KR102167883B1 - Oxo-biodegradable composition, and film using the same - Google Patents

Abstract

The present invention relates to an oxo-biodegradable composition which contains a polyolefin-based resin and an additive which helps oxidative biodegradation of the polyolefin-based resin, wherein the additive contains a catalyst, an accelerator, or a mixture thereof, the catalyst contains an amino acid metal salt, and the accelerator contains a hydroxy acid metal salt. The present invention facilitates oxidation by light or heat in a natural environment, promotes biodegradation of products manufactured by using the same, does not cause deterioration of physical properties, and can control the rate of biodegradation.

Description

Oxidative biodegradable composition and film using the same {Oxo-biodegradable composition, and film using the same}

The present invention relates to an oxidized biodegradable composition and a film using the same, and more specifically, to a composition and a manufacturing method comprising an oxidizing biodegradable additive that induces and accelerates the oxidative decomposition of a polyolefin-based resin, and an eco-friendly manufactured using this composition It is about the film.

Herein, background art related to the present disclosure is provided, and these do not necessarily mean known art.

Polyethylene, polypropylene, and polystyrene, which are general-purpose plastics, are representative polymer raw materials for plastics that are widely used in our daily lives. These general-purpose plastics are applied to various packaging materials in the form of films and food containers such as bottles and spoons, which are plastic injection products, and their consumption is increasing. The increase in the amount of plastic used has been pointed out as a cause of environmental problems as a counter benefit, and recently, it has come to be treated as a deadly hazardous substance called fine plastic.

Currently, polyolefin resins are recycled through separate garbage collection, but the recycling rate is lower than expected, and most of them are removed by separate incineration. In this way, harmful gases such as dioxin are generated during disposal and incineration after separate collection, which threatens environmental problems more seriously. In the case of landfill, the decomposition rate requires hundreds of years, which can cause further environmental problems.

In order to solve these environmental problems, biodegradable plastics have been manufactured, and biodegradable plastics are proceeding in two directions. It can be classified into completely biodegradable plastics and biodegradable plastics. Completely biodegradable plastics are made of plastic in the state of polymerizing or processed natural products. First, lactic acid is polymerized with a biodegradable resin made to decompose in nature by polymerizing natural products. Polylactic acid (PLA), polybutylene succinate (PBS) using succinic acid, polyhydroxyalkanoate (PHA) and polyhydroxyalkanoate (PHA) using bacteria and blue-green algae in soil Poly-hydrolyvalerate (PHV), polycaprolactone (PCL), and the like. Second, it can be classified into plastics processed by natural plant fibers and plastics manufactured by molding thermoplastic starch (TPS) at high temperature using corn and cassava as raw materials, and it is used as a completely pollution-free biodegradable plastic.

Biodegradable plastic is a product in which polyethylene phthalate, polycarbonate, polyethylene, polypropylene, etc. are mixed with polylactic acid (PLA) or thermoplastic starch (TPS) mentioned above, and polylactic acid and thermoplastic starch are mixed in a certain ratio or higher. It is made to decompose in nature and is used separately from completely biodegradable plastics.

Polylactic acid, which is a completely biodegradable plastic, has been disclosed that it can be applied to various eco-friendly products such as film sheets in a number of prior documents including Patent Publication No. 10-2008-0067424. In addition, Registration Patent No. 10-0962387 discloses a biodegradable resin molding container by mixing polylactic acid with a polyolefin resin, but it was found that the physical properties of the molded product were limited. In this way, polylactic acid is not easily broken, its glass transition temperature and melting point are not high, its mechanical properties are low, and its properties are largely deteriorated due to hydrolysis, so its commercial range is limited as an industrial molding. There are also problems in the manufacturing process.

Currently, improvement is being made by using a method such as crosslinking polymerization in which polylactic acid is modified to solve the above problem, but the level of desirable physical properties has not yet been obtained. As an alternative, technologies using an oxidation biodegradation catalyst have been introduced.

Oxidation biodegradation catalysts are proposed in Registration Patent No. 10-1904757 that acetyl carbamate metal salts such as ferric acetyl carbamate, aluminum acetyl carbamate, and manganese acetyl carbamate of iron, aluminum, and manganese play a role in accelerating the photooxidation reaction. , Registration patent 10-1798778 uses a metal acetylacetone complex containing a metal selected from among Mn, Al, Ti, Zr, Ni, Cu, Fe, Co, Zn and V as a biodegradation catalyst. It has been suggested to increase the property, and in Registration Patent 10-1365615, the metals included in the carboxylic acid metal salt constituting the oxidative biodegradation accelerator are iron, copper, manganese, cobalt, vanadium, zinc, chromium, cerium, scandium, titanium, nickel, etc. It is suggested that the carboxylic acid may be selected from polyhydric fatty acids such as stearic acid, oleic acid, erucic acid, and linoleic acid.

