight, there is a burden of cost increase.

Plant powders are generally poor in flow, and conventionally the plant powder content in the production of finished products was difficult to exceed 5 parts by weight. Sufficient graft bonding can improve finished product productivity in injection molding, sheet production, and film extrusion molding, and can increase the content of poor physical properties and poor flowability, such as plant powder.

Graft bonding occurs well when reacted at a screw rotational speed of 300 to 800 rpm at a temperature of 100 to 300 in an extruder such as a single or twin extruder. If the reaction temperature is 100 or less, the added raw materials do not melt and cannot react. If the reaction temperature is 300 or more, carbonization occurs or the temperature is too high to melt the resin to form pellets. In addition, if the screw rotational speed is less than 300rpm, not only productivity is bad, but also sufficient mixing and reaction is difficult, and if more than 800rpm, the internal pressure of the screw rises and the temperature rise by the pressure deepens the plant biomass carbonization.

Meanwhile, starch may be further added to the input as one of plant biomass. The reason for adding more starch is 1) the highest biodegradability among vegetable biomass, 2) cheaper than other raw materials, 3) resource abundance and ease of supply, 4) non-toxicity of raw materials, 5) plasticization This is because it is easy to paint and has excellent physical properties such as plastic. When starch is added, it is preferable to add an additional starch plasticizer. When the starch plasticizer is added, the starch plasticizer is modified at high temperature and high pressure to change the properties of the starch into thermoplastic starch, thereby improving molding processability when producing a finished product (injection, extrusion, film product). If the starch plasticizer is not added, even if the finished product is produced, the physical properties of the product deteriorate due to flowability, moldability, and carbonization. Since starch is a biomass like a plant, plastic resin-starch graft coupling structures as shown in FIG. 2 are generated by peroxides and organic acids like plant powders. The plastic resin-plant graft bond structure and the plastic resin-starch graft bond structure are collectively referred to as a plastic resin-biomass graft bond structure. It will be appreciated that the plant powder and starch may be simultaneously bonded to the plastic resin chain, and a schematic diagram of the plastic resin-biomass graft bonding structure is shown in FIG. 4. The starch plasticizer is suitably 10 to 30 parts by weight of the starch weight. If it is less than 10 parts by weight, starch denaturation is not easy, and if it exceeds 30 parts by weight, the price is high and economical efficiency is lowered. The starch plasticizer uses any one or more selected from glycerin and sorbitol.

Higher plant biomass content in the final product is desirable in terms of lower carbon dioxide emissions.In general, plants have poor physical properties such as elongation, strength, and flowability, and therefore cannot add a large amount to the finished product, thereby increasing the amount of insufficient plant biomass. As a role, the location of starch is important. The particle size of the starch is acceptable because it is used by plasticizing the starch and converting it into thermoplastic starch. Starch materials can vary, but the properties of underground starch (starch sweet potatoes, potatoes, Taupica, etc.) are better. In Korea, however, the price is too high. As an alternative to this, ground starch (corn, wheat, rice starch, etc.) may be used. Corn is preferable because of various conditions.

A compatibilizer is used as a material that gives compatibility by removing the releasability between the non-polar plastic resin polymer and the polar plant biomass. The compatibilizing agent can be used without limitation as long as it is commonly used in the art, including glycidyl methacrylate, ethylene vinyl alcohol, polyvinyl alcohol and ethylene vinyl acetate. However, more preferably, a polyolefin-based polymer of Formula 1 or a polyolefin-derived polymer of Formula 2 may be used. Commercially available products include, for example, ADPOLY PH-200, EM-200, and SMS-554 (Honam Petrochemical Co., Ltd.). The compatibilizer is preferably used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the total environmentally friendly bio-based pellets of the present invention. If it is used in an amount less than 0.5 parts by weight is insufficient compatibility may occur between the delamination, when used in an amount of more than 5 parts by weight it is not possible to obtain an economic effect. More preferably used in an amount of 0.5 to 3 parts by weight, based on the total weight of the composition.

