KR102400400B1 - Method for Manufacturing Antimicrobial Bio-fillers for Plastics and Antimicrobial Bio-fillers by Using the Same - Google Patents

Abstract

The present invention relates to a method for manufacturing an antibacterial bio-filler for plastic addition and to an anti-bacterial bio-filler for plastic additive produced thereby, and more particularly, to an oleophilic from hydrophilic lignocellulosic biomass. ) relates to a method for manufacturing an antibacterial bio-filler for plastic addition and to an anti-bacterial bio-filler for plastic additive manufactured thereby.

Description

Method for manufacturing antimicrobial bio-fillers for plastic addition and antimicrobial bio-fillers for plastic addition manufactured thereby

The present invention relates to a method for manufacturing an antibacterial bio-filler for plastic addition and to an anti-bacterial bio-filler for plastic additive produced thereby, and more particularly, to an oleophilic from hydrophilic lignocellulosic biomass. ) relates to a method for manufacturing an antibacterial bio-filler for plastic addition and to an anti-bacterial bio-filler for plastic additive manufactured thereby.

Recently, as global warming and environmental pollution problems have been seriously raised, interest in biomaterials that can replace petroleum-derived materials is increasing. In particular, most plastic materials are derived from petroleum and are intensively used for automobile interior materials, building materials, and packaging materials. related technologies are attracting attention.

In general, materials for manufacturing plastic products are largely divided into three categories. The first is a material for the basic resin for the production of plastic products such as polyethylene (PE), polypropylene (Polypropylene, PP), and polyvinylchloride (PVC) and polystyrene. It is a material for additives that adds additional functions such as properties and UV stability. Finally, it is composed of a material for fillers to increase the physical properties of plastics such as strength and rigidity. A plastic product is produced by properly mixing the above three materials, manufacturing a composite resin, and injecting and extruding the composite resin prepared in this way to suit the product.

Various bioplastic material production technologies related to research to substitute biomaterials for materials for plastic products have been reported so far, and among them, a technology that utilizes non-edible lignocellulosic biomass as a raw material for bioplastic materials. A lot of research has been done on this recently.

This lignocellulosic biomass is a natural polymer material composed of cellulose, hemicellulose and lignin. In particular, the lignin component has antibacterial properties, so it can be used as a natural antibacterial agent.

However, most of lignin is produced as a by-product of the pulp process and is produced in the form of hydrolyzed, modified low molecular weight (kraft lignin), 98% of lignin is used as fuel, and this lignin is utilized as a functional material for plastic manufacturing. In order to achieve this, it must be functionalized so that it can be used for each application field, but the related technology has not yet been properly developed.

For example, the molecular weight of lignin generated in the pulping process is only tens to several thousand, and hydrophilicity increases during the process, but in general, lignin by-products must be hydrophobized and polymerized in order to be used in the manufacture of antibacterial plastics.

As a prior art for manufacturing a bio-filler for plastic addition from biomass containing such lignin, Korean Patent No. 10-2087724 relates to chemical modification of lignin, hydrophobizing lignin produced in the pulping process by attaching fatty acids, and obtaining A method for producing an antibacterial lignin-derived material by reacting and polymerizing xyloxylic acid-lignin particles with allylated cellulose fibers or its particles has been proposed, but this is difficult to put into practical use due to the complicated process and increased production cost. Have.

As another prior art, in Patent Registration No. 10-1889744, the lignin extract and pulp of the pulp process are pulverized through a mechanical method to produce nanocellulose modified with a silane-based compound, and then mixed to produce a modified lignin-nanocellulose composite. Although a technology for producing a lignin composite for plastic manufacturing by mixing a polypropylene material graphed with maleic anhydride has been described, this also includes expensive nanocellulose, and the process is very complicated, so a material for manufacturing general-purpose antibacterial plastics It has limitations in its application.

As another prior art, Korean Patent No. 10-1809564 suggests that lignin can be extracted from lignocellulosic biomass through a concentrated sulfuric acid pretreatment process and applied as a plastic filling material, but this is due to the use of high concentration of concentrated sulfuric acid. In addition, lignin in the lignocellulosic biomass is less than 30% by weight, making it difficult to secure economic feasibility when considering the process yield. It has a limit in that it cannot be applied to plastic materials.

As another prior art, in the case of Registered Patent Publication No. 10-1962239, a method for producing a plastic filler in a yield of at least 30% by weight or more by treating the lignocellulosic biomass with a strong acid catalyst to hydrophobically reform the entire biomass is presented. However, in the case of the hemicellulose component among the biomass components, the thermal decomposition properties are poor ( Yang H, Yan R, Chen H, Lee DH, Zheng C (2007) Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel 86 (12)) :1781-1788) When used as a plastic filler, thermal decomposition occurs during the plastic manufacturing process, which has a limitation in which defects occur on the surface of plastic products.

