KR20150048791A - A bio-based polymer additive, a process for preparing the bio-based polymer additive and a biodegradable polymer composition comprising said bio-based polymer additive - Google Patents

Abstract

The present invention discloses a biodegradable polymer composition comprising a bio-based polymer additive, a method for producing the same, and the bio-based polymer additive for use in the production of a biodegradable plastic. The additive is prepared from biomass of pulverized microbial cells such as microalgae, yeast or other microorganisms. In particular, the bio-based polymer additive improves flow properties and / or biodegradability of the polymer. In particular, the additive is used as a pigment.

Description

TECHNICAL FIELD The present invention relates to a biodegradable polymer composition comprising a biocompatible polymer additive, a method for preparing the biocompatible polymer, and a biodegradable polymer composition comprising the biocompatible polymer additive -based polymer additive}

The present invention relates to a biocompatible polymer additive, a method for producing the biocompatible polymer additive, and a biodegradable polymer composition including the biochemical additive. According to a particular aspect, the bio-based polymer additive is used as a pigment.

The fast-growing biotechnology industry is creating new kinds of contamination problems due to solid residues derived from microbial biomass. Microorganisms are used as a single cell factory, for example, brewer yeast produces ethanol used as alternative energy in the automotive industry through fermentation processes, and yeast remains as a by-product or waste after the purification of ethanol.

Similarly, the microalgae conventionally used in the food production and food additive industries have received the attention of the biofuel industry in recent years, as some species can produce oil and lipids. Microalgae are good candidates for fuel production because of the combination of advantages such as high photosynthetic efficiency, biomass production and faster growth compared to other energy crops. Microalgae are grown in large scale photobioreactors for industrial scale production of biofuels, which leaves a large amount of microalgae after the oil extraction process. After the end of the production process, the abandoned microorganisms remain as a large amount of solid waste, causing a new kind of contamination problem as described above. To address this pollution problem, there is a need to find better ways to treat microbial waste or add economic value.

One common method of treating microbial solid wastes by the biotechnology industry is to treat these tons of wastes with landfill. Several other solutions have also been proposed. For example, Shiho et . al ., (2011) suggested that wastes from microalga Botryococcus biomass could be used as a heat generator, where the heat of combustion of solid components was measured experimentally and at 31% to 34 MJ / kg. < / RTI > However, the drying process before obtaining such a very low moisture content is expensive and inefficient. In another example, yeast solid waste from the bio-ethanol industry was used as feed supplement. However, this consumption is very limited due to the difficulty in controlling the quality of the yeast solid waste. Thus, the proposed application can not be an ongoing solution to remove large amounts of yeast biomass.

Another solution proposed for this problem is to incorporate biomass into the plastic. U. S. Patent No. 5,346, 929 discloses a process for preparing a resin made from a mixture of starch from a synthetic biodegradable polymer and Aspergillus , but the resin production process / process including its advantages is not clear . U.S. Patent No. 8026301 discloses a method of increasing the biodegradability of a polymer by combining a petroleum resin (e.g., polyethylene, polypropylene, polystyrene and polyvinyl chloride) with cellulose, a chemically based nitrogen source, a blue-green algae, Teaches a polymer composition comprising a complex of natural nutrients from yeast.

However, the incorporation of biomass into plastics additionally requires the addition of additives, for example, the addition of a compatibilizer to maintain polymer properties and their compatibility, otherwise the amount of biomass added to the plastic is very high Will be limited. In addition, any known method not only improves the biodegradability of the biodegradable polymer, but also increases the use of the biomass to enhance properties such as viscosity or compatibility of the biodegradable polymer composition, which is critical for the production of biodegradable plastics Does not teach or suggest valuable skills.

Biodegradable plastics are considered environmentally friendly. They are produced from plants and their derivatives or some other renewable resource. Biodegradable plastics can deteriorate when attacked by microorganisms under natural or artificial conditions, thereby decreasing the molar mass of degraded biodegradable plastics, which can be transferred to microorganisms and can be supplied to appropriate metabolic pathways It is plastic. As a result, the end product of this metabolic process includes water and carbon dioxide (CO ₂ ) along with newly generated biomass. A good example of biodegradable plastics is polylactide or polylactic acid (PLA). PLA can be produced by the polymerization of bacterially fermented lactic acid, which is believed to solve environmental problems without the use of non-renewable resources. Therefore, PLA is attracting attention as a material alternative to existing plastics or fibers made from petroleum roots. Another example of a biodegradable plastic is poly (butylene succinate) (PBS).

Indeed, currently available biodegradable resins require the addition of polymeric additives such as color thickeners or pigments for their application. There have been attempts to proceed with color enrichment in standard equipment and use techniques known in the plastics industry. For example, U.S. Patent No. 8,133,558 discloses a process for making a PLA blown film made of 1 to 20% titanium oxide (TiO ₂ ) to express a particular color of a PLA blown film. U.S. Patent No. 7,273,896 discloses a method of visualizing medical biomaterials from polysaccharides by the use of Fluorescein. U.S. Patent No. 7,687,568 discloses a process for preparing polyester coloring thickeners by the use of carbon black pigments, Monoazo pigments, Disazo pigments, phthalocyanine pigments, anthraquinone pigments or quinacridone pigments .

None of the above patents teach or suggest a method of making a biodegradable product entirely of a biocompatible material. All of the coloring additive materials described in these patents are derived from non-renewable sources and cause much more serious environmental problems, because molecules that are dispersed around when the biodegradation process of the resin occurs, such as fluorescein It is toxic to the human body.

On the other hand, natural colorants derived from natural products and / or by-products of the main ingredient or material provide an effective solution to eliminate or reduce contamination on the earth. For example, U.S. Pat. No. 5,205,863 discloses a process for making bioplastics from starch acetate (starch acetate polymer) using 1% of a red natural pigment from Berry fruit as a coloring additive. However, this method causes at least two new problems. First, the above-mentioned production is faced with the difficulty of controlling the quality of the raw materials, in particular the color of the fruit, because the color of the fruit is influenced by climate and physical parameters such as light intensity, water supply, It depends. Secondly, there is a problem of securing raw materials, because these fruits are required in large quantities, which can directly affect human food supply. Therefore, commercial production by this method is almost impossible.

The present inventors have argued the problems of the prior art, and have found that a sustainable solution to the above problems and better utilization and treatment of waste of microbial biomass, There is provided a biocompatible polymer additive prepared from biomass of microbial cells including biomass. Also provided is a biodegradable polymer composition comprising the biocompatible polymeric additive prepared from the microbial cell biomass.

Accordingly, there is provided a biocompatible polymer additive for use in the production of a biodegradable polymer. The bio-based polymer additive is prepared from the biomass of pulverized microbial cells. There is also provided a biodegradable polymer composition comprising a biodegradable polymer and a biocompatible polymeric additive prepared from the biomass of the pulverized microbial cells according to the present invention. In particular, the bio-based polymer additive according to any aspect of the present invention is in the form of a powder obtained by pulverizing the biomass of pulverized microbial cells or by concentrating the biomass solution.

According to a particular aspect of the invention, the microbial cells of the microbial biomass comprise at least one colored molecule. According to this aspect, the bio-based polymer additive according to the present invention is used as a pigment. Accordingly, the bio-based polymer additive according to the present invention includes a bio-based polymer additive pigment or a bio-based polymer additive pigment. Accordingly, biodegradable plastics comprising the biochemical additives of the present invention made entirely of natural colorants are also provided, wherein the components or materials used are derived from products prior to agricultural or biotechnological industries such as biomass, Production and quality control are easy and economically significant. According to this aspect, the bio-based polymer additive according to the present invention can be used as a coloring agent. In the present invention, microbial biomass containing colored molecules in some biotechnology industries are used as natural pigments.