Formula 1

In which R is H or CH ₃

(2)

In which R is H or CH ₃

In addition, an oxidant is additionally added to accelerate decomposition of the polymer material such as plastic resin and the like and to promote thermal decomposition and photolysis. The oxidizing agent may be one or more of oleic acid, linoleic acid, linolenic acid, arachidonic acid, palmitoleic acid, etc. as an unsaturated fatty acid series. The amount of the oxidizing agent added may be used in an amount of 0.2 parts by weight to 6 parts by weight based on 100 parts by weight of the eco-friendly bio-based pellet. If the amount of the oxidizing agent is less than 0.2 parts by weight, the oxidative decomposition function of the polymer material such as plastic resin is weakened, and when used in excess of 6 parts by weight, there is a problem in that the product properties are lowered and the productivity deteriorates during production.

Since natural plant biomass has a large molecular weight and is not melted by heat, there is a problem in that the flowability is poor in the production of pellets. The eco-friendly bio-based pellets may further include a lubricant as it is necessary to enable smooth production of the pellets by improving the flowability when using the natural product / plant raw materials. The lubricant may be one or a mixture of two or more selected from the group consisting of stearic acid salts, palmitate salts and laurate salts, which are environmentally friendly natural products. More preferably, calcium stearate, zinc stearate or mixtures thereof may be used. The lubricant is preferably used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the eco-friendly bio-based pellets. When the amount is less than 0.5 parts by weight, the lubricant has a weak role, and when used in excess of 5 parts by weight, debris such as debris occurs in the die, and the cost increases.

The eco-friendly bio-based pellet may further include an inorganic filler. The content of the inorganic filler is preferably 10 parts to 65 parts by weight based on 100 parts by weight of the eco-friendly bio-based pellets. When the inorganic filler is used in less than 10 parts by weight, the cost reduction is less affected, and when using more than 65 parts by weight, the physical properties such as tensile strength, elongation of the product. In order to improve the physical properties, the inorganic filler is used in the amount of 1 to 50 parts by weight of nano-sized powder in 100 parts by weight of the total. More preferably, those containing 80 to 100 powder in an amount of 10 to 30 parts by weight are used.

The powdery mixture produced through the above process is completed. Since such a composition is in a powder state, a material that serves as a binder for tangling the powder is required. Plastic resins used as binder materials include linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), vinyl acetate (PVAc), and polyamide (PA). , Polycarbonate (PC) and acrylonitrile butadiene styrene (ABS) can be used. The binder may be used in an amount of 15 parts by weight to 70 parts by weight based on 100 parts by weight of eco-friendly bio-based pellets. If the content of the binder is less than 15 parts by weight, there is a risk that the finished pellets are fragile or cracked, and if the content of the binder exceeds 70 parts by weight, the economical efficiency of the finished pellets is lost.

     Then, in step E, the mixture in which the above-mentioned materials are mixed is discharged through a discharge port while performing a plastic resin-plant graft bonding using a uniaxial or biaxial extruder, and the discharged strand is conveyed through a conveyor belt, Or a die-face hot-cutting method to produce an eco-friendly bio-based pellet composition that is a plastic resin-plant biomass graft bond structure composition.

In addition, a moisture resorption prevention system using a dehumidified constant temperature silo can be operated.

     In the manufacturing process, the synthetic resin is decayed to the accumulation of light, heat, mechanical energy, etc. in the nature through the initial oxidation process of the oxidizing agent is reduced in molecular weight while undergoing the decomposition process. Reducing the molecular weight, the first collapsed resin is converted to the natural source of natural microorganisms containing the carbonyl group in the terminal portion by a continuous oxidation reaction is reduced to nature. Resins with a molecular weight of 20,000 or less become a food source for various microorganisms present in the environment and can be processed in an ecological cycle. Inorganic fillers, which were originally part of the soil as natural minerals in nature, are decomposed and decomposed and then released from the base metal, are released into nature, and reduced to soil. In addition, the plant biomass is released from the mid-stage base material after the start of decay and reduced to the natural ecological circulation. As described above, the bio-based plastic of the present invention may be oxidized and biodegraded through separate landfilling, incineration, and the like, and then recovered as a resource by using heat.

The eco-friendly bio-based pellets according to the present invention can be molded into a product to be manufactured by injection molding, extrusion molded article, etc. by mixing a conventional thermoplastic polymer resin, such as plastic and other composition components on the fly according to the application. 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 in advance, and then may be molded back into a desired product if necessary.