As another prior art, recently, with respect to the development of nanomaterials derived from lignocellulosic biomass, International Patent Publication WO 2015-200584 discloses sulfur dioxide, ethanol and water in lignocellulosic biomass. Most of the hemicellulose and lignin are dissolved in a low-molecular form by treatment, and a small amount of the remaining low-molecular lignin component is adsorbed to obtain a cellulose fiber, which is then treated with a cellulase enzyme to remove the amorphous cellulose component through hydrolysis. A technique for producing a lignin-nanocellulose complex after mechanical grinding has been proposed, but this is an amorphous form through an additional cellulase enzyme treatment to nanoize the cellulose fibers and increase the crystallinity to 60% or more during the chemical grinding process. In addition to the high cost of hydrolyzing the cellulosic component, among the components of lignocellulosic biomass, lignin (15 to 35% by weight of the total lignocellulosic biomass component) and hemicellulose (total lignocellulosic biomass component) 5-20% by weight of the biomass component) is mostly removed, so the yield does not exceed 47% at most, and the lignin component is decomposed and mostly dissolved in an ethanol/water solution in a low-molecular form and also mechanically pulverized It consumes a lot of energy, and sulfur dioxide added during the reaction reacts with the lignin component and remains in the form of a covalent bond, while toxic gas in the form of SOx is generated during plastic manufacturing, which limits its application. It is difficult to secure economic feasibility due to the high production cost due to the complicated process and cannot be used as a furnace.

Therefore, the process is simple using inexpensive lignocellulosic biomass as a raw material, and while hemicellulose is removed, the thermal properties are excellent, and the lignin is functionalized so that antibacterial properties can be expressed. The need for the development of a novel antibacterial bio-filler for adding plastic and a method for manufacturing the same is more urgently required.

Registered Patent Publication 10-2087724 (2020.03.12) Registration Deok Heo Gongbo 10-1889744 (2018.08.21) Registered Patent Publication 10-1809564 (2017.12.15) Registered Patent Publication 10-1962239 (2019.03.27) International Patent Publication No. WO 2015-200584 (2015.12.30)

The technical problem to be solved by the present invention is that hemicellulose is removed from non-edible lignocellulosic biomass without complicated and high production cost, and while hemicellulose is removed, lignin is functionalized so that it can exhibit excellent thermal properties and antibacterial properties. , to provide a method for producing an antibacterial bio-filler for plastic additive with improved dispersibility in plastic production in high yield due to excellent lipophilicity and hydrophobicity.

In addition, another technical problem in the present invention is to provide a lighter and more eco-friendly antibacterial bio-filler for plastic addition and an antibacterial plastic material comprising the same, manufactured according to the above manufacturing method.

In order to achieve the above object, the present invention comprises the steps of (a) removing at least a portion of hemicellulose components from lignocellulosic biomass comprising lignin and cellulose and hemicellulose; (b) reforming the lignocellulosic biomass by adding an acid to the lignocellulosic biomass from which hemicellulose has been removed; and (c) adding a base to the reactant obtained in step (b) to neutralize the residual acidic component, and then removing the water-soluble material from the neutralized reactant to obtain solid particles; A method for producing a bio-filler for plastic addition comprising ) provides a method for manufacturing a bio-filler for plastic addition, characterized in that the following.

In one embodiment, in step (b), the acid (acid) is an organic acid having 1 to 20 carbon atoms; or an inorganic acid selected from sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, or a mixture thereof; or a mixture of the organic and inorganic acids; or a mixture of an organic acid and a mixture of inorganic acids; can be selected from

As an embodiment, the content of hemicellulose-derived components in the solid particles obtained in step (c) may be 3 weight (wt%) or less based on the total of lignin, cellulose, and hemicellulose-derived components in the solid particles.

In one embodiment, in step (c), the solid material contains 1 wt% to 99 wt% of lignin-derived components based on the total of lignin, cellulose and hemicellulose-derived components, or lignin, cellulose and hemicellulose-derived components Based on the total of the components, 1 wt% to 99 wt% of the cellulose-derived component may be included.

In one embodiment, in step (c), the solid material contains 20 wt% to 80 wt% of lignin-derived components based on the total of lignin, cellulose and hemicellulose-derived components, and 20 wt% of cellulose-derived components It may contain 80 wt% in

As an embodiment, in the step (a), the removal of the hemicellulose component from the biomass is performed in a heat treatment process, a hot water process, a steam explosion process, and an acid steam explosion containing acids process. It may include one selected process or a mixture thereof, and preferably, the removal of the hemicellulose component in step (a) may include a hot water process.

As an embodiment, as the acid in step (b), sulfuric acid having a sulfuric acid concentration in the range of 0.5 to 70 wt% based on the total content of the aqueous solution including the pulverized biomass and the acid may be used.

In one embodiment, the base in step (c) is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia (NH ₃ ), lithium hydroxide (LiOH), calcium carbonate ( CaCO ₃ ), potassium carbonate (K2CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), magnesium hydroxide (Mg(OH) ₂ ), calcium oxide (CaO), magnesium oxide (MgO) and carbonate At least one selected from sodium hydrogen (NaHCO ₃ ) or a mixture thereof may be used.

The present invention may also provide an antimicrobial bio-filler for plastic addition, which is produced by the method for manufacturing the bio-filler for plastic addition.