In the bio-based polymer additive according to any of the aspects of the invention, the microorganisms of the biomass may be selected from microalgae, yeast and bacteria or mixtures thereof. In particular, the microorganisms may be selected from the group consisting of Cyanophyta , Prochlorophyta , Rhodophyta , Chlorophyta , Dinophyta , Chrysophyta , Pseudomonas aeruginosa , Prymnesiophyta , Bacillariophyta , Xanthophyta , Eustigmatophyta , Rhaphidophyta , Phaeophyta , Proteoobacteria , (Proteobacteria), cyanobacteria door (cyanobacteria), oil bacteria door (Eubacteria), spirochaete door (Spirochetes), Chlamydia door (Chlamydiae), junction gyunmun (Zygomycota), fungal door (Eumycota) or may be combinations thereof have.

In particular, in the biodegradable polymer composition comprising the biodegradable polymer and the biocompatible polymeric additive made from the biomass of the pulverized microbial cells according to the present invention (for example used as a pigment), the biocompatible polymeric additive may be present in an amount of from 0.05 to 10 By weight. More particularly, the bio-based polymer additive ranges from 0.5 to 5% by weight.

The biodegradable polymer may be any biodegradable polymer suitable for the purposes of any aspect of the present invention. In particular, the biodegradable material may be selected from biodegradable polyesters, for example, poly (butylene succinate) (PBS) and / or lactic acid (PLA).

The biodegradable polymer composition according to the present invention provides improved flow properties over biodegradable polymer compositions that do not contain additives. In addition, the biodegradable polymer composition according to the present invention provides enhanced biodegradation characteristics compared to a biodegradable polymer composition containing no additives.

Accordingly, there is also provided a method for improving the flow characteristics of a polymer comprising the step of adding a biocompatible polymer additive according to any of the aspects of the present invention to the polymer. Also provided is a method for improving biodegradability of a biodegradable polymer comprising the step of adding a biocompatible polymer additive according to any of the aspects of the present invention to the biodegradable polymer. In addition, when the bio-based polymer additive is a bio-based polymer additive pigment, the present invention also provides a method for coloring a polymer comprising the step of adding the bio-based polymer additive pigment according to the present invention to the polymer.

A method of making a biocompatible polymeric additive comprising the steps of:

(a) providing microbial biomass; And

(b) pulverizing the microbial cells of the biomass obtained from the step (a).

In particular, the method for producing the bio-based polymer additive may further include the step of pulverizing the biomass of the pulverized microorganism cells obtained in the step (c) as step (c). The pulverization step may be selected from thermal or cold pulverization methods. The thermal pulverization method may be selected from powder drying, evaporation, rotary drying, flash drying, disk drying, cascade drying, and superheated steam drying. The cold-grinding method may be selected from freeze drying, spray coagulation or spray cooling. Alternatively, (c) may comprise concentrating the biomass of the pulverized microbial cells obtained from step (b).

The microbial biomass of step (a) can be obtained by collecting from a natural resource, a bioreactor or a fermenter. In particular, the microbial biomass may be added to the aqueous solution at a solids concentration of 50 to 200 grams per liter. Particularly, step (b) of the above method may be a mechanical cell crushing method performed at a temperature of 20 to 80 ° C. The mechanical cell grinding method may be selected from a homogenization method, a sintering method, a freezing-thawing method, a mortar and pestle method, or an ultrasonic method.

An article made of a biodegradable polymer composition according to any of the aspects of the present invention is also provided.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photograph of a biodegradable resin (PBS) in which the biocompatible polymer additive pigment from the microalgae biomass powder is introduced in several ratios.
FIG. 2 is a photograph of a biodegradable resin (PLA) into which a biocompatible polymer additive pigment from microalgae powder is introduced in several ratios.
3 is a photograph of a biodegradable resin (PBS) in which a biocompatible polymer additive pigment from yeast powder is introduced in several ratios.
Figure 4 is a photograph of a biodegradable resin (PLA) in which the biochemical additive pigment from the yeast powder is introduced in several ratios.
5 is an optical microscope photograph showing a biodegradable polymer, showing a poly (butylene succinate) (PBS) in which a bio-based polymer additive prepared from microalgae biomass was introduced at a rate of 1.0% ((A) 500x (Left) and (B) 1000x (right)).
6 is an optical microscope photograph showing a biodegradable polymer, showing poly (butylene succinate) (PBS) in which a biosynthetic polymer additive prepared from microalgae biomass was introduced at a rate of 5.0% ((A) 500x (Left) and (B) 1000x (right)).
FIG. 7 is an optical microscope photograph showing a biodegradable polymer, showing a polylactic acid (PLA) in which a biosynthetic polymer additive prepared from microalgae biomass was introduced at a rate of 1.0% ((A) 500x (left) and B) 1000x (right)).
8 is an optical microscope photograph showing a biodegradable polymer, showing a polylactic acid (PLA) in which a biosynthetic polymer additive prepared from microalgae biomass was introduced at a rate of 5.0% ((A) 500x (left) and B) 1000x (right)).
9 is an optical microscope photograph showing a biodegradable polymer, showing poly (butylene succinate) (PBS) in which a biosynthetic polymer additive prepared from yeast biomass was introduced at a rate of 1.0% ((A) 500x Left) and (B) 1000x (right)).
10 is an optical microscope photograph showing a biodegradable polymer, showing poly (butylene succinate) (PBS) in which a biosynthetic polymer additive prepared from yeast biomass was introduced at a rate of 5.0% ((A) 500x Left) and (B) 1000x (right)).
11 is an optical microscope photograph showing a biodegradable polymer, showing a polylactic acid (PLA) in which a biosynthetic polymer additive prepared from yeast biomass was introduced at a rate of 1.0% ((A) 500x (left) and ) 1000x (right)).
12 is an optical microscope photograph showing a biodegradable polymer, showing a polylactic acid (PLA) in which a biopolymer additive prepared from yeast biomass was introduced at a rate of 5.0% ((A) 500x (left) and ) 1000x (right)).
Figure 13 shows a bar chart showing the melt flow rate (MFR) value of a polylactic acid (PLA) polymer to which an additive derived from microalgae according to exemplary embodiments of the present invention is introduced.
Figure 14 shows a bar chart showing the melt flow rate (MFR) of a polylactic acid (PLA) polymer into which yeast-derived additives are incorporated according to exemplary embodiments of the present invention.
Figure 15 shows a bar chart showing the percentage of increased biodegradability of the poly (butylene succinate) (PBS) polymer into which the microalgae-derived additive is incorporated according to exemplary embodiments of the present invention.
Figure 16 shows a bar chart showing the percentage of poly (butylene succinate) (PBS) polymer into which yeast-derived additives are incorporated according to exemplary embodiments of the present invention.
17A is a photograph showing a biodegradable polymer, showing poly (butylene succinate) (PBS) in which Spirulina cells were introduced at 0 wt%, 0.001 wt% and 0.005 wt% without cell disruption according to the prior application do. 17B is a photograph showing a biodegradable polymer. As shown in the present invention, pulverized spirulina cells were coated with poly (butylene stearate) having 0 wt%, 0.5 wt%, 1.0 wt%, 3.0 wt% and 5.0 wt% (PBS). ≪ / RTI >

All aspects disclosed herein are also intended to include applications to any other aspects of the invention, unless otherwise stated.

The technical and scientific terms used herein have the same definitions as will be understood by one of ordinary skill in the art, unless otherwise stated.

The use of singular nouns or pronouns means, when used in conjunction with the term " comprising " in the claims and / or the specification, " One or more than one ".