In addition, a variety of well-known components that can be used as additives for plastic production can be added in a predetermined amount to improve processability, product stability, product performance, and the like. For example, a surface treating agent may be added in a predetermined amount to enhance bonding strength and reduce repulsion, and a stabilizer may be added to maintain the physical and chemical properties of the resin during the life of the plastic product so as not to decompose. It can be added in an amount of. In the present invention, linear organic thermal stabilizers and antioxidants (irganox 1010 or 1076 series) having a molecular weight of less than 2,000 are added in predetermined amounts in order to prevent deformation and carbonization of the compound to maintain mechanical properties and processing stability. It is also desirable to.

Hereinafter, the present invention will be described in more detail by way of examples. The following examples are intended to illustrate the invention and are not intended to limit the invention thereto.

<Examples 1-8>

Preparation of Eco-friendly Bio-Based Pellets

&Lt; Example 1 >

   Oxygen, a by-product generated during the manufacture of corn starch, was pulverized to about 150 mesh to produce octane powder, and then heated and dried at 100 to 30 minutes to prepare a dried octane powder. 1.5 parts by weight of LC wax 102N (from Lion Chemical) was added to the dried octane powder, followed by high speed agitation at 500 rpm to coat the octave powder surface. With respect to 100 parts by weight of the eco-friendly bio-based pellet composition, 25 parts by weight of the surface-coated oxime powder, 25 parts by weight of polypropylene, 10 parts by weight of LLDPE, 0.5 parts by weight of maleic acid, 0.01 parts by weight of dicumyl peroxide, 20 parts by weight of corn starch 4 parts by weight of sorbitol, 0.3 parts by weight of linoleic acid, 1.0 part by weight of calcium stearate, 1 part by weight of EM-200 (Honam Petrochemical), and the remainder were added to a high speed stirrer, followed by stirring at 400 rpm to form a mixture. Using a twin screw extruder, an eco-friendly bio-based pellet made of plastic resin-biomass graft bond was prepared.

<Example 2>

Except that 30 parts by weight of the oxidized powder in Example 1 to produce the same composition for pellets as in Example 1, to prepare a pellet.

<Example 3>

Except that 35 parts by weight of the oxidized powder in Example 1 to produce the same composition for pellets as in Example 1, to prepare a pellet.

<Example 4>

Except that 40 parts by weight of the oxidized powder in Example 1 to produce the same composition for pellets as in Example 1, to prepare a pellet.

<Example 5>

In Example 1, 0.5 parts by weight of citric acid was added instead of 0.5 parts by weight of maleic acid, and 0.02 parts by weight of benzoyl peroxide was added instead of 0.01 parts by weight of dicumyl peroxide to produce the same composition for pellets as in Example 1. To prepare pellets.

<Example 6>

In Example 5, except that 30 parts by weight of the oxid powder was produced in the same composition for pellets as in Example 6, to prepare a pellet

&Lt; Example 7 >

In Example 5, except that 35 parts by weight of the oxid powder was produced in the same composition for pellets as in Example 6, to prepare a pellet.

&Lt; Example 8 >

In Example 5, except that 40 parts by weight of the oxidized powder was produced in the same pellet composition as in Example 6, to prepare a pellet

&Lt; Comparative Example 1 &

In Example 1, except that 0.5 parts by weight of maleic acid, 0.01 parts by weight of dicumyl peroxide was subtracted to produce the same composition for pellets as in Example 1, to prepare a pellet.

Comparative Example 2

In Example 5, except that 0.5 parts by weight of citric acid and 0.02 parts by weight of benzoyl peroxide was removed, the same composition for pellets as in Example 5 was produced to prepare pellets.

<Examples 9-16>

Manufacturing of Eco-friendly Injection Molded Products

&Lt; Example 9 >

30 parts by weight of the pellets prepared in Example 1 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Hunan Petrochemical products

&Lt; Example 10 >

30 parts by weight of the pellets prepared in Example 2 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Hunan Petrochemical products

<Example 11>

30 parts by weight of the pellets prepared in Example 3 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Hunan Petrochemical products

&Lt; Example 12 >

30 parts by weight of the pellets prepared in Example 4, 70 parts by weight of polypropylene (PP), and 15 parts by weight of homo polypropylene were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Hunan Petrochemical products

&Lt; Example 13 >

30 parts by weight of the pellets prepared in Example 5 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Hunan Petrochemical products

&Lt; Example 14 >

30 parts by weight of the pellets prepared in Example 6 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Honam Petrochemical.

&Lt; Example 15 >

30 parts by weight of the pellets prepared in Example 7 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Honam Petrochemical.