The present invention may also provide an antimicrobial plastic composition comprising an antimicrobial bio-filler for plastic addition, which is produced by the method for manufacturing the bio-filler for plastic addition, and preferably, the plastic composition comprises a bio-filler for plastic addition. It may be included in an amount of 0.1 to 90% by weight based on the total weight of the composition.

The present invention can also provide an antibacterial product comprising the plastic composition.

The manufacturing method of the bio-filler for plastic addition according to the present invention is a low-cost, non-edible lignocellulosic biomass from non-edible lignocellulosic biomass through a chemical treatment process according to specific conditions without complicated and high production costs. Although the process is simple, the hemicellulose is removed so that it has excellent thermal properties and at the same time, lignin is functionalized so that antibacterial properties can be expressed. It has the advantage of being able to manufacture in yield.

In addition, the composite plastic product including the antibacterial bio-filler for plastic addition manufactured by the manufacturing method according to the present invention has improved antibacterial properties and at the same time significantly reduced weight compared to plastic products produced using a mineral-based filler such as talc. Because it is effective, it has the advantage of being highly applicable to products that require antibacterial and light weight, such as materials for vehicles, buildings, and packaging.

In addition, since the bio-filler for plastic addition obtained from lignocellulosic biomass according to the present invention is a plant-derived material, it can be completely burned when incinerated compared to existing mineral-based materials, so it is easy and convenient to process, so it is very eco-friendly have a negative advantage

1 is for the evaluation of the antibacterial properties of the bio-filler according to the present invention, after plating Escherichia coli and Staphylococcus aureus in M9 agar medium containing 1 to 10 wt % of the bio-filler prepared in Example, followed by culturing for 12 h. is the picture shown.
FIG. 2 is a diagram showing ASTM standard specimens for each content of a bio-filler prepared using a dry composite resin for dispersibility evaluation of the bio-filler prepared according to an embodiment according to the present invention.
3 is an ASTM standard specimen prepared by injecting a PP composite resin containing 10 wt% of each of the bio-fillers prepared in Examples and Comparative Examples of the present invention for evaluation of the surface properties of plastics according to the present invention. It's a picture.

The manufacturing method of the bio-filler for plastic addition according to the present invention comprises the steps of: (a) removing at least a portion of hemicellulose components from lignocellulosic biomass including lignin, cellulose, and hemicellulose; (b) reforming the lignocellulosic biomass by adding an acid to the lignocellulosic biomass from which hemicellulose has been removed; and (c) adding a base to the reactant obtained in step (b) to neutralize the residual acidic component, and then removing the water-soluble material from the neutralized reactant to obtain solid particles; A method for producing a bio-filler for plastic addition comprising ) is characterized by the following.

Hereinafter, the manufacturing method according to the present invention will be described in more detail.

The lignocellulosic biomass in step (a) according to the present invention contains lignin and is a material containing at least one of cellulose and hemicellulose, and preferably includes both lignin, cellulose and hemicellulose. And, such lignocellulosic biomass can be applied to lignocellulosic biomass (common wood) such as herbaceous, coniferous or broad-leaved trees, or various biomass such as rice straw, corn stalk, palm husk, and sugar cane. can

The lignocellulosic biomass may be pulverized in the step of removing the hemicellulose component. and more preferably in the range of 10 to 0.001 mm.

In addition, in the step of removing the hemicellulose component, the lignocellulosic biomass may be subjected to a drying process to reduce water content. The drying process comprises drying the moisture content of the lignocellulosic biomass to 30 wt% or less, preferably 20 wt% or less, more preferably 10 wt% or less, based on the lignocellulosic biomass after drying. Preferably, the drying process can be used without limitation as long as it is a method capable of reducing the moisture content of the lignocellulosic biomass, such as oven drying, natural drying in a well-ventilated place, or hot air drying.

In the present invention, the grinding process or the drying process may be applied independently, and when the grinding process and the drying process are applied together, the grinding and drying steps may be performed regardless of the order. That is, the lignocellulosic biomass may be subjected to a drying process after the grinding process, or may be subjected to a grinding process after the drying process, which is based on the surrounding environment or the type and drying of the lignocellulosic biomass. It can change depending on the state.

For example, if the drying process is very good, the drying process may be omitted, and preferably, drying the lignocellulosic biomass having an increased surface area after the pulverization step may be preferred from the viewpoint of efficiency.

On the other hand, the process of removing at least a portion of the hemicellulose component from the lignocellulosic biomass in step a) corresponds to a technical feature of the present invention, and through this, the bio for plastic addition with improved thermal decomposition properties In order to obtain a filler, the content of the hemicellulose-derived component is 5 weight (wt%) or less, preferably 3 weight (wt%) or less, based on the total of lignin and cellulose and hemicellulose-derived components in the finally obtained solid particles. can be controlled.

Here, the removal of the hemicellulose is one process selected from heat treatment process, hot water process, steam explosion process, and steam explosion containing acids process for lignocellulosic biomass or It may include a mixed process thereof, but as long as it is a process in which the hemicellulose is removed from the lignocellulosic biomass, the method may be applied without limitation, and preferably, the hemicellulose component in step (a) is removed. may include a hot water process.