As used herein, the term "microbial biomass" refers to a biomass derived from a microorganism, which is derived from a biotechnology industry that includes biomass of microbes. The microorganisms according to the present invention may be microalgae, yeast and / or bacteria. Other microorganisms suitable for the present invention may be used. The microbial biomass may be a natural resource, a bioreactor or a fermenter, or a portion of a solid waste from the biotechnology industry (e.g., brewer's yeast after the production of ethanol in a fermentation process, Saccharomyces cerevisiae ). Throughout this application, all types of microorganisms can be referred to as single cell, multicellular, or both.

As used herein, the term " microbial cells comprising an additive pigment "or" microbial cells comprising a colored pigment "refers to microbial cells comprising natural pigmented pigment, for example microalgae, yeast and / or bacteria . For example, the colored molecules may be selected from anthocyanins, chlorophyll, carotenoids, and picobillins, or mixtures thereof.

As used herein, the term "bio-based polymer additive" refers to the additive (s) obtained by breaking down the cells of the microbial biomass.

As used herein, the term "bio-based polymer additive pigment" refers to additive pigment (s) obtained by milling cells of microbial biomass, wherein the microbial cells comprise colored molecules.

As used herein, the term "pigment" refers to insoluble or soluble colored particles.

As used herein, the term "biodegradable polymer composition" refers to a composition comprising at least one biodegradable polymer and at least one bio-based polymer additive, e.g., a bio-based polymer additive pigment according to the present invention.

Throughout this application, the term "about" used to specify any value shown or presented herein may be altered or varied. Such variations or deviations may be caused by errors in the apparatuses and methods used to measure the various values.

The terms " comprise, " " hvae, "and " include" The terms such as " comprise, " " comprise, " " comprise, "" having, " One or more of these verbs are also open ended. For example, any method of " comprise, "" comprise, " include, or" include " one or more steps is not limited to just owning the one or more steps, It covers the steps not specified.

 Any instrument, apparatus, method, or reagent referred to herein is intended to mean an instrument, apparatus, method, or reagent that is commonly used or performed by one of ordinary skill in the art, unless otherwise indicated. do.

Microorganisms are an important tool in biotechnology. Several developments in microbial cultivation within bioreactors have occurred for a long time. For example, the brewer's yeast Saccharomyces cerevisiae plays an important role in ethanol production through fermentation processes, where by-products are also important as alternative energy sources in the automotive industry as well as in beer production. After purification of ethanol in a fermentor, yeast biomass is considered as a by-product or waste. It is known that Saccharomyces cerevisiae biomass contains an anthocyanin which is a red molecule and can be used as a coloring agent. Therefore, a large amount of Saccharomyces cerevisiae yeast biomass is regarded as a by-product or waste in such an ethanol production plant and can be used as a natural coloring agent.

Algae production is well known in food and food additive applications. In recent years, microalgae have been attracting attention in the biofuel industry, with several types known to produce oils and lipids. After biomass fractionation, it causes an ester exchange reaction with methanol, which will provide the formation of biodiesel. Thus, microalgae has been proposed as an excellent candidate for fuel production due to the combination of advantages such as high photosynthetic efficiency, biomass production and faster growth compared to other energy crops. In addition, since these organisms can grow photoautotrophically, their simple growth requirements are suitable for growing in large-scale photobioreactors for the production of industrial-scale biofuels in the 21st century.

 Microalgae contain organic pigments for light energy harvesting. There are three main species of pigment: chlorophyll, carotenoid and picobillin. Chlorophyll (green pigments) and carotenoids (yellow or orange pigments) are lipophilic and are associated with chlorophyll-protein complexes, while picobilins are hydrophilic. The chlorophyll molecule consists of a tetrapyrrole ring containing a magnesium atom in the center and a long chain terpenoid alcohol. Structurally, the various types of chlorophyll molecules designated as a, b, c, and d differ in lateral substituents on the tetrapyrrole ring. All chlorophyll molecules have two major absorption bands: blue or blue-green (450-475 nm) and red (630-675 nm).

Chlorophyll a is part of the core and a reactive center pigment protein complex that appears in all oxygenated photoautotrophs and is accompanied by chlorophyll b or chlorophyll c in a light-harvesting antennae.

Carotenoids represent a large group of biological chromophores with an absorption range of 400 to 550 nm. The basic structural element of carotenoids is the two hexacarbon rings linked by 18 carbons conjugated to a double bond chain. They are generally derived from hydrocarbons (carotene, for example alpha-carotene, beta-carotene) or oxygenated hydrocarbons (xanthophylls such as lutein, violaxanthin, zeaxanthin, , Fucoxanthin, peridinin).

Carotenoids play several roles in photosynthesis mechanisms: (1) auxiliary light harvesting pigments that transfer excitation to chlorophyll a, (2) structural entities and reaction center pigment-protein complexes in light harvesting; And (3) functions as a molecular, chlorophyll triplet and reactive oxygen species required for protection against overexposure.

In cyanobacteria and red algae such as Spirulina species, the main antenna contains a phycobilin, such as phycoerythrobilin, phycocyanobilin and phycourobilin. These auxiliary pigments absorb blue-green, blue, green, or orange light (500-650 nm). Phycobiliprotein is water-soluble and the pigments are covalently bound to apoprotein.

In the present invention, the microalgae are prokaryotic algae of Cyanophyta and Prochlorophyta ; Or Rhodophyta , Chlorophyta , Dinophyta , Chrysophyta , Prymnesiophyta , Bacillariophyta , Xanthophyta , Eustigmatophyta , Rhaphidophyta and Rhododendrons are the most common phytonutrients in Korea . Can be selected from the eukaryotic algae of Phaeophyta . Examples of prokaryotic algae are Spirulina species, which include chlorophyll, phycocyanin , phycoerythrin, beta - carotene , Beta creep torque Santin (beta - cryptoxanthin) and the Southern Dynasties plants containing zeaxanthin (Zeaxanthin) is a no-contact cyano bacteria. An example of eucaryotic algae is the nanochlorophysi sp.

 In the present invention, the microorganism can be selected from a prokaryotic microorganism containing a coloring molecule in a proteobacteria gate, a cyanobacteria gate, a uracilum bacteria gate, a spirocheta gate and a chlamydia gate.

In the present invention, the microorganism can be selected from eukaryotic microorganisms containing colored molecules in the junctional germs and fungus gates, for example, Saccharomyces cerevisiae containing red molecules of anthocyanin.

In one aspect, the present invention provides a bio-based polymer additive for use in the production of a biodegradable polymer composition. The bio-based polymer additive is prepared from the biomass of pulverized microbial cells.

In the bio-based polymer additive according to one aspect of the present invention, the biomass of the microorganism may be selected from microalgae, yeast and bacteria or a mixture thereof. Particularly, the biomass can be used in a variety of fields such as a southern plant gate, a prokaryotic green plant gate, a red flora gate, a green plant gate, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Chlamydia gates, junction gates or fungal gates, or combinations thereof. More specifically, the biomass is selected from microalgae biomass or yeast biomass or a combination thereof.

In another aspect of the present invention, there is provided a biodegradable polymer composition comprising a biodegradable polymer and a biocompatible polymeric additive prepared from biomass of comminuted microbial cells. More preferably, the amount of the bio-based polymer additive ranges from 0.05 to 10% by weight. Most preferably, the bio-based polymer additive ranges from 0.5 to 5% by weight. Any biodegradable polymer suitable for the purposes of any aspect of the invention may be used. The biodegradable polymer may be selected from biodegradable polyesters. Thus, for example, the biodegradable polyester can be, but is not limited to, poly (butylene succinate) (PBS) or polylactic acid (PLA) or a mixture thereof.

