KR101217788B1 - Biomass pellet by using corn cob and its preparing method - Google Patents

Abstract

The present invention relates to a biomass pellet and a method for producing the same using a corn core which is a plant biomass, and more particularly, (A) grinding corn cores into fine particles of 80 to 400 mesh or less to produce corn core powder; (B) heat-drying the corn core powder at 50 ° C. to 150 ° C. to remove moisture, and adding wax to the heat-dried corn core powder and stirring to produce a coated corn core powder; (C) adding a plastic resin polymer serving as a binder and the organic acid and a peroxide to the coated corn core powder, and mixing the mixture to produce a mixture; (D) Injecting the mixture into a twin extruder to make a plastic resin-plant graft bonding, and the pellets are produced by cutting or face-cutting after cooling the air while conveying the strand discharged through the die through a conveyor belt It relates to a biomass pellet using a plant corn core and a method for producing the same, comprising: producing biomass pellets using plant corn cores. By utilizing the present invention, it is possible to produce biomass pellets that are endowed with natural decomposition properties and have a high content of corn core powder.

Description

Biomass pellets and its manufacturing method using plant corn core {Biomass pellet by using corn cob and its preparing method}

The present invention relates to biomass pellets using corn cores of plant biomass and a method of manufacturing the same, and more particularly, to process injection molded products such as baby products, bathroom products, and kitchen products, and food packaging materials, vinyl, and industrial packaging materials. The present invention relates to a biomass pellet capable of naturally degrading in a natural state and a method of manufacturing the same.

Biomass plastics are plastics containing 25% or more of so-called biomass derived from plants such as corn, and the effect of suppressing the increase in the concentration of carbon dioxide in the atmosphere by using a plant resource in which carbon in the atmosphere is fixed by photosynthesis as a raw material In addition, it is possible to reduce the consumption of petroleum, a limited resource, and since it is decomposed by microorganisms after disposal, has recently attracted attention as an environmentally friendly degradable material.

Natural decomposition involving biomass 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 step is a chemical decomposition (molecular weight reduction) step, the automatic oxidation reaction proceeds by the carboxylic acid, ketones, aldehydes, etc. generated due to the natural decomposition, the surface gradually becomes hydrophilic to promote thermal and chemical 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. What is needed is a biodegradable composition to contribute to the decomposition of the first and second stages above.

Corn is a perennial crop belonging to the flower family, and it varies depending on the region. However, it grows well without being affected by drought or rainy season and the soil is not oiled.

Corn core is a sorghum-like part inside the corn stalk and the rest of the corn kernels, which is one of the biomass raw materials. If you use corn core, unlike other natural products, it can be purchased at a low price, has the advantage of easy powdering, and has an excellent decomposition effect. However, unlike other plants, corn core has a low content of fiber, which causes severe carbonization during injection molding, and it is hard to exceed 5% due to poor flowability. Therefore, there is a demand for developing an effective method for increasing the content of corn cores in corn core compositions used for injection molding and using corn cores in large quantities.

The first problem to be solved by the present invention is to disclose a method for producing biomass pellets with a high content of corn core, one of the plant biomass.

Another problem to be solved by the present invention is to disclose a biomass pellet with a high content of corn core.

In order to achieve the object of the present invention, (A) grinding the corn core into fine particles of 80 to 400 mesh or less to produce corn core powder; (B) heating the corn core powder at 50 to 150 ° C. to remove moisture, and adding wax to the heat dried corn core powder and stirring to produce a coated corn core powder; (C) adding a plastic resin polymer serving as a binder and the organic acid and a peroxide to the coated corn core powder, and mixing the mixture to produce a mixture; (D) Injecting the mixture into a twin extruder to achieve a plastic resin-plant graft bond, and discharge the material made of the plastic resin-plant graft bond through the discharge port, the discharged strands to the conveyor belt Using a large amount of plant corn core, characterized in that it comprises a; comprising the step of preparing a biomass pellet composition which is a plastic resin-plant graft bonding structure composition by drying after blowing air blowing while transporting through A method of making a given biomass pellet is presented.

In the step (C), the starch and starch plasticizer is further added before mixing the input, wherein the starch is 5 to 50 parts by weight based on 100 parts by weight of the biomass pellet composition endowed with the biodegradable properties. desirable.