Here, the heat treatment process is a process of obtaining a solid material after reacting the lignocellulosic biomass at 100 to 400 ℃, preferably 150 to 330 ℃ for 10 minutes to 5 days, preferably 20 minutes to 1 day In addition, the hot water process is a mixture containing lignocellulosic biomass and water at 80 ~ 250 ℃, preferably 120 ~ 200 ℃ 10 minutes to 5 days, preferably may include a process of filtering the solids after reacting for 20 minutes to 1 day, and the steam explosion process is to inject water vapor into the lignocellulosic biomass, but 100 to 250 ° C., preferably may include a process of filtering the solids after reacting at 130 to 190 ° C for 10 minutes to 5 days, preferably 20 minutes to 1 day, and the steam explosion containing acids process is The detonation process may include a process of adding an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, or an organic acid having 1 to 20 carbon atoms, or a mixture thereof.

At this time, in the hot water process, the content ratio of lignocellulosic biomass and water is in the range of 5:1 to 1:30 based on the mass of the lignocellulosic biomass:water is input. Also, in the case of the acid steam blasting, the content of the input acid (10% (v/v basis)) is 100 based on the ratio of lignocellulosic biomass: acid to each input mass It may range from :1 to 5:1.

In addition, the present invention is a process of washing with water after the process of filtering the solids obtained according to the heat treatment process, hot water process, steam explosion process and steam explosion containing acids process, or A drying process may be further included.

When most of the hemicellulose is removed from the lignocellulosic biomass by the heat treatment process, hot water process, steam explosion process, and steam explosion containing acids process in the present invention, Residual components in lignocellulosic biomass remain lignin and cellulose components as main components, and when these are hydrophobized and polymerized through acid treatment, the bio-filler for plastic addition having antibacterial properties in the present invention is can be manufactured.

That is, after most of the hemicellulose is removed from the lignocellulosic biomass, in step (b) according to the present invention, an acid is added to the lignocellulosic biomass from which the hemicellulose has been removed. Modification according to polymerization is made so that a part of lignin and at least part of cellulose have a chemically bonded polymer form, and also modification into a modified lignocellulosic solid material having hydrophobicity and lipophilicity is made.

Here, in step (b), the acid (acid) is an organic acid having 1 to 20 carbon atoms; or an inorganic acid selected from sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, or a mixture thereof; or a mixture of the organic and inorganic acids; or a mixture of an organic acid and a mixture of inorganic acids; can be selected from

In this case, in the case of the organic acid, as a carbon compound containing carboxylic acid, monocarboxylic acid, biscarboxylic acid, triscarboxylic acid, tetracarboxylic acid, etc. can be used depending on the number of carboxylic acids, Depending on the number of carbon atoms, an organic acid having 1 to 20 carbon atoms, preferably an organic acid having 1 to 15 carbon atoms, may be used, and more preferably, acetic acid, formic acid, propionic acid, or the like may be used.

In addition, as a preferred example of the acid component used as the inorganic acid, sulfuric acid or hydrochloric acid or a mixture thereof may be used, and preferably 0.5 to 70 wt% based on the total content of the aqueous solution including the pulverized biomass and the acid. Preferably in the range of 0.6 to 65 wt%, more preferably in the range of 0.7 to 60 wt%, sulfuric acid may be used.

Here, the content of the strong acid is an example of adding 75% (v/v) sulfuric acid, the 75% (v/v) sulfuric acid is added, and the final concentration standard (including pulverized biomass and sulfuric acid) Based on the total content of the aqueous solution), the sulfuric acid concentration may be used in a concentration range of 0.5 wt% to 70 wt%, preferably, a concentration of 0.6 wt% to 65 wt%, more preferably a concentration of 0.7 to 60 wt% range can be used. The above ratio can be used by changing the optimal conditions in various ways depending on the type of biomass, and even when hydrochloric acid is used, the number of moles in a similar range can be calculated and used, and even when a mixed solution of sulfuric acid and hydrochloric acid is used Based on the above range, it is possible to appropriately determine the amount of strong acid input.

On the other hand, by adding the acid catalyst, the molecular structure of the cellulose and lignin complex as residual components constituting the lignocellulosic biomass is changed, and many hydroxyl groups (-OH) present therein are dehydrated and carboxyl groups (COOH) can be removed through decarboxylation reaction to make it hydrophobic, and lignin-cellulose molecules in a modified form are formed by polycondensation reaction and especially partial hydrolysis of cellulose components, and the weight ratio between lignin and cellulose molecules is reduced. By diversifying, it is possible to prepare a solid material having various physical properties.

To explain this in more detail, an acid component such as hydrochloric acid and sulfuric acid is added to the lignocellulosic biomass and a part of hydrophilic cellulose among the materials constituting the lignocellulosic biomass is hydrolyzed while physically stirring. Hydrophobization by removing or inducing a decarboxylation reaction of a hydroxyl group (R-OH group) of a cellulose/lignin molecule, a decarboxylation reaction of a carboxy group (R-COOH), and at the same time, between various functional groups present in lignin and cellulose molecules As the condensation/polymerization reaction proceeds, hydrophobic solid particles of a polymer having a very complex structure may be formed.