Since the microbial cells of the pulverized biomass provide a biodegradable polymer more compatible with the biochemical additive as compared with the micro-pulverized microbial cells, the characteristics and characteristics of the biodegradable polymer composition prepared therefrom And the like). In particular, in the case of using such a composition comprising a biodegradable polymer and a biocompatible polymer additive prepared from the microbial biomass of the pulverized microbial cells according to the present invention, the biodegradable polymer may be a compatibilizer for improving the mixing efficiency Can be efficiently mixed with the additive without the addition of oil). Therefore, it is suggested that the step of pulverizing the microbial cells is important in order to produce the microorganism derived from the bio-based polymer additive, without the addition of the additional additive (different from the bio-based polymer additive according to the present invention).

In a method known in the prior art, microorganisms are generally first dried and then ground. In contrast, in the process of the present invention, the microbial cells are first crushed and then processed for the preparation of the additive, for example, by a drying step or a solution concentration step. In particular, the inventors have found that it is advantageous to crush these cells prior to the drying or concentration step, because after the cell walls and / or cell membranes have been destroyed, the additive molecules, for example additive pigment molecules, It can be. On the other hand, the drying step prior to crushing the cells causes dehydration of water in the cells without collapse of the cell wall / cell membrane. As a result, the additive molecules (including the pigment) are trapped in the dried cells, making it difficult to release additive molecules (including pigments) from the dried cells.

In another aspect of the present invention, the present invention relates to a method for preparing a bio-based polymer additive comprising the steps of:

(a) providing microbial biomass; And

(b) pulverizing the microbial cells of the biomass obtained from the step (a).

The step (a) may include harvesting a microalgae or other colored molecule-containing microorganism from a natural lake or lagoon, an open pond, a closed photobioreactor. The microbial biomass of step (a) can be obtained by collecting it from a natural resource, a bioreactor or a fermenter. In particular, the microbial biomass may be added at a solids concentration of 50 to 200 grams per liter in an aqueous solution. Particularly, the step (b) may be a mechanical cell crushing method performed at a temperature of 20 to 80 ° C. Mechanical cell grinding can be selected from homogenization, sintering, freezing-thawing, mulch and pestle or ultrasonication.

In particular, the method for producing the bio-based polymer additive may further comprise, as step (c), pulverizing the biomass of the pulverized microorganism cells obtained from the step (b). The pulverization step may be selected from thermal or cold pulverization methods. The thermal pulverization method may be selected from spray drying, evaporation, rotary drying, air drying, disk drying, cascade drying, superheated steam drying. The cold-grinding method may be selected from freeze drying, spray coagulation or spray cooling.

Alternatively, in step (c), the preparation of the additive may be obtained in a different manner from the pulverization. For example, the additive may be prepared by concentrating the biomass of the pulverized microbial cells. More particularly, this step involves concentrating the biomass of the pulverized microorganism and then dispersing it in a suitable liquid carrier compatible with the resin (polymer) to be processed. More particularly, according to this alternative step (c), the additive can be obtained by mixing a concentrated pigment dispersion comprising water and an aromatic hydrocarbon in an amount necessary for complete elimination of water in the dispersion by azeotropic distillation. The resulting homogeneous slurry can then be heated at a temperature below 90 DEG C under reduced pressure to remove residual water and aromatic hydrocarbons and lower alcohols added as an azeotrope.

According to one aspect of the present invention, there is provided a biocompatible polymer additive for use in a method of making a biodegradable polymer composition. The bio-based polymer additive is prepared from biomass of degraded microbial cells. The biomass may be selected from the group consisting of a southern vegetation door, a prokaryotic greenhouse door, a red flame door, a greenhouse door, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Derived or derived from solid biomass of a microorganism selected from chlamydia gates, junctional gut or fungal gates, or combinations thereof. In particular, the biomass is selected from microalgae or yeast or a combination thereof. More particularly, said microalgae biomass is selected from Spirulina, while said yeast biomass is selected from Saccharomyces. The additives according to the present invention can be prepared as described above, i. E. Comprising the following steps:

(a) providing microbial biomass; And

(b) pulverizing the microbial cells of the biomass obtained from the step (a).

Additionally, the method may comprise (c) pulverizing the biomass of the pulverized microbial cells obtained from step (b). Alternatively, (c) may comprise concentrating the biomass of the pulverized microbial cells.

According to a particular embodiment of the invention, the biocompound polymer additive from the microbial biomass according to the invention can be prepared by a process comprising the following steps:

(a) obtaining microbial biomass, said microbial biomass being obtainable by collecting the biomass of the microbes discarded as a by-product waste from the biotechnology industry, which is generally in the form of solid waste. It is also possible that the biomass is harvested from natural sources such as natural lakes, lagoons, open ponds or cultivated plants / reactors, bioreactors or fermentation tanks.

(b) pulverizing the microbial cells of the biomass obtained from the step (a), wherein, in an exemplary embodiment, the biomass obtained from the step (a) comprises a biomass diluted in an aqueous solution and dried, A mixture of positive biomass can be obtained. In an exemplary embodiment, the amount of biomass is 50 to 200 grams per liter in solid concentration. The mixture of biomass is then mechanically cell-milled at a temperature of 20 to 80 캜. Mechanical cell grinding can be selected from homogenization, sintering, freezing-thawing, mulch and pestle or ultrasonication.

(c) pulverizing the biomass of the pulverized microbial cells obtained from the step (b), wherein the mixture of the pulverized microbial cells from step (b) is diluted in an aqueous solution, A polymer additive is obtained. In this step, the pulverization process may be carried out by thermal pulverization (e.g., spray drying, evaporation, rotary drying, air drying, disk drying, cascade drying or superheated steam drying) Coagulation or spray cooling).

 The biodegradable polymer composition according to the present invention provides improved flow properties over biodegradable polymer compositions that do not contain additives. The biodegradable polymer composition according to the present invention also provides enhanced biodegradation properties compared to biodegradable polymer compositions that do not contain additives.

Accordingly, there is also provided a method for improving the flow characteristics of a polymer comprising the step of adding a biocompatible polymer additive according to any of the aspects of the present invention to the polymer. There is also provided a method for improving biodegradability of a biodegradable polymer comprising the step of adding a biocompatible polymer additive according to any of the aspects of the present invention to a biodegradable polymer.

According to a particular aspect of the present invention, the microbial cells of the microbial biomass comprise at least one colored molecule. According to this aspect, the bio-based polymer additive according to the present invention is particularly used as a pigment for coloring a biodegradable polymer. Accordingly, the bio-based polymer additive according to this aspect of the present invention may comprise a bio-based polymer additive pigment or a bio-based polymer additive pigment. Accordingly, biodegradable plastics are provided which comprise a biochemical additive (pigment) made entirely of natural colorants, wherein the components or materials used are derived from products prior to agricultural or biotechnological industries such as microbial biomass, Production and quality control are easy and economically significant. According to this aspect, the bio-based polymer additive according to the present invention can be used as a coloring agent.

In particular, there is provided a biocompatible polymer additive pigment which is used as a colorant in the preparation of a biodegradable polymer, wherein the additive pigment is derived from the biomass of the pulverized microbial cell.

In the bio-based polymer additive used as a pigment according to aspects of the present invention, the microorganisms of the biomass may be selected from microalgae, yeast and bacteria or mixtures thereof.

Particularly, the microorganisms are selected from the group consisting of a southern plant gate, a proton keratinocyte gate, a red flour gate, a green plant gate, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Phytoplankton, Chlamydia gates, junctional gut or fungal gates, or combinations thereof.