In the step (C), it is to add any one or more of a lubricant, an oxidant and an inorganic filler before mixing the input, the lubricant is 0.5 to 5 parts by weight based on 100 parts by weight of the biomass pellet composition, The oxidizing agent is preferably 0.2 to 6 parts by weight based on 100 parts by weight of the biomass pellet composition.

The inorganic filler is preferably 10 to 65 parts by weight based on 100 parts by weight of the biomass pellet composition.

The peroxide is any one of dicumyl peroxide, benzoyl peroxide, di-tributyl peroxide, and 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.

The organic acid is any one or more of citric acid, citric acid, malic acid, maleic acid, acetic acid, and the amount of the organic acid is 0.2 to 100 parts by weight of the biomass pellet composition. It is preferable that it is 5 weight part.

The glidants may be used without limitation, those generally known, and specifically, one or more of zinc stearate and calcium stearate, and the oxidizing agent is any one or more of oleic acid, linoleic acid, linolenic acid, arachidonic acid, and palmitoleic acid, The inorganic filler is preferably one or more of calcium carbonate, clay, talc and loess.

The inorganic filler is preferably 10 to 65 parts by weight based on 100 parts by weight of the biomass pellet composition.

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 corn core powder is 10 to 50 parts by weight based on 100 parts by weight of the biomass pellet composition, the combined content of the corn core and starch is increased as the content of the plastic resin is increased, The content is increased as the content of the plastic resin increases, and the content of the organic acid is preferably increased as the combined content of the corn core and starch increases.

The binder resin of step (C) is any one of linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS) and acrylonitrile butadiene styrene (ABS) It is preferable that it is above.

The binder resin is preferably a pellet having a melt index of 3.0 or more.

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

In order to achieve another object of the present invention, there is proposed a biomass pellet using a plant corn core endowed with natural decomposition properties produced by the above-described manufacturing method.

Utilizing the present invention, it is possible to produce biomass pellets with increased use of corn cores.

1 is an exemplary flow chart of a method for producing biomass pellets using the plant corn core of the present invention.
FIG. 2 is a schematic diagram in which a plastic resin-plant graft bonding structure is produced. FIG.

Hereinafter, it demonstrates in detail, referring drawings.

1 is a flow chart of an embodiment of a method for producing biomass pellets using corn cores of the present invention.

The present invention is a method for producing biomass pellets using plant corn core is largely divided into four steps. Step A is a step of producing corn core powder by grinding the corn core. Corn cores are pulverized into fine powder so as to be about 80 to 400 mesh. If the particle size 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, injection molded product, extruded product, etc. is deteriorated, If it exceeds 400 mesh, the particle size is very small, so the product quality is excellent, but the grinding process time is too long, resulting in lower overall productivity and lower price competitiveness due to higher costs.

Subsequently, in step B, the corn core powder is coated with wax to produce a coated corn core powder. In the coating step, the corn core powder is dried by heating at 50 to 150 degrees to remove moisture, and the wax is added to the heat dried corn core powder and stirred to produce a coated corn core 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 not enough drying or drying takes a long time, and if the drying temperature is higher than 150 degrees, there is a problem that corn cores and the like are likely to be carbonized, thereby deteriorating product quality.

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.

Wax was added to the dried corn core powder and stirred at 300 to 800 rpm at high speed to coat the surface of the corn core powder. The added wax is dissolved by self heating (self-heating) and coated on the surface of corn core powder. The coated corn core powder is prevented from reabsorbing moisture. Wax has the advantage of low molecular weight and low melting point can also perform a function as a lubricant aid when preparing the additive composition 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% of the content of corn core powder. When used less than 1%, the lubricant has a weak role, and when used more than 20%, debris such as debris occurs in the die, the cost increases. If a lot of wax is used, the coating for water resistance is excellent, but it is recommended to use 1 to 5 parts by weight based on 100 parts by weight of the biomass pellet composition because debris is generated in the production equipment die in injection, extrusion and film production. Even better.

In the coating step, the wax is added and then stirred at high speed at 300-800 rpm. Thus, the wax is naturally melted by the self-heating by the high speed stirring, and the surface of the corn core powder is coated. The coating time is not specified and the coating is finished in the point that the coated corn core powder becomes a certain lump form. In general, the coating finishes in a little lump form in about 10 to 30 minutes.