In particular, according to the present invention, the lignin in the solid particles obtained later by appropriately controlling the cellulose hydrolysis reaction while controlling the chemical reaction conditions (reaction time, reaction temperature, acid concentration, reaction pressure, etc.) by the acid component -By making it possible to control the cellulose ratio in various ways, it is possible to produce antibacterial bio-fillers for adding plastics with various physical properties.

At this time, in the reaction according to the addition of the acid component, the reaction temperature may be in the range of 30 ~ 250 ℃, preferably in the range of 70 ~ 140 ℃, the reaction time is in the range of 5 minutes to 12 hours. can

On the other hand, in the present invention, step (c) is a step of neutralizing residual acid by adding a base to the reaction mixture obtained from step (b) and removing a water-soluble substance from the neutralized reactant. In the step of neutralizing the acid, if the acid component used in step b) remains and remains in the post-process, it may become a problem in plastic manufacturing, so it is removed by neutralizing it using a base.

The base used at this time is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia (NH ₃ ), lithium hydroxide (LiOH), calcium carbonate (CaCO ₃ ), potassium carbonate (K ₂ ) CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), magnesium hydroxide (Mg(OH) ₂ ), calcium oxide (CaO), magnesium oxide (MgO) and sodium hydrogen carbonate (NaHCO ₃ ) It may be at least one selected or a mixture thereof, but may be used without being limited to the type of base that can neutralize the acid component.

At this time, in the present invention, a modified lignocellulosic biomass reactant obtained by reacting the lignocellulosic biomass in step b) with an acid component before neutralizing the residual acid between steps b) and c) It may additionally include a step of washing the remaining acid component by adding water, and the acid contained in the aqueous solution obtained after washing can be recovered and reused.

In the present invention, the step of removing the water-soluble material from the neutralized reactant in step (c) in the present invention is a step of removing the water-soluble material contained in the reactant by dehydrating the neutralized reactant and washing with water and recovering a solid product. , wherein the water-soluble material is any one of a water-soluble material such as residual sugar derived from biomass, a material derived from an acid addition process, and a material derived from the addition of a base, and means a component that can be dissolved in an aqueous solution .

The water-soluble substance may be removed by, for example, a washing process using an aqueous solution. More specifically, the water-soluble salt obtained by washing the product obtained by the neutralizing step of step (c) with an aqueous solution and adding it to the acidic component and the basic component, hydrolyzed from the components in the lignocellulosic biomass Some of the sugars can be removed, and as a result, based on the total weight of the obtained solid particles, excluding a certain amount of polysaccharides hydrolyzed by the acid component, at least 30% by weight relative to the dry weight of the input biomass, Preferably 40% by weight or more, more preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more of lignocellulosic biomass can be obtained in a modified form. And, the obtained lignocellulosic biomass-modified solid material can show good physical properties such as antibacterial properties and dispersibility in the above yield.

Meanwhile, the present invention may further include, as an additional step, after step (c), (d) pulverizing the solid particles obtained by removing the water-soluble material from the neutralized reactant.

The step of pulverizing the solid particles in step (d) is used as an antibacterial bio-filler for plastic addition, and has better dispersibility, compatibility with additives, etc. As such, the step (d) includes drying the solid material from which the water-soluble substances have been removed by washing in step (c) to less than 5% by weight of moisture, and then pulverizing it to an average particle size of 0.1 to 100 μm or less. can

Meanwhile, in the step (c) in the present invention, the obtained solid material may contain 1 wt% to 99 wt% of the lignin-derived component based on the total of the lignin, cellulose and hemicellulose-derived components, and preferably 20 wt% % to 80 wt%, more preferably 25 wt% to 75 wt%, more preferably 30 wt% to 70 wt% of a component derived from lignin.

In addition, in step (c), the obtained solid material may contain 1 wt% to 99 wt% of a cellulose-derived component based on the total of lignin, cellulose and hemicellulose-derived components, and preferably 20 wt% to 80 wt% %, more preferably 25 wt% to 75 wt%, more preferably 30 wt% to 70 wt% of the cellulose-derived component.

In addition, as a preferred component of the solid material obtained in step (c) in the present invention, the solid material contains 20 wt% to 80 wt% of a lignin-derived component based on the total of lignin, cellulose and hemicellulose-derived components, In addition, 20 wt% to 80 wt% of a cellulose-derived component may be included.

On the other hand, as the type of plastic that can be used for the bio-filler for plastic addition according to the present invention, plastics requiring antibacterial properties can be mixed and used without being limited to the type, preferably polypropylene (PP), polyethylene (PE) , polyvinyl chloride (PVC), polystyrene (PS), polyurethane, polycarbonate, polyurea, polyimide, polyamide, polyacetal, polyester, nylon, epoxy resin, acrylic resin, acrylonitrile butadienestyrene (acrylonitrile) -butadiene-styrene, ABS), polylactic acid, polybutylene adipate terephthalate, polybutylene succinate (polybutylene succinate) at least one plastic component selected from the group consisting of can use

In addition, in the bio-filler prepared according to the method for manufacturing the bio-filler for plastic addition according to the present invention, the hemicellulose component having low thermal decomposition properties is removed, and the lignin component and the cellulose component are reacted by various reaction times, temperature and pressure under acid catalytic conditions. It corresponds to a material obtained by mixing various reactions such as dehydration reaction/decarboxylation reaction/condensation reaction/polymerization reaction, and its structure is usually not a single compound, but a complex mixture of polymers, etc., and the lignin component is hydrophobized to plastic When used as an additive bio-filling material, antibacterial properties are expressed, and when used as a substitute for talc, a lightweight plastic material can be manufactured.