The colored molecules may be selected from the group consisting of anthocyanins, chlorophyll, carotene (e.g., alpha carotene, beta carotene or oxidized hydroxycarbonophosphate (e.g., lutein, violaxanthin, zeaxanthin, fucoxanthin, , Porphyrin, picobillin)), or a mixture thereof.

A biodegradable polymer composition comprising a biocompatible polymeric additive prepared from the biomass of the pulverized microbial cells according to the present invention for use as a biodegradable polymer and pigment is also provided. The amount of the bio-based polymer additive is in the range of 0.05 to 10% by weight. More particularly, the bio-based polymer additive ranges from 0.5 to 5% by weight.

The biodegradable polymer may be any biodegradable polymer suitable for the purposes of any aspect of the present invention. In particular, the biodegradable material may be selected from biodegradable polyesters, for example, poly (butylene succinate) (PBS) and / or polylactic acid (PLA).

When the bio-based polymer additive is a pigment of a bio-based polymer additive, in addition to the characteristics already described for the biodegradable polymer composition comprising the bio-based polymer additive and the bio-based polymer additive according to the present invention, And adding a biocompatible polymer additive pigment to the polymer. ≪ Desc / Clms Page number 2 >

An article made of a biodegradable polymer composition according to any of the aspects of the present invention is also provided.

The method for producing the bio-based polymer additive according to the principles of the present invention described above will now be discussed in detail with the examples. In the present specification, the detailed description of the present invention is shown by way of example. This is meant to illustrate various embodiments of the present invention and is not meant to limit the principles or concepts of the present invention.

Example  1: Microalgae From biomass Biological system Polymer  Preparation of Additive Pigment

The following examples are intended to prepare green biosynthetic pigments from microalgae spirulina biomass.

Spirulina cells, microalgae harvested from the closed bioreactor, were obtained. The cells were then added to deionized water to prepare a mixture having a concentration of 200 g dried cells per liter. The Spirulina cells in the mixture were then mechanically pulverized using a homogenizer at 10,000 rpm for 30 minutes, at which time the temperature was maintained below about 80 ° C. The mixture resulting from the grinding of the Spirulina cells was diluted with deionized water to prepare a mixture having a concentration of 50 g dried cells per liter. Thereafter, the mixture was dried at a feed rate of about 0.3 L / h at about 160 DEG C to obtain a polymer additive pigment powder derived from microalgae. The particle size of the obtained polymer additive pigment powder from the microalgae was measured with a particle size analyzer-Malvern Instrument (Mastersizer 2000). The average distribution of the particles was about 6 to 9 microns.

Example  2: Yeast From biomass Biological system Polymer  Preparation of Additive Pigment

Yeast Saccharomyces biomass is known to contain red-orange colored particles, anthocyanins, in the cells. The following example aims to prepare a red-orange biomass additive pigment from yeast saccharomyces biomass.

Yeast Saccharomyces biomass was obtained from the fermenter. The cells were then added to deionized water to prepare a mixture having a concentration of 200 g dml of cells dried per liter. The saccharomyces cells in the mixture were then mechanically pulverized using a homogenizer at 10,000 rpm for 30 minutes, at which time the temperature was maintained below about 80 ° C. The mixture resulting from the grinding of saccharomyces cells was diluted with deionized water to prepare a mixture having a concentration of 50 g dried cells per liter. Then, the mixture was dried at a temperature of about 160 DEG C at a feed rate of about 0.3 L / h to obtain a polymer additive pigment powder derived from yeast. The particle size of the yeast-derived polymer additive pigment powder was measured with a particle size analyzer-Malvern Instrument (Mastersizer 2000). The average distribution of the particles was about 6 to 9 microns.

 Turning now to another aspect of the present invention, the present invention discloses a biodegradable polymer composition comprising a biodegradable polymer and a biocompatible polymer additive for use in preparing a biodegradable polymer. The bio-based polymer additive is prepared according to the above-described method.

A biodegradable polymer composition according to an exemplary embodiment of the present invention comprises a biodegradable polymer selected from biodegradable polyesters, preferably polylactic acid (PLA) or poly (butylene succinate) (PBS) Based polymer additive prepared by the method as described.

In one embodiment, the biodegradable polymer composition according to the present invention comprises a biodegradable polymer selected from biodegradable polyesters, for example, polylactic acid (PLA) or poly (butylene succinate) (PBS) 10% by weight of a biocompatible polymeric additive.

In one embodiment, the biodegradable polymer composition according to the present invention comprises a biodegradable polymer selected from biodegradable polyesters, for example, polylactic acid (PLA) or poly (butylene succinate) (PBS) 5% by weight of a biocompatible polymer additive.

In one embodiment, the biodegradable polymer composition comprises a biocompatible polymeric additive made from microalgae biomass selected from PBS and Spirulina, wherein the additive ranges from about 0.5 to 5 wt%.

In one embodiment, the biodegradable polymer composition comprises a biocompatible polymeric additive prepared from microalgae biomass selected from PLA and Spirulina, wherein the additive ranges from about 0.5 to 5 wt%.

In one embodiment, the biodegradable polymer composition comprises a bio-based polymer additive made from yeast biomass selected from PBS and Saccharomyces, and the additive ranges from about 0.5 to 5 wt%.

In one embodiment, the biodegradable polymer composition comprises a biocompatible polymeric additive made from yeast biomass selected from PLA and Saccharomyces, and the additive ranges from about 0.5 to 5 wt%.

The biodegradable polymer composition according to the present invention can be prepared by a method commonly known to those skilled in the art. The method comprises the following steps:

Mixing the biodegradable polymer and the bio-based polymer additive prepared according to the present invention at a predetermined ratio;

- extruding said mixture by feeding said mixture to an extruder at a predetermined feed rate (the axis of the extruder is heated at a predetermined temperature and the axial speed is set at a predetermined speed);

Cutting the extruded material into small pieces;

- the step of obtaining a molded specimen by injection molding

The biodegradable polymer composition according to the present invention can be produced using a method / process according to the following embodiments.

Example  3: PBS  And microalgae From biomass  Manufactured Biological system Polymer  Containing additives Polymer  Composition

In this example, poly (butylene succinate) (PBS) FZ71PD from Mitsubishi Chemical Corporation was mixed with the bio-based polymer additive powder derived from Example 1 at a ratio of 0.5, 1.0, 3.0 and 5.0 wt% Lt; / RTI > The mixture was fed to an extruder, specifically an extruder line and a mixer (Haake Rheometer Os) at a feed rate of about 1.5 g per minute, at which time the axis of the extruder was heated to about 170 ° C and the axial velocity was set at 120 RPM. The extruded polymer composition was then cut with Haake Rheometer OS to reduce its size. Thereafter, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg / h. At an injection pressure of 200 MPa, injection was carried out at a barrel temperature of 165 ° C and a molding temperature of 40 ° C. Thereafter, the performance of the completed specimen (FIG. 1) was tested.

Example  4: PLA  And microalgae From biomass  Manufactured Biological system Polymer  Containing additives Polymer  Composition

In this example, polylactic acid (PLA) 2002D from Naturework was mixed with the bio-based polymer additive powder prepared according to Example 1 at a ratio of about 0.5, 1.0, 3.0, and 5.0 wt%. The mixture was fed to an extruder, specifically an extruder line and a mixer (Haake Rheometer Os) at a feed rate of about 1.5 g / min, at which time the shaft was heated to about 170 ° C and the axial velocity was set at 120 RPM. The extruded polymer composition was then cut with Haake Rheometer OS to reduce its size. Thereafter, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg / h. At an injection pressure of 200 MPa, injection was carried out at a barrel temperature of 165 ° C and a molding temperature of 40 ° C. The performance of the completed specimen (FIG. 2) was then tested.