Subsequently, the step of forming a mixture by adding and mixing the plastic resin polymer, organic acid and peroxide serving as a binder to the corn core powder coated in step C. Peroxides chemically cut the polymer chains of plastic resins. The organic acid serves as an intermediate for bonding plants such as corn cores to the terminal portion of the cut plastic resin polymer. 2 shows this schematic diagram. Peroxides and organic acids allow plastic resin-plant graft bonding structures such as those of FIG. 2 to be produced. The organic acid binds to the polymer terminal group cut by the peroxide. The peroxide is preferably the peroxide is any one of dicumyl oxide, benzoyl peroxide, di- triple butyl peroxide. Peroxides include azo-bis-isobutylnitrile, tributyl hydroperoxide, dicumyl peroxide, 2,5 dimethyl-2,5 di (thibutylperoxy) hexane (2,5-Dimethyl-2,5- di (t-butyl peroxy) hexane), 1,3-bis (ti-butylperoxy-isopropyl) benzene (1,3-Bis (t-buthyl peroxy-isoproply) benzene), etc. may also be used, but the experimental results Mill oxide, benzoyl peroxide, and di-triple butyl peroxide were good, and the effect of producing graft-bonded structures of corn core powder and plastic polymer of dicumyl oxide was the most preferable, resulting in the best productivity of finished products such as injection molded products.

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, it is difficult to expect graft bonding, that is, commercialization function, there is a problem that the corn core content of the final product is reduced, and the final decomposition period is long due to the natural decomposition and oxidation effect of the plastic resin is reduced There is. 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 0.5 part by weight based on 100 parts by weight of the biomass pellet composition may be used.

The organic acid binds to the polymer terminal group cut by the peroxide and serves as an oxidative decomposition agent. The organic acid is preferably at least one selected from citric acid, malic acid, maleic acid, acetic acid, and the content of the organic acid is 100 parts by weight of the biomass pellet composition. 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.

Corn core powder, like other plant powders, was poor in flowability, and the corn core powder content was hard to exceed 5% in the manufacture of injection molded articles. If graft bonding is sufficient, the productivity of finished products such as sheet production and extrusion molding as well as injection molding can be improved, and the content of poor physical and flowable substances such as corn core powder can be increased.

Graft bonding occurs well when extruders such as twin extruders react at screw speeds of 200 to 600 rpm at temperatures of 100 to 200 ° C. If the reaction temperature is 100 ℃ or less, the added raw materials are not melted and can not be reacted. If the temperature is higher than 200 ℃, carbonization occurs, or the temperature is too high, so that the resin melts like water and cannot be pelletized.

Meanwhile, starch may be further added to the input as one of the biodegradable plants. 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. Starch is also a naturally degradable plant, such as corn core, so that the plastic resin-plant graft bond structure shown in FIG. The plastic resin-corn deep powder graft bond structure and the plastic resin-starch graft bond structure are collectively referred to as a plastic resin-plant graft bond structure. It will be apparent that corn core powder and starch may be simultaneously bound to the plastic resin chain, and a schematic diagram of the plastic resin-plant graft bonding structure is shown in FIG. 2. The starch plasticizer is suitably 10% to 30% by weight of the starch weight. If it is less than 10%, starch denaturation is not easy, and if it exceeds 30%, the price is high and economic efficiency is low.

Higher plant biomass content in the final product is desirable in terms of reducing carbon dioxide emissions. Corn cores are not suitable for adding a large amount to finished products due to poor physical properties such as elongation, strength, and flowability, which increases the amount of insufficient plant biomass. As is the position of the starch is important. The particle size of the starch is fine because the starch can be plasticized and used as a thermoplastic starch. Starch materials can vary, but the properties of underground starch (starch sweet potatoes, potatoes, Taupica, etc.) are better. However, there is a problem that the price is too expensive in Korea. As an alternative to this, ground starch (corn, wheat, rice starch, etc.) may be used. Corn is preferable because of various conditions.

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 used as 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 0.2 to 6 parts by weight or more based on 100 parts by weight of the biomass pellet composition. 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.