In addition, the hydrophobicity of polyolefin-based (Polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), etc.) The miscibility with polymers (polybutylene adipate terephthalate (PBAT), polylactic acid (PLA), polybutylene succinate (PBS)) is increased, and the mechanical properties of plastics can also be increased.

In addition, the present invention can provide an antimicrobial bio-filler for plastic addition, which is produced by the method for manufacturing the bio-filler for plastic addition, and the present invention can also provide an antimicrobial plastic composition comprising the anti-bacterial bio-filler. there is.

That is, when manufacturing a plastic composite material including the bio-filler according to the present invention, it is a technology with high commercial utility because it can provide antibacterial properties while maintaining the physical properties of existing petroleum-based plastics.

In general, the separated cellulose or lignin may have low versatility due to various problems in manufacturing plastics due to hydrophilicity, but the bio-filler for plastic addition obtained according to the present invention is hydrophobized through acid treatment and neutralization reaction, so that general-purpose plastics Compatibility and handling are easy, and the content of hemicellulose is 5 weight (wt%) or less, preferably 3 weight (wt%) based on the total of lignin, cellulose and hemicellulose in the final solid particles obtained. By controlling it to a very low level below or almost removing it, it has the advantage of improving the thermal decomposition characteristics of the plastic material including the bio-filler for plastic addition and the surface characteristics thereof.

In addition, since the specific process for each step used in the present invention performs the hemicellulose removal and acid treatment process using lignocellulosic biomass directly as a raw material without the need to separately purify each cellulose or lignin, conventional Compared to technology, the process is simple and economically, it has the advantage of being able to manufacture a high-yield antibacterial bio-filler.

On the other hand, the conventional bio-filler may have different physical properties of the manufactured plastic material or product depending on the content thereof. The bio-filler for plastic addition according to the present invention may contain 0.1 to 90 wt% of the bio-filler for plastic addition based on the total weight of the composition, preferably 0.5 to 40 wt%, more preferably 1 to 20% by weight.

For example, by mixing 0.1 to 30% by weight of the bio-filler powder obtained according to the present invention and other additives with petroleum-based basic resins such as PP, PE and PVC to prepare an antibacterial plastic composite resin composition, and using the injection/extrusion It can produce plastic materials and products.

In addition, the plastic composite resin composition may further contain various additives such as antioxidants, colorants, release agents, lubricants, light stabilizers, and rubber, and the amount of these additives used is appropriately adjusted according to various factors including the desired end use and properties. and can be applied.

The present invention can also provide an antibacterial product comprising the plastic composition.

Hereinafter, in order to help the understanding of the present invention, it will be described in more detail through examples. However, various conditions may be changed in the embodiments described in the present invention, and thus the scope of the present invention is not limited to the following embodiments. The following examples of the present invention are merely for the purpose of explaining in more detail to those of ordinary skill in the art.

[Experimental Example 1] Lignocellulosic biomass modification reaction

The biomass used to reform the lignocellulosic biomass was domestic pine, and the diameter was pulverized to less than 1 mm before hydrothermal treatment. For hydrothermal treatment, reference was made to the literature (Bioresource Technology, 2016, vol. 216. pp:862-869, Liquid hot water pretreatment of multi feedstocks and enzymatic hydrolysis of solids obtained thereof).

First, pine powder and water as the biomass were added to a stainless steel reactor at a mass ratio of 1:10 and reacted at 190° C. for 60 minutes. After the reaction, the reactor was cooled to less than 100 °C, the solid was recovered through a filter process, washed twice with water, and dried in a dryer at 70 °C to obtain a lignocellulose solid from which hemicellulose was removed.

The obtained lignocellulosic solids were prepared using 75% (v/v) sulfuric acid as shown in Table 1, at a reaction temperature of 120 ° C. A solid reactant sample was obtained while varying the acid catalyst concentration and reaction time. The obtained sample was washed with water twice, neutralized to pH 7.0 with 10 N potassium hydroxide solution, and washed twice again with water to obtain a final solid. Thereafter, the washed solid was dried in a dryer at 120 ° C. for 6 hours, and then pulverized to a particle size of 0.1 to 50 μm to prepare a bio-filler roll.