Example  5: PBS  And yeast From biomass  Manufactured Biological system Polymer  Containing additives Polymer  Composition

In this example, poly (butylene succinate) (PBS) from Mitsubishi Chemical Corporation was mixed with the bio-based polymer additive prepared from the yeast biomass of Example 2 and 0.5, 1.0, 3.0 and 5.0 wt% By weight. The mixture was then fed to an extruder, specifically an extruder line and a mixer (Haake Rheometer Os) at a feed rate of about 1.5 grams per minute, where the axis of the extruder was heated to about 170 DEG C and the axial velocity was set at 120 RPM . The extruded polymer composition was then cut with Haake Rheometer OS to reduce its size. Thereafter, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg / h. At an injection pressure of 200 MPa, injection was carried out at a barrel temperature of 165 ° C and a molding temperature of 40 ° C. Thereafter, the performance of the completed specimen (FIG. 3) was tested.

Example  6: PLA  And yeast From biomass  Manufactured Biological system Polymer  Containing additives Polymer  Composition

In this example, polylactic acid (PLA) 2002D from Naturework was mixed with the bio-based polymer additives made from the yeast biomass of Example 2 in proportions of about 0.5, 1.0, 3.0, and 5.0 wt%. The blend material was fed to an extruder, specifically an extruder line and a mixer (Haake Rheometer Os) at a feed rate of about 1.5 g / min, at which time the shaft was heated to a temperature of about 170 ° C and the axial velocity was set at 120 RPM. The extruded polymer composition was then cut with Haake Rheometer OS to reduce its size. Thereafter, the mixture was made into a dumbbell-shaped specimen using an injector EC100II2A (Toshiba) having a capacity of 61 kg / h. At an injection pressure of 200 MPa, injection was carried out at a barrel temperature of 165 ° C and a molding temperature of 40 ° C. The performance of the completed specimen (FIG. 4) was then tested.

Using PBS or PLA in all Examples 3-6 and the microalgae biomass of the pulverized microbial cells according to the present invention or a composition comprising the biocompound polymer additives made from the yeast biomass, both PBS and PLA can be used as an oil It is noted that they can be efficiently mixed with the additive without the addition of a compatibilizer to improve mixing efficiency.

Additionally, it should be noted that it is possible to vary the ratio between the biocompatible polymer additive and the biodegradable polymer, depending on the desired properties of the end product. According to the present invention and the examples, various ratios of the biocompatible polymer additive and the biodegradable polymer were determined based on maintaining the mechanical properties of the biodegradable polymer composition. The range of the bio-based polymer additive is 0.05 to 10% by weight, preferably 0.5 to 5% by weight. 1 to 17 illustrate various features and characteristics of an article molded from a biodegradable polymer composition produced using the bio-based polymer additive according to the present invention. When the weight percentage of the biocompatible polymer additive is less than 0.05, the characteristics of the biocompatible polymer additive are significantly reduced, and thus the biodegradable polymer composition produced from the biodegradable polymer containing the additive has a desired property It is noticed that it does not have. In contrast, undesirable mechanical properties have been observed in biodegradable polymer compositions comprising greater than 10% of the bio-based polymer additives.

Therefore, the biodegradable polymer composition produced from the biodegradable polymer comprising the biocompatible polymer additive prepared from the biomass of the pulverized microbial cells according to the present invention has a higher polymer property as well as a higher production efficiency ≪ / RTI > These advantages will become more apparent with reference to the following comparative examples.

Comparative Example  One

A PBS composition was prepared in the same manner as in Examples 3 and 5 except that the microalgae biomass according to the present invention or the biopolymer additive prepared from the yeast biomass was not used. The composition was then extruded and molded into a molded article. The performance of the finished specimen was then tested.

Comparative Example  2

PLA compositions were prepared in the same manner as in Examples 4 and 6 except that the microalgae biomass or yeast biomass according to the present invention did not use the bio-based polymer additives prepared from the biomass. The composition was then extruded and molded into a molded article. The performance of the finished specimen was then tested.

According to the present invention, Biomass  Or yeast From biomass Derived Biological system Polymer  Biodegradability including additives Polymer  Measurement of Mechanical Properties of Composition

The mechanical properties of the biodegradable polymers from Examples 3 to 6 and Comparative Examples 1 and 2 were measured using the methods described below. The results are shown in Table 1. Tensile strength and elongation at break were tested according to the method specified in ASTM D638 using an universal testing machine (brand: Zwick / Roell, Model: Z050 TE). The test was conducted at a temperature of 23 캜 and a humidity of 50 캜. The breaking tensile stress was measured by the following formula (1), and the breaking elongation was measured by the following formula (2).

Tensile strength (MPa) = Breaking load (N) / Cross section (mm ² ) (1)

Elongation at break (%) = [(Elongation at break - Weekly distance) / Weekly distance] x 100 (2)

Table 1 shows the mechanical properties of the biodegradable polymer composition containing the bio-based polymer additive.

Sample name E (MPa) Tensile stress Elongation at break (%) Upon surrender maximum Fracture PLA without additive 3740 ± 86 77.5 ± 0.5 77.5 ± 0.5 65.7 ± 1.2 5.1 ± 0.9 PLA + microalgae 0.5% 3800 ± 74 71.9 ± 0.7 71.9 ± 0.7 59.3 ± 1.8 5.4 ± 1.4 PLA + microalgae 1% 3750 ± 127 69.1 ± 0.4 68.5 ± 1.0 61.8 ± 5.4 3.5 ± 1.4 PLA + microalgae 3% 3650 ± 101 64.1 ± 0.9 64.1 ± 0.9 53.6 ± 0.9 4.6 ± 0.8 PLA + microalgae 5% 3760 ± 56 62.0 ± 0.2 57.4 ± 6.9 53.6 ± 4.9 2.4 ± 1.0 PLA + yeast 0.5% 3830 ± 145 69.3 ± 0.3 69.3 ± 0.3 59.6 ± 3.2 5.7 ± 2.3 PLA + yeast 1% 3920 ± 168 66.7 ± 0.3 66.7 ± 0.3 55.3 ± 1.3 5.9 ± 1.0 PLA + yeast 3% 3720 ± 127 59.2 ± 0.6 59.2 ± 0.6 51.4 ± 4.4 5.9 ± 3.1 PLA + yeast 5% 3790 ± 90 56.4 ± 0.3 56.4 ± 0.3 50.2 ± 3.2 3.2 ± 0.8 PBS without additives 786 ± 26 41.4 ± 0.3 41.4 ± 0.3 40.4 ± 0.9 17 ± 1.7 PBS + microalgae 0.5% 815 ± 31 41.1 ± 0.4 40.9 ± 0.5 40.3 ± 1.0 16 ± 2.3 PBS + microalgae 1% 814 ± 8.5 40.0 ± 0.2 40.1 ± 0.2 38.6 ± 1.6 16 ± 1.1 PBS + microalgae 3% 829 ± 15 36.7 ± 0.2 36.8 ± 0.2 35.9 ± 0.9 13 ± 1.2 PBS + microalgae 5% 862 ± 28 34.7 ± 0.4 34.6 ± 0.3 34.0 ± 0.4 12 ± 0.8 PBS + yeast 0.5% 799 ± 23 40.5 ± 0.5 40.5 ± 0.3 39.8 ± 0.8 16 ± 1.5 PBS + yeast 1% 814 ± 34 39.3 ± 0.1 39.2 ± 0.2 38.5 ± 0.9 14 ± 0.8 PBS + yeast 3% 828 ± 47 37.0 ± 0.2 37.0 ± 0.3 36.3 ± 0.6 14 ± 0.7 PBS + yeast 5% 869 ± 38 34.8 ± 0.2 35.1 ± 0.4 34.4 ± 0.9 14 ± 1.0

The results showed that the mechanical properties of both the PLA and the PBS resin containing the bio-based polymer additive decreased with the increase of the additive content. This suggests that undesirable mechanical properties limit the percentage of additive incorporated into PLA and PBS resin.