Natural plants have a high molecular weight and are not melted by heat, and thus have poor flowability in the production of pellets. The biomass pellet composition may further include a lubricant as it is necessary to improve the flowability when using such natural materials / plant raw materials to enable smooth production of the pellets. Suitable lubricants are zinc stearate and calcium stearate. The amount of the lubricant is preferably 0.5 parts by weight or more and less than 5 parts by weight based on 100 parts by weight of the biomass pellet composition. 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 biomass pellet composition may further include an inorganic filler. The content of the inorganic filler is preferably 10 parts by weight to 65 parts by weight based on 100 parts by weight of the biomass pellet composition. 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.

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. The plastic resin used as the binder material may be linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS) and acrylonitrile butadiene styrene (ABS). . The binder may be used in an amount of 15 parts by weight to 60 parts by weight based on 100 parts by weight of the biomass pellet composition. 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 60 parts by weight, the economical efficiency of the finished pellets is lost.

Subsequently, in step D, the mixture containing the above-mentioned materials is discharged through a discharge port while the plastic resin-plant graft is bonded using an extrusion apparatus such as a twin screw extruder, and the blown strand is blown dry while conveying the discharged strand through the conveyor belt. The biomass pellet composition, which is a plastic resin-plant graft bonding structure composition, is prepared by cutting or face cutting.

The biomass pellet composition according to the present invention may be molded into a product to be manufactured by injection molding, extrusion molded article, etc., by mixing a mixture of a conventional thermoplastic polymer such as plastic and other composition components in accordance with 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.

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>

Plant Corn core  Used Biomass  Manufacture of pellets

&Lt; Example 1 >

Corn core was pulverized to about 150 mesh to produce corn core powder, and then heated and dried at 100 ° C. for 30 minutes to prepare dried corn core powder. 1.5 parts by weight of LC wax 102N (Lion Chemical) was added to the dried corn core powder, and the corn core powder surface was coated by high speed stirring at 500 rpm. 100 parts by weight of the plastic resin-biomass pellet composition, 25 parts by weight of surface-coated corn core powder, 25 parts by weight of polypropylene, 10 parts by weight of linear low density polyethylene (LLDPE), 20 parts by weight of corn starch, 4 parts by weight of sorbitol , 0.3 part by weight of linoleic acid, 1.0 part by weight of zinc stearate, 0.5 part by weight of maleic acid, 0.01 part by weight of dicumyl peroxide and the remainder were added to a high speed stirrer with calcium carbonate, followed by stirring at 400 rpm to produce a mixture. Biomass pellets were made using the plastic resin-plant graft bond.

<Example 2>

In Example 1, except that 30 parts by weight of corn core powder and 0.02 parts by weight of dicumyl peroxide were prepared, the same composition for pellets as in Example 1 was produced to prepare pellets.

<Example 3>

Except 35 parts by weight of corn core powder in Example 1, 0.03 parts by weight of dicumyl peroxide was added to produce the same composition for pellets as in Example 1, to prepare a pellet.

 <Example 4>

40 parts by weight of corn core powder was added in Example 1, except that 0.04 parts by weight of dicumyl peroxide was added to produce the same composition for pellets as in Example 1 to prepare pellets.

<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 corn core powder and 0.03 parts by weight of benzoyl peroxide, the same composition for pellets as in Example 6 was produced to prepare pellets.

 &Lt; Example 7 >

In Example 5, except that 35 parts by weight of corn core powder, and 0.04 parts by weight of benzoyl peroxide, the same composition for pellets as in Example 6 was produced to prepare a pellet.

 &Lt; Example 8 >

 In Example 5, except that 40 parts by weight of corn core powder, and 0.05 parts by weight of benzoyl peroxide to produce the same composition for pellets 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 produced to produce the same pellet composition 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 with Natural Degradation Properties

&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 articles were manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. 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 articles were manufactured under the conditions of an injection pressure of 65 bar and an injection temperature of 240 ° C. 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 articles were manufactured under the conditions of an injection pressure of 65 bar and an injection temperature of 240 ° C. 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 the injection molded article was subjected to an injection pressure of 65 bar and an injection temperature of 240 ° C. using a conventional injection molding machine. Was prepared. 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 articles were manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. 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 articles were manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. 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 articles were manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. 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 articles were manufactured under the conditions of an injection pressure of 65 bar and an injection temperature of 240 ° C. 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 manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. using a conventional 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 articles were manufactured at a injection pressure of 65 bar and an injection temperature of 240 ° C. 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