<Reaction conditions of lignocellulose> # Acid catalyst concentration
(wt%) reaction time
(min) solid recovery
(%) of the solid obtained after the reaction
Lignin : Cellulose : Hemicellulose content ratio (%) note 0-1
0 0 100 31.7:46.3:22.0 control 0-2 60 96 31.6:46.2:18.3 control 0-3 0.1 30 90 37.3:55.7: 7.0 control One One 10 80 39.6:57.9:2.5 2 20 75 39.9:60.1:0.0 3 60 71 43.2:56.8:0.0 5 2 10 78 39.4:60.6:0.0 6 20 71 42.9:57.1:0.0 7 60 63 48.7:51.3:0.0 8 5 10 73 42.1:57.9:0.0 9 20 67 45.8:54.2:0.0 10 60 58 59.0:40.1:0.0 11 50 10 50 90:10:0 12 20 46 95:5:0 13 60 43 99:1:0

In Table 1, the lignin: cellulose content ratio was determined according to the analytical procedure of the NREL Institute of America (Degermination of structural carbohydrates and lignin in biomass, revision 09-03-2012).

In addition, each obtained solid is ethanol, acetone, butanol, hexane, toluene, cyclohexane (cycle hexane), dimethyl sulfoxide (dimethyl sulfoxide), dimethylformamide (dimethyl formamide), etc., solubility is less than 1%, and it was confirmed that it is a macromolecular substance that does not dissolve in any solvent.

[Experimental Example 2] Antibacterial properties of biomaterials

The bio-filler prepared under the #10 condition of Experimental Example 1 was pulverized to a particle size of 0.1 to 50 μm, and the antibacterial properties for each content thereof were evaluated. First, M9 agar containing biomaterials of 1 wt%, 5 wt%, and 10 wt%, respectively, was prepared.

M9 salt contains 64 g Na ₂ HPO ₄ -7H ₂ O, 15 g KH ₂ PO ₄ , 2.5 g NaCl, 5.0 g NH ₄ Cl in 1 L of DW, respectively. M9 agar medium was prepared by adding 800ml of the M9 salt solution, 2ml of 1M MgSO ₄ , 20ml of 20 wt% glucose, 100ul of 1M CaCl ₂ , and 15g of agar.

Gram-negative bacteria E. coli and Gram-positive bacteria Staphylococcus aureus ( S. aureus ) were seed cultured until about OD ₆₀₀ = 1, diluted to 10 ^-6 , and smeared on the prepared M9 agar medium, respectively. was confirmed, and this is shown in FIG. 1 .

1 is a result of culturing E. coli and Staphylococcus aureus in M9 agar medium containing 1% biomaterial, followed by culturing for 12 h. As shown in FIG. 1, sample #10 is 1% by weight, 5% by weight, E. coli and Staphylococcus aureus did not grow at all in M9 agar medium containing 10% by weight, confirming the antibacterial properties of the material. On the other hand, in the case of M9 agar medium containing sample #0-3, when the sample content is 1%, it can be confirmed that E. coli and Staphylococcus aureus grow. As the sample content increases, the antibacterial property increases, but it can be seen that the antibacterial property is lower than that of sample #10.

[Experimental Example 3] Dispersibility and surface properties of biomaterials in plastics

In addition, dispersibility and surface properties in plastics of samples prepared by hydrophobization under the conditions #0-1, #0-3 and #1 of Experimental Example 1 were evaluated.

More specifically, for the production of plastic resin, a PP (J-370, Lotte chemical) composite resin containing 5 wt%, 10 wt%, and 20 wt% of the biomaterial of sample #1 condition, respectively, was prepared and until the specimen was manufactured. The moisture content was maintained at less than 0.1% by weight, and an ASTM standard specimen was prepared using a dry composite resin, which is shown in FIG. 2 . As shown in FIG. 2, high dispersibility of the material can be confirmed in the plastic specimen containing each biomaterial.

In addition, sample #0-1, sample #0-3, and sample #10 were each pulverized to a particle size of 0.1 to 50 μm to prepare a biomaterial. A PP (J-370, Lotte chemical) composite resin containing 10% by weight of each of the manufactured biomaterials was manufactured and injected at 250 ^o C to prepare an ASTM standard specimen as shown in the figure and observe the surface properties, which are shown in Fig. 3 shown in

Here, in the case of samples #0-1 and #0-3 from which hemicellulose is not removed, it can be seen that silver streak occurs on the surface by the gas generated during the thermal decomposition of hemicellulose during the injection process. On the other hand, in the case of Sample #1 with less than 2.5% residual hemicellulose, it was confirmed that the plastic surface defects were significantly reduced. The surface properties of plastics are not important in agricultural materials such as mulching films or plastic honeycombs, but are very important physical properties that are considered first in the high value-added plastics industry, where the aesthetics of the surface of products such as vehicles and home appliances are important.

[Experimental Example 4] Physicochemical properties of biomaterial-containing plastics

As shown in Table 2, after adding 0% and 10% of the biomaterial of the #10 condition to PP (Y-120, Lotte Advanced Materials), respectively, a PP composite resin was prepared, an ASTM standard specimen was prepared, and the physical properties of the plastic were checked.