According to the invention Biological system Polymer  Biodegradability containing additives Polymer  Measurement of thermal properties of the composition

Thermal characteristics of the biodegradable polymer composition including the biocompatible polymer additive pigment were analyzed according to the method specified in ASTM D3418 using a differential scanning calorimeter (DSC) (brand: NETZSCH, model: DSC 204 F1). In addition, blended resins were analyzed using a thermogravimetric analyzer (TGA) (Brand: NETZSCH, Model: TG 209 F1). The results are shown in Table 2.

Table 2 shows the thermal properties of PBS and PLA containing biocompatible polymer additives according to the present invention as biodegradable plastics.

Sample name Tm (占 폚) Tg / Tc (占 폚) Td (占 폚) PLA 2002D 152.9 57.1 358 PLA 0.5% algae 156.1 56.2 348 PLA 1% algae 155.4 54.9 328 PLA 3% algae 152.9 52.1 320 PLA 5% algae 148.5 48.4 302 PLA 0.5% yeast 155.0 56.4 349 PLA 1% yeast 155.3 55.8 356 PLA 3% yeast 155.1 53.7 341 PLA 5% yeast 154.8 53 337 PBS FZ71PD 113.6 68.5 378 PBS 0.5% algae 113.8 70.8 382 PBS 1% algae 113.7 71.0 377 PBS 3% algae 113.5 69.7 376 PBS 5% algae 113.3 69.3 373 PBS 0.5% yeast 113.7 69.5 384 PBS 1% yeast 113.6 70.9 384 PBS 3% yeast 113.3 70.8 383 PBS 5% yeast 113.1 70.3 381

Tm = melting temperature; Tg = glass transition temperature; Tc = crystallization temperature, Td = decomposition temperature

According to the invention Biological system Polymer  Biodegradability including additives Polymer  The fluidity test of the composition

The flow behavior at low shear was measured by melt flow rate (MFR). MFR was measured using a melt flow index tester (brand: Gottfert, model: MI-4, test conditions = PLA: 2.16 kg, 190 占 폚). As shown in Figure 13, the MFR value of PLA polymer compositions with microalgae biomass increased sharply with an additional amount of particles. In addition, as shown in Figure 14, the MFR value of PLA polymer compositions with yeast biomass also increased with an additional amount of particles. The addition of microalgae and yeast biomass results in an increase in flow properties, for example, a decrease in the viscosity of the PLA polymer. The reduced viscosity is advantageous during formation into the product.

According to the invention Biological system Polymer  Biodegradability including additives From polymer  Generated biodegradability Polymer  Biodegradability test of the composition

The term biodegradable polymer composition generally refers to the attack of insoluble polymeric materials (plastics) by microorganisms. This means that the biodegradation of the polymer is usually a heterogeneous process. Due to the lack of water solubility and the size of the polymer molecules, the microorganisms can not directly transfer the polymer material to the cells where the biochemical process takes place the most. Rather, they must first secrete extracellular enzymes that depolymerize the polymer out of the cell. Consequently, if the molar mass of the polymer is sufficiently reduced to form soluble intermediates, they can be delivered to the microorganism and fed to the appropriate metabolic pathway (s). As a result, the end products of these metabolic processes include new biomass with water, carbon dioxide and methane (in the case of anaerobic digestion).

Static culture titration (Zibilske et al., 1994. Carbon mineralization. Chapter 38. P. 835-863. In Methods of Soil Analysis , Part 2. Microbiological and Biochemical Properties. SSSA Book Series No. 5 Soil Science Society of America, Madison Wis.) To measure the evolution of CO ₂ of the polymer. A PBS polymer containing the biosynthetic polymer additives of Examples 3 and 5 and Comparative Example 1 was prepared as a powder using a Grinder grass planting (Retsch). Each sample was mixed with fertilizer (1 part by weight of sample and 99 parts by weight of fertilizer). Tests were conducted at normal temperature (37 +/- 2 DEG C). During the test, the humidity was maintained at 60 ± 5 ° C. The test period was 3 months. A blank test was conducted using domestic soil. The increase in biodegradability was measured by equation (3).

Increase in biodegradability (%) = [(CO ₂ of the polymer composition containing the biochemical additive Amount-bio-based additive is a CO ₂ generation amount of the polymer composition does not) / bio-based additive is a CO ₂ generation amount of the polymer composition is not] x 100 (3)

The results are shown in Figs. 15 and 16. The biodegradable polymer composition with biochemical additives prepared from microalgae biomass and yeast biomass according to the present invention shows increased biodegradability as compared to polymers without additives.

According to the invention Biological system Polymer  Biodegradability containing additives Polymer  Measure the color characteristics of the composition

Using a color spectrophotometer (Brand: Data Color, Model: D 650), the color reproduction of the biodegradable polymer including the biocompatible polymer additive pigment was observed according to the method specified in ASTM E313. The results are shown in Table 3.

Table 3 shows the colors of PBS and PLA containing biocompatible polymer additives according to the present invention as biodegradable plastics.

Sample name DE DL Da Db PLA 2002D 0.11 -0.11 0.01 0.02 PLA + 1% Algae pigment powder 45.77 -45.65 3.28 0.35 PLA + 5% Algae pigment powder 50.97 -50.34 2.87 -7.41 PLA + 1% yeast pigment powder 35.40 -27.27 8.77 20.80 PLA + 5% yeast pigment powder 42.87 -41.57 10.08 2.88 PBS FZ71PD 0.13 -0.13 0.00 0.01 PBS + 1% Algae pigment powder 39.19 -35.05 -7.64 15.81 PBS + 5% Algae pigment powder 50.00 -49.28 -1.62 8.30 PBS + 1% yeast pigment powder 22.53 -13.03 4.49 17.83 PBS + 5% yeast pigment powder 38.22 -27.75 10.58 24.06

DL = lightness difference of each sample (from completely white 100 to black 0) for the standard sample PLA 2002D or PBS FZ71PD,

Da = red difference of each sample for standard sample PLA 2002D or PBS FZ71PD (positive for red, 0 for gray, negative for green)

Db = yellowish green difference (positive for yellow, gray for zero and blue for negative) of each sample for standard sample PLA 2002D or PBS FZ71PD,

^{DE = (DL 2 + Da 2} + Db 2) 1/2

Particle distribution

Particle distribution of pigment of bird additive pigment and yeast additive pigment powder in PBS was observed with a Canon microscope. The results are shown in Figures 5, 6, 9 and 10. The particle distribution of the pigment additive powder and the yeast additive pigment powder in the PLA were observed with a Canon microscope. The results are shown in FIGS. 7, 8, 11 and 12.

The biodegradable polymer composition according to the present invention exhibits excellent compatibility with conventional biodegradable polymers such as PLA and PBS without the addition of further compatibilizers such as oils. They do not have a significant impact on the mechanical properties of each polymer and thus satisfy their use as polymer additives in several respects.

Since the microbial cells of the pulverized biomass provide better compatibility of the biodegradable polymer and the biochemical additive compared to the micro-pulverized microbial cells, the characteristics and characteristics of the resulting biodegradable polymer composition, for example, It is important to note that improving the characteristics. This can be seen in FIG. 17, which shows large aggregates of spiked Spirulina cells added at very low levels (0.005% non-pulverized cells) to the PBS polymer. Figure 18, on the other hand, shows that additive prepared from the pulverized cells of the Spirulina microalgae biomass according to the invention in high content (5% or 1,000 times higher than the addition of micronized cells) is highly compatible with the PBS polymer . ≪ / RTI > Therefore, the present invention suggests that the step of pulverizing microorganisms is important in order to prepare a microbial-derived bio-based polymer additive without additional additives.