&Lt; Example 16 >

30 parts by weight of the pellets prepared in Example 8 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Honam Petrochemical.

<Example 17>

30 parts by weight of the pellets prepared in Comparative Example 1 and 70 parts by weight of polypropylene (PP) were mixed and then injection molded articles were produced by using an ordinary injection molding machine. PP used Honam Petrochemical.

&Lt; Example 18 >

30 parts by weight of the pellets prepared in Comparative Example 2 and 70 parts by weight of polypropylene (PP) were mixed, and then injection molded products were manufactured using a conventional injection molding machine. PP used Honam Petrochemical.

Experimental Example 1

Example  Mechanical property test of eco-friendly injection molded parts manufactured according to 9 ~ 18

Tensile strength and elongation were measured for the samples cut to 25102 mm according to the ASTM D 3826 method for the injection molded article prepared in Examples 9-18. In order to reduce the measurement error, the number of injection molded samples was measured 10 times for each measurement item and the average value was taken out of the maximum and minimum values. Load cell was used 50kg and UTM (Universal Testing Machine, Daekyung Tech, Korea) machine was used, the tensile speed of the machine was set to 50mm / min and the experiment was carried out, the results are summarized in Table 1 below.

Mechanical property test result division The tensile strength(/) Elongation (%) PP products 286 200 Example 9 283 200 Example 10 279 197 Example 11 275 195 Example 12 273 193 Example 13 282 198 Example 14 278 196 Example 15 274 193 Example 16 272 192 Example 17 269 179 Example 18 267 176

As can be seen in Table 1, the injection molded article using the octaphy, one of the plant biomass according to the present invention can be seen that the tensile strength and elongation similar to the existing product despite the inclusion of starch, organic acid, peracid. In Examples 17 and 18 corresponding to Comparative Examples 1 and 2, it can be seen that the tensile strength and the elongation are lower than those of Examples 9 to 16, which correspond to the existing products or examples of the present invention.

<Experimental Example 2>

Example  Of eco-friendly injection molded products manufactured according to 9 ~ 18 Photodegradable  evaluation

Photodegradation was performed by irradiating ultraviolet rays for 200 hours using a QUV Accelerated Weathering Tester according to ASTM D15 UV treatment test method, and then measuring the tensile strength and elongation of the sample. At this time, the type of ultraviolet (UV) lamp was UVB 313, the light intensity (Irradiance) was 0.60w / nf (310) and the results are shown in Table 2 below.

Photodegradability Test Results division Strength retention rate (%) % Retention PP products 97.6 97.2 Example 9 2.3 1.4 Example 10 0.7 0.3 Example 11 0.5 0.0 Example 12 0.2 0.0 Example 13 2.9 1.4 Example 14 1.5 0.7 Example 15 1.0 0.2 Example 16 0.6 0.0 Example 17 36.3 30.5 Example 18 37.1 32.1

As can be seen from Table 2, the strength retention and elongation retention of the existing PP products are hardly reduced even after UV irradiation, whereas the injection molded articles to which the bio-based pellets according to the present invention are applied have a significantly reduced strength retention and elongation retention. It became. In Examples 17 to 18 without using an organic acid and a peroxide, strength and elongation were reduced by more than 60% compared to the PP product. That is, it can be seen that the injection molded article of the present invention can be decomposed to a considerable extent in a natural state by light such as ultraviolet rays. In addition, it can be seen that as the plant content increases, the degree of decomposition further increases.

<Experimental Example 3>

Example  Eco-friendly manufactured according to 9-18 Of injection molded products  Biodegradability Assessment

Evaluation of the biodegradability by the fungus of injection molded articles made from pellets using octaves in the plant biomass of the present invention was tested according to the ASTM G 21 method. That is, the AAS that after cutting the sample to a predetermined size by using a solid agar medium without a carbon source as a medium commonly found in the soil and this switch Aspergillus (Aspergillus niger ), Penicillium piniphilum), while tomyum Globo Island (Chaetomium globosum), glycidyl Eau radium by lances (Gliocladium and evaluated according to virens), and Aureobasidium pullulans (Aureobasidium pullulans) ASTM G 21 how the degree of mold covered a period of 60 days a sample of mixed fungal spore suspension was sprayed under aseptic conditions at 10 day intervals was measured biodegradability.