The injection molded article prepared in Examples 9 to 18 and polypropylene (PP) were cut to 25 × 102 mm according to the ASTM D 3826 method for a PP product produced at a injection pressure of 30 bar and an injection temperature of 240 ° C. in a conventional injection molding machine. Tensile strength and elongation were measured for the samples. 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 Tensile Strength (㎏ / ㎠) Elongation (%) PP products 280 200 Example 9 280 201 Example 10 278 196 Example 11 271 193 Example 12 270 191 Example 13 277 200 Example 14 276 195 Example 15 270 192 Example 16 270 189 Example 17 267 178 Example 18 265 176

As can be seen from Table 1, the injection molded product using corn core, one of the plant biomass according to the present invention, despite the inclusion of corn core powder, organic acid, peroxide, etc., it can be seen that the tensile strength and elongation are similar to the existing products. have. 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 (310nm) and the results are shown in Table 2 below.

Photodegradability Test Results division Strength retention rate (%) % Retention PP products 97.3 96.7 Example 9 2.5 1.6 Example 10 0.9 0.5 Example 11 0.7 0.1 Example 12 0.5 0.0 Example 13 3.2 1.8 Example 14 1.3 0.9 Example 15 1.1 0.5 Example 16 0.7 0.2 Example 17 37.2 32.8 Example 18 38.0 34.1

 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 biomass pellets according to the present invention are significantly reduced in 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 corn core content increases, the degree of degradation increases.

<Experimental Example 3>

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

Evaluation of biodegradability by mold of injection molded articles made from pellets using corn cores of 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 The biodegradability was determined by spraying a mixed mycelium suspension of virens ) and Aureobasidium pullulans in a sterile state and evaluated the extent of mold cover on the samples for 60 days in accordance with ASTM G 21 method at intervals of 10 days.

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

 At the same time, the sample of the eco-friendly injection molded product is taken out 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 ° C. It was measured by the ratio.

In the case of bacteria, the relative humidity was fixed at 85% and the internal temperature of 37 ° C., 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 94.3 74.2 58.3 Example 10 One 2 3 4 4 4 93.2 71.6 52.1 Example 11 One 2 3 4 4 4 92.8 68.3 50.3 Example 12 2 3 3 4 4 4 91.2 63.2 47.7 Example 13 One 2 2 3 4 4 95.6 74.6 61.7 Example 14 One 2 3 3 4 4 94.8 72.2 55.4 Example 15 One 2 3 4 4 4 93.3 69.4 51.7 Example 16 2 3 3 4 4 4 92.8 64.2 50.7 Example 17 One 2 2 2 3 3 96.2 78.4 67.5 Example 18 One 2 2 2 3 3 96.9 78.3 68.0

^* 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 99.9 99.9 Example 9 One 2 2 3 4 4 95.2 73.4 57.7 Example 10 One 2 3 3 4 4 93.9 72.1 53.4 Example 11 One 2 3 4 4 4 92.5 69.6 51.5 Example 12 2 3 3 4 4 4 90.9 63.1 48.9 Example 13 One 2 2 3 4 4 96.1 75.8 62.4 Example 14 One 2 3 3 4 4 94.9 73.3 55.4 Example 15 One 2 3 4 4 4 92.2 69.7 53.9 Example 16 2 3 3 4 4 4 91.0 64.4 51.4 Example 17 One 2 2 2 3 4 96.7 79.2 68.4 Example 18 One 2 2 2 3 3 97.0 78.8 68.1

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, a large amount of biomass, such as corn core, can be seen that bacteria and mold growth is faster.

The present invention can be used in various manufacturing industries, such as carbon dioxide reduction, biomass plastics industry by replacing plastics.