<Physical properties of biomaterial-added plastics> Evaluation items Test Methods unit Biomaterial content (%) 0
(control group; J-120) 20
(Experimental group) MI (230℃, 2160g) D1238 g/10min 1.0 2.0 importance D792 g/cm ³ 0.91 0.92 The tensile strength D638 kgf/cm ² 370 365 flexural modulus D790 kgf/cm ² 12107 17833 flexural strength D790 kg/cm ² 422 444 IZOD 23℃ D256 kg.cm/cm 3.9 4.2 ROCKWELL hardness D785 R-scale 99 85

As shown in Table 2, it can be seen that the MI (melt index) was improved by 100%, the flexural modulus was improved by 47%, and the impact strength was improved by about 7.7%.

[Experimental Example 5] Physicochemical properties of plastics by biomaterial type

As shown in Table 3, after adding 10% of biomaterials of various lignin:cellulose content ratios to PP (J-350, Lotte Chemical), PP composite resins were prepared, ASTM standard specimens were prepared, and the physical properties of plastics were checked.

<Effect of lignin: cellulose composition ratio of biomaterials on plastic properties> Evaluation items Test Methods unit Y-120 Biomaterial content: 20% by weight #2 #10 #11 MI (230℃, 2160g) D1238 g/10min 1.0 1.3 1.7 2.1 importance D792 g/cm ³ 0.92 0.96 0.94 0.92 The tensile strength D638 kgf/cm ² 370 517 432 274 flexural modulus D790 kgf/cm ² 12107 17833 16993 16230 flexural strength D790 kg/cm ² 422 396 404 414 IZOD impact strength 23℃ D256 kg.cm/cm 3.9 4.5 4.2 3.9 ROCKWELL hardness D785 R-scale 99 - - 83

As shown in Table 3, it can be confirmed that the flexural modulus and impact strength are improved as the content of the modified cellulose according to the present invention increases.

Claims (13)

(a) removing at least a portion of the hemicellulose component from the lignocellulosic biomass comprising lignin and cellulose and hemicellulose;
(b) modifying the lignocellulosic biomass by adding an acid to the lignocellulosic biomass from which the hemicellulose has been removed; and
(c) adding a base to the reactant obtained in step (b) to neutralize the residual acidic component, and then removing the water-soluble material from the neutralized reactant to obtain solid particles; As a method of manufacturing a bio-filler for plastic addition comprising a,
The solid particles obtained in step (c) have a content of hemicellulose of 5 weight (wt%) or less based on the total of lignin, cellulose, and hemicellulose-derived components in the solid particles.
The method of claim 1,
In step (b), the acid (acid) is an organic acid having 1 to 20 carbon atoms; or an inorganic acid selected from sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid, or a mixture thereof; or a mixture of the organic and inorganic acids; or a mixture of an organic acid and a mixture of inorganic acids; A method for manufacturing a bio-filler for plastic addition, characterized in that it is selected from
The method of claim 1,
The solid particles obtained in step (c) have a hemicellulose content of 3 weight (wt%) or less based on the total of lignin, cellulose and hemicellulose-derived components in the solid particles.
The method of claim 1,
In step (c), the solid material contains 1 wt% to 99 wt% of lignin-derived components based on the total of lignin, cellulose and hemicellulose-derived components, or lignin, cellulose, and cellulose based on the total of hemicellulose-derived components A method for manufacturing a bio-filler for plastic addition, characterized in that it contains 1 wt% to 99 wt% of the derived component.
The method of claim 1,
In step (c), the solid material contains 20 wt% to 80 wt% of lignin-derived components based on the total of lignin, cellulose and hemicellulose-derived components, and 20 wt% to 80 wt% of cellulose-derived components A method for producing a bio-filler for plastic addition, characterized in that it.
The method of claim 1,
In step (a), the removal of the hemicellulose component from the biomass is one process selected from a heat treatment process, a hot water process, a steam explosion process, and a steam explosion containing acids process. Or a method for manufacturing a bio-filler for plastic addition, characterized in that it comprises a mixed process thereof.
The method of claim 1,
The method of manufacturing a bio-filler for plastic addition, characterized in that the removal of the hemicellulose component in step (a) includes a hot water process.
The method of claim 1,
The acid (acid) in step (b) is pulverized biomass; and an acid-containing aqueous solution; based on the total content, sulfuric acid in a concentration range of 0.5 to 70 wt% is used.
The method of claim 1,
The base in step (c) is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca(OH) ₂ ), ammonia (NH ₃ ), lithium hydroxide (LiOH), calcium carbonate (CaCO ₃ ), carbonate Potassium (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydrogen carbonate (KHCO ₃ ), magnesium hydroxide (Mg(OH) ₂ ), calcium oxide (CaO), magnesium oxide (MgO) and sodium hydrogen carbonate ( NaHCO ₃ ) Method for producing a bio-filler for plastic addition, characterized in that at least one selected from or a mixture thereof.
According to any one of claims 1 to 9, which is produced by the method according to any one of claims, antibacterial bio-fillers for plastic addition.
An antimicrobial plastic composition comprising the bio-filler for plastic addition according to claim 10.
12. The method of claim 11,
The plastic composition is an antimicrobial plastic composition, characterized in that it comprises 0.1 to 90% by weight of the bio-filler for plastic addition based on the total weight of the composition.
An antimicrobial product comprising the plastic composition according to claim 12 .

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