In addition, the biodegradability evaluation by bacteria was tested according to the ASTM G 22 method. A cell mixture suspension of Pseudomonas aeruginosa and Baccllus subtillus was applied to the sample in a sterile state on a solid agar medium without a carbon source. The biodegradability was measured according to the evaluation, and Table 3 shows the biodegradation notation method.

Biodegradation Notation Method Growth in Observed Samples Rating  none 0  Growth traces (less than 10%) One  Slight growth (10-30%) 2  Medium growth (30-60%) 3  Overgrowth (60% ~ completely cover the surface) 4

In addition, at the same time, the sample of the eco-friendly injection molded product is sampled every 20 days while being kept in a constant temperature and humidity chamber fixed at a relative humidity of 85% and an internal temperature of 30, and the weight loss degree of the sample according to the degree of growth of the mold is proportional. Was measured.

In the case of bacteria, the relative humidity was fixed at 85% and the internal temperature 37, and the weight loss was measured in the same manner as described above.

In order to reduce the measurement error, the number of injection molded samples was measured 10 times for each measurement item and the average value was taken out of the maximum and minimum values.

* The results are shown in Tables 4 and 5 below.

Evaluation of biodegradation by mold and weight loss test results division Degree of biodegradation (%) Weight loss rate (%) ^* 10 days 20 days 30 days 40 days 50 days 60 days 20 days 40 days 60 days PP products 0 0 0 0 0 0 99.9 99.9 99.9 Example 9 One 2 2 3 4 4 94.0 72.8 58.1 Example 10 One 2 3 4 4 4 92.7 70.9 53.1 Example 11 One 2 3 4 4 4 91.8 66.3 49.8 Example 12 2 3 3 4 4 4 90.4 63.2 45.7 Example 13 One 2 2 3 4 4 94.5 73.7 60.9 Example 14 One 2 3 3 4 4 92.9 72.3 56.7 Example 15 One 2 3 4 4 4 91.8 68.9 52.1 Example 16 2 3 3 4 4 4 91.6 67.3 51.1 Example 17 One 2 2 2 3 3 95.3 77.2 68.3 Example 18 One 2 2 2 3 3 95.7 77.4 67.5

* Weight loss rate (%) = weight after sampling / weight of original sample 100

Evaluation of the degree of biodegradation by bacteria and weight loss test results division Degree of biodegradation (%) Weight loss rate (%) ^* 10 days 20 days 30 days 40 days 50 days 60 days 20 days 40 days 60 days PP products 0 0 0 0 0 0 99.9 99.8 99.8 Example 9 One 2 2 3 4 4 94.2 72.3 54.8 Example 10 One 2 3 3 4 4 92.8 71.4 52.3 Example 11 One 2 3 4 4 4 92.1 68.3 50.1 Example 12 2 3 3 4 4 4 90.6 63.1 47.4 Example 13 One 2 2 3 4 4 95.1 73.9 61.6 Example 14 One 2 3 3 4 4 94.2 71.8 56.1 Example 15 One 2 3 4 4 4 92.6 69.8 52.3 Example 16 2 3 3 4 4 4 91.7 68.2 51.1 Example 17 One 2 2 2 3 4 95.9 78.1 67.8 Example 18 One 2 2 2 3 3 96.1 77.8 67.8

As can be seen from Tables 4 and 5, the existing PP products are hardly decomposed by bacteria or molds over time, and only partially decompose in the case of Examples 17 to 18 without using organic acids and peroxides. It was a progress. Eco-friendly injection molded article according to the present invention can be seen that significantly progressed by the bacteria and mold over time. In addition, if the biomass content, such as plants, it can be seen that the growth of bacteria and fungi faster.

The present invention can be utilized in various manufacturing industries, such as carbon dioxide reduction, biodegradability and bio-based plastics industry by replacing plastics.

Claims (11)