In addition, the bio-based polymer additive according to the present invention can be completely decomposed because it is a bio-based material. Thus, degradation of the biodegradable polymer composition does not leave toxic substances in the soil. It is safe for use in food packaging products or other applications related to the use of animals and humans.

Because the addition of the bio-based polymer additive lowers the viscosity of the biodegradable polymer composition, the failed injection of the biodegradable polymer composition injection grade is reduced. At the same time, due to the reduced viscosity, the extrusion of such a biodegradable polymer composition is superior to a conventional biodegradable polymer composition. In addition, the bio-based polymer additives accelerate biodegradation of PLS and PBS.

These results indicate that biochemical additive pigments, such as those derived from microbial biomass including microalgae, yeast and bacteria, work well with PBS and PLA plastics. In addition, it was also shown that both PBS and PLA were well colored by using the biochemical additive pigment powder from the microbial biomass, without the addition of oil to improve mixing efficiency. Various percentages of additives Biodegradable plastics derived from pigment powder demonstrate various properties suitable for various plastics applications in various industries.

Finally, it is particularly advantageous to provide biodegradable plastics of biochemical additives from microbial biomass, such as microalgae, yeast, bacteria, for example, biochemical additive pigments, from the description and data according to the invention It is clear. The biodegradable plastics according to the present invention provide a better solution to reduce environmental problems, and such production is feasible, sustainable and economical.

Claims (34)

A biopolymer additive for use in the production of a biodegradable polymer, wherein the additive is derived from biomass of pulverized microbial cells, the microorganism being selected from the group consisting of Cyanophyta, Prochlorophyta, (Dinophyta), Chrysophyta, Prymnesiophyta, Bacillariophyta, Xanthophyta, Eustigmatophyta, Rhaphidophyta, Phaeophyta, Proteobacteria, Cyanobacteria, Eubacteria, Spirochetes, Chlamydiae, Zygomycota, fungi, and the like. (Eumycota), or a combination thereof. The method according to claim 1,
Wherein the microorganism comprises at least one colored molecule. 3. The method of claim 2,
Wherein said colored molecules are selected from anthocyanins, chlorophyll, carotinoids and picobillins, or mixtures thereof. 4. The method according to any one of claims 1 to 3,
Wherein the microorganism derived from the southern plant phloem is Spirulina. 4. The method according to any one of claims 1 to 3,
Wherein the microorganism derived from the fungus is Saccharomyces. 6. The method according to any one of claims 1 to 5,
Wherein the additive is in the form of a powder obtained by pulverizing the biomass of pulverized microbial cells. 7. The method according to any one of claims 2 to 6,
Wherein the additive is used as a pigment. 8. The method of claim 7,
Wherein the additive pigment is a pigment of a biopolymer additive pigment which colors the biodegradable polymer (s). As a biodegradable polymer composition,
At least one biocompatible polymeric additive ranging from 0.05 to 10% by weight; And
A biodegradable polymer,
The bio-based polymer additive is derived from the biomass of the pulverized microorganism cells, and the microorganism is derived from a plant selected from the group consisting of a southern plant gland, a prokaryotic gland plant gland, a giant phoenix plant gland, a sulfur gland plant gland, Or a combination thereof, selected from the group consisting of a plant door, a zinnia plant door, a zodiac phoenix door, a grazing plant door, a proteobacterial door, a cyanobacterial door, a uracilian door, a spirothermal door, a chlamydia door, , Biodegradable polymer composition. 10. The method of claim 9,
Wherein the bio-based polymer additive is in a range of 0.5 to 5 wt%. 11. The method according to claim 9 or 10,
Wherein the microorganism comprises at least one colored molecule. 12. The method of claim 11,
Wherein said colored molecules are selected from anthocyanins, chlorophyll, carotenoids and picobillins, or mixtures thereof. 13. The method according to any one of claims 9 to 12,
Wherein the microorganism derived from the aquatic plants is spirulina. 13. The method according to any one of claims 9 to 12,
Wherein the microorganism derived from the fungus is a saccharomyces biodegradable polymer composition. 15. The method according to any one of claims 9 to 14,
Wherein the biodegradable polymer is selected from biodegradable polyesters. 16. The method according to any one of claims 9 to 15,
Wherein the biodegradable polymer is selected from poly (butylene succinate) (PBS) or polylactic acid (PLA) or mixtures thereof. 17. The method according to any one of claims 9 to 16,
Wherein the bio-based polymer additive improves the flow properties of the additive-free biodegradable polymer composition. 17. The method according to any one of claims 9 to 16,
The biodegradable polymer composition according to claim 1, wherein the biodegradable polymer is a biodegradable polymer. 17. The method according to any one of claims 11 to 16,
Wherein the additive is used as a pigment for coloring the biodegradable polymer composition. A method for producing a biocompatible polymeric additive derived from a biomass of pulverized microbial cells,
(a) providing microbial biomass;
(b) pulverizing the microbial cells of the biomass of the step (a); And
(c) pulverizing or concentrating the biomass of the pulverized microbial cells obtained in the step (b). 21. The method of claim 20,
The microbial biomass may be selected from the group consisting of a southern vegetation door, a prokaryotic vegetable door, a phalaenopsis phoenix door, a phalaenopsis phoenix door, a phoenix phoenix phoenix door, a diatomaceous phoenix door, a phoenix phoenix door, A method of making a biocompatible polymeric additive selected from the group consisting of a door, a proteobacterial door, a cyanobacterial door, a uracil bacterium door, a spirotherapy door, a chlamydia door, a synovial or fungal door, or a combination thereof. 22. The method according to claim 20 or 21,
Wherein the microorganism comprises at least one colored molecule. 23. The method of claim 22,
Wherein the colored molecule is selected from anthocyanin, chlorophyll, carotinoid, and picobillin, or a mixture thereof. 24. The method according to any one of claims 20 to 23,
Wherein the microbial biomass is collected from a natural resource, a bioreactor or a fender, and is added at a solid concentration of 50 to 200 grams per liter in an aqueous solution in the step (a). 25. The method according to any one of claims 20 to 24,
Wherein the step (b) is performed at a temperature of 20 to 80 캜. 26. The method of claim 25,
Wherein the mechanical cell pulverization method is selected from the homogenization method, the sintering method, the freeze-thaw method, the mortar and pestle method or the ultrasonic method. 27. The method according to any one of claims 20 to 26,
Wherein the step (c) is selected from a thermal powdering method or a cold-milling method. 28. The method of claim 27,
Wherein the thermal pulverization method is selected from spray drying, evaporation, rotary drying, flash drying, disk drying, cascade drying, and superheated steam drying. 28. The method of claim 27,
Wherein said cold-grinding method is selected from freeze drying, spray coagulation, or spray cooling. 30. The method according to any one of claims 22 to 29,
Wherein the additive is used as a pigment. 9. A method of coloring a biodegradable polymer comprising the step of adding a biocompatible polymer additive according to any one of claims 2 to 8 to a biodegradable polymer. 9. A method for improving flow properties of a biodegradable polymer comprising the step of adding a biocompatible polymeric additive according to any one of claims 1 to 8 to a biodegradable polymer. 9. A method for improving biodegradability of a biodegradable polymer comprising the step of adding the biocompatible polymer additive according to any one of claims 1 to 8 to a biodegradable polymer. An article made from the biodegradable polymer composition according to any one of claims 9 to 19.

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