Claims (10)

delete (A) pulverizing the corn core into fine particles of 100 to 300 mesh or less to produce corn core powder;
(B) drying the corn core powder at 80 degrees to 130 for 1.0 hour to 12 hours to remove water, and 1.0 to 5.0 parts by weight of LC wax is added to 100 parts by weight of pellet composition in the dried corn core powder. And stirring at a stirring speed 300 to 800 RPM to produce a coated corn core powder to prevent resorption of water;
(C) adding 10 to 50 parts by weight of the coated corn core powder and 100 parts by weight of the pellet composition and a plastic resin polymer serving as a binder, an organic acid and a peroxide, and mixing to form a mixture;
(D) Injecting the mixture into the extruder to form a plastic resin-plant graft bond, discharge the material made of the plastic resin-plant graft bond through the discharge port, the discharged strand through the conveyor belt In the manufacturing method of biomass pellets comprising; pellet manufacturing step of producing a pellet by cutting or face-cutting after blow drying while transporting,
In the step (C), 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 biomass pellets, characterized in that 10 to 30 parts by weight based on 100 parts by weight of the starch.
(A) pulverizing the corn core into fine particles of 100 to 300 mesh or less to produce corn core powder;
(B) drying the corn core powder at 80 degrees to 130 for 1.0 hour to 12 hours to remove water, and 1.0 to 5.0 parts by weight of LC wax is added to 100 parts by weight of pellet composition in the dried corn core powder. And stirring at a stirring speed 300 to 800 RPM to produce a coated corn core powder to prevent resorption of water;
(C) adding 10 to 50 parts by weight of the coated corn core powder and 100 parts by weight of the pellet composition and a plastic resin polymer serving as a binder, an organic acid and a peroxide, and mixing to form a mixture;
(D) Injecting the mixture into the extruder to form a plastic resin-plant graft bond, discharge the material made of the plastic resin-plant graft bond through the discharge port, the discharged strand through the conveyor belt In the manufacturing method of biomass pellets comprising; pellet manufacturing step of producing a pellet by cutting or face-cutting after blow drying while transporting,
In the step (C), it is to add any one or more of the lubricant, oxidant and inorganic filler before mixing the input,
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 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 a method for producing biomass pellets, characterized in that any one or more of calcium carbonate, clay and loess.
(A) pulverizing the corn core into fine particles of 100 to 300 mesh or less to produce corn core powder;
(B) drying the corn core powder at 80 degrees to 130 for 1.0 hour to 12 hours to remove water, and 1.0 to 5.0 parts by weight of LC wax is added to 100 parts by weight of pellet composition in the dried corn core powder. And stirring at a stirring speed 300 to 800 RPM to produce a coated corn core powder to prevent resorption of water;
(C) adding 10 to 50 parts by weight of the coated corn core powder and 100 parts by weight of the pellet composition and a plastic resin polymer serving as a binder, an organic acid and a peroxide, and mixing to form a mixture;
(D) Injecting the mixture into the extruder to form a plastic resin-plant graft bond, discharge the material made of the plastic resin-plant graft bond through the discharge port, the discharged strand through the conveyor belt In the manufacturing method of biomass pellets comprising; pellet manufacturing step of producing a pellet by cutting or face-cutting after blow drying while transporting,
The peroxide is any one of dicumyl oxide, benzoyl peroxide, di- triple butyl peroxide,
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 biomass pellets.
(A) pulverizing the corn core into fine particles of 100 to 300 mesh or less to produce corn core powder;
(B) drying the corn core powder at 80 degrees to 130 for 1.0 hour to 12 hours to remove water, and 1.0 to 5.0 parts by weight of LC wax is added to 100 parts by weight of pellet composition in the dried corn core powder. And stirring at a stirring speed 300 to 800 RPM to produce a coated corn core powder to prevent resorption of water;
(C) adding 10 to 50 parts by weight of the coated corn core powder and 100 parts by weight of the pellet composition and a plastic resin polymer serving as a binder, an organic acid and a peroxide, and mixing to form a mixture;
(D) Injecting the mixture into the extruder to form a plastic resin-plant graft bond, discharge the material made of the plastic resin-plant graft bond through the discharge port, the discharged strand through the conveyor belt In the manufacturing method of biomass pellets comprising; pellet manufacturing step of producing a pellet by cutting or face-cutting after blow drying while transporting,
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 content of the organic acid is a method for producing biomass pellets, characterized in that 0.2 to 5 parts by weight based on 100 parts by weight of the pellet composition. delete delete delete delete delete

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