(A) milling the plant into fine particles of 80 to 300 mesh or less to produce a plant powder;
(B) heating the plant powder at 50 degrees to 150 for 0.5 hours to 24 hours to remove moisture;
(C) adding wax to the heat-dried plant powder and stirring the mixture for 10 to 30 minutes at a stirring speed of 300 to 800 RPM to produce a coated plant powder;
(D) a plastic resin serving as a binder to the coated plant powder, including an organic acid and a peroxide, and adding and mixing to form a mixture;
(E) Injecting the mixture into the extruder so that the plastic resin-biomass graft coupling is performed, and discharges the plastic resin-biomass graft coupling material through the discharge port, and discharges the discharged strand on the conveyor belt. Method for producing eco-friendly bio-based pellets comprising the; comprising; pellet manufacturing step of manufacturing the pellet by cutting or die-face hot-cutting after blowing through the air blowing
The method of claim 1,
In the step (D), the starch and starch plasticizer is further added before mixing the input,
The starch is 5 to 50 parts by weight based on 100 parts by weight of the pellet composition,
The starch plasticizer is one or more of glycerin and sorbitol,
The content of the starch plasticizer is a method for producing eco-friendly bio-based pellets, characterized in that 10 to 30 parts by weight based on 100 parts by weight of the starch based on the starch content.
The method of claim 1,
In the step (D), one or more of a compatibilizer, a lubricant, an oxidant and an inorganic filler is further added before mixing the inputs,
The compatibilizer is 0.5 to 5 parts by weight based on 100 parts by weight of the pellet composition,
The lubricant is 0.5 to 5 parts by weight based on 100 parts by weight of the pellet composition,
The oxidizing agent is 0.2 to 6 parts by weight based on 100 parts by weight of the pellet composition,
The inorganic filler is 10 to 65 parts by weight based on 100 parts by weight of the pellet composition,
The compatibilizer is one or more of glycidyl methacrylate, ethylene vinyl alcohol, polyvinyl alcohol and ethylene vinyl acetate, ADPOLY PH-200, EM-200, SMS-554,
The lubricant is one or more of zinc stearate and calcium stearate,
The oxidizing agent is any one or more of oleic acid, linoleic acid, linolenic acid, arachidonic acid and palmitoleic acid,
The inorganic filler is any one or more of calcium carbonate, clay, ocher, talc and kaolin,
The inorganic filler is a method for producing eco-friendly bio-based pellets, characterized in that the nano-size powder of 1 to 50 parts by weight of 100 parts by weight in total.
The method of claim 1,
The peroxides are azo-bis-isobutylnitrile, tributyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-tributylbutyloxide, 2,5 dimethyl-2,5 di (thibutylperoxy) Hexane (2,5-Dimethyl-2,5-di (t-butyl peroxy) hexane), 1,3-bis (thi-butylperoxy-isopropyl) benzene (1,3-Bis (t-buthyl peroxy- isoproply) benzene),
The content of the peroxide is 0.01 to 5 parts by weight based on 100 parts by weight of the plastic resin manufacturing method of eco-friendly bio-base pellets.
The method of claim 1,
The organic acid is any one or more of citric acid (Citric acid), malic acid (Malic acid), maleic acid (Maleic aicd), acetic acid (acetic acid),
The amount of the organic acid is 0.2 to 5 parts by weight based on 100 parts by weight of the pellet composition, the method for producing eco-friendly bio-based pellets.
The method of claim 1,
The wax is any one or more of paraffin wax, liquid paraffin wax, beeswax, drive wax, emulsion wax, candelilla wax, P. wax, P. wax,
The content of the wax is a method for producing eco-friendly bio-based pellets, characterized in that 1.0 to 5.0 parts by weight based on 100 parts by weight of the pellet composition.
The method of claim 1,
The content of the plant is 10 to 50 parts by weight based on 100 parts by weight of the pellet composition,
The sum of the contents of the plant and starch is increased as the content of the plastic resin increases,
The content of the peroxide is increased as the content of the plastic resin increases,
The content of the organic acid is a method of producing an eco-friendly bio-base pellets, characterized in that the increase in the content of the sum of the contents of the plant and starch increases.
The method of claim 1,
The plastic resin of the binder role is linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS), vinyl acetate (PVAc), polyamide (PA), poly One or more of carbonate (PC) and acrylonitrile butadiene styrene (ABS),
The content of the plastic resin is 15 to 70 parts by weight based on 100 parts by weight of the pellet composition,
Melt index (MI) of the plastic resin is a manufacturing method of eco-friendly bio-based pellets, characterized in that 3.0.
The method of claim 1,
The plant is a method of producing an environmentally-friendly bio-based pellets, characterized in that the grain shell, organic industrial waste generated in the processing process in the food factory, grain bar or a mixture thereof.
The method of claim 1,
The coating step of step (B) and the step (C) is an environmentally-friendly method for producing bio-base pellets, characterized in that is carried out at the same time.
Eco-friendly bio-based pellets prepared by the method of any one of claims 1 to 9

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