The oxidative biodegradation catalyst or the oxidative biodegradation accelerator does not specify the technical characteristics of manufacturing the oxidative biodegradation agent, and is described as simply reacting carboxylic acid and metal, so its manufacturing method is not clear, and some react rare earth and carboxylic acid. In the case of producing metal salts using iron, the color is limited because it becomes a catalyst having a red color, and fatty acids are reacted in a strong alkali state, and environmental problems are also likely to occur. In addition, most fatty acids are oily, and in the case of saturated fatty acids, most of them have a melting point below 80℃, and in the case of unsaturated fatty acids, most of them are liquid products at room temperature lower than that. In addition, due to deterioration or acid waste in the distribution of fatty acids, costs are incurred in the process of separation and purification, and it is difficult to remove unreacted fatty acids, and there is a high possibility of environmental problems as the reaction proceeds in a strong alkali state. These unreacted fatty acids cause an odor, making it difficult to work in the field. In the case of a metal salt of a fatty acid, the melting point is low and gas may be generated or decomposed when mixed extrusion injection with a general-purpose plastic. For this reason, it cannot be used for polyacetal or nylon with a high melting point. In order to compensate for this part, in Patent No. 10-1797944, an oxidation catalyst was prepared using an unsaturated carboxylic acid salt having an aromatic substituent, but there is a possibility that environmental problems due to some aromatics may occur.

1. Korean Patent Publication No. 10-2008-0067424 (2008.07.21) 2. Korean Patent Registration No. 10-0962387 (2010.06.01) 3. Korean Patent Registration No. 10-1904757 (2018.09.28) 4. Korean Patent Registration No. 10-1365615 (2014.02.14) 5. Korean Patent Registration No. 10-1797944 (2017.11.09)

The present invention facilitates oxidation by light, heat, etc. in a natural environment to promote biodegradation of a product manufactured using it, does not cause degradation of physical properties, and provides an oxidizing biodegradable composition capable of controlling the biodegradation rate and a method for manufacturing the same. Thus, it is to provide an eco-friendly film capable of photolysis, pyrolysis, and biodegradation.

However, the objects of the present invention are not limited to the above-mentioned objects, and other objects that are not mentioned will be clearly understood by those skilled in the art from the following description.

All technical and scientific terms used in the present specification have the same meaning as commonly understood by those of ordinary skill in the art unless otherwise stated. Also throughout the specification and claims, unless otherwise stated, the term "comprise, comprises, comprising" means to include the recited object, step or group of objects, and steps, and any other It is not used to exclude objects, steps, or groups of objects or steps.

The oxidation biodegradation composition according to the present invention includes a polyolefin-based resin and an additive that aids in the oxidation biodegradation of the polyolefin-based resin, and the additive includes a catalyst, an accelerator, or a mixture thereof. In addition, the additive may further include a photosensitizer. The film produced by using the oxidized biodegradable composition according to the present invention easily undergoes oxidation reactions due to light, heat, etc. in a natural environment without deteriorating physical properties, thereby promoting biodegradation, and the biodegradation rate can also be easily controlled.

Hereinafter, each composition will be described in more detail.

The polyolefin-based resin does not necessarily contain one type of polymer, and a mixture of two or more types of polymers may be used. In addition, it does not necessarily have to be a homopolymer, and may be a copolymer in which two or more monomers are copolymerized. Such copolymers are, for example, ethylene or an α-olefin having 4 to 8 carbon atoms, such as 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and their It may contain a monomer selected from a combination.

Preferred examples of polyolefin-based resins may be those selected from the group consisting of polyethylene, polypropylene, polybutylene, and polystyrene, and among them, polyethylene, polypropylene, or polystyrene is preferable, and in particular, polyethylene, polypropylene, polybutylene, and polystyrene are preferable, and in particular, it is easy to mold and inexpensive polyethylene This may be more desirable.

The content of the polyolefin-based resin may be 80% to 99.5% by weight based on the total weight of the composition, preferably 90% to 99% by weight, more preferably 95% to 99% by weight I can. If it is contained in an amount of less than 80% by weight, the physical properties of the polyolefin-based resin are deteriorated, making it difficult to use as a product. If it is contained in an amount exceeding 99.5% by weight, it cannot be sufficiently decomposed. Cannot achieve characteristics.

The additive may include a catalyst or an accelerator alone, may include a mixture of a catalyst and an accelerator, and may further include a photosensitizer. Additives are generally added to improve or supplement the physical properties of the polymer, and the catalyst or accelerator of the present invention serves to help the polyolefin resin to be decomposed by light or heat. However, since there are some additives that weaken the original physical properties of the polymer, it is preferable to add the additive in a small amount so that the physical properties of the polymer are not weakened while fulfilling the function of the additive.

The additive may be 0.5% by weight to 20% by weight based on the total weight of the composition, preferably 1% by weight to 10% by weight, more preferably 1% by weight to 5% by weight. Biodegradability is achieved by adjusting the content of the catalyst, accelerator, and photosensitizer within the above additive range, while maintaining good physical properties of the polyolefin-based resin.

The catalyst is characterized in that it contains an amino acid (Amino acid) metal salt. The amino acid metal salt includes at least one or more metal salts of any one or more amino acids selected from the group consisting of amino acids including amino groups and carboxyl groups, amino acids including hydroxy groups or sulfur groups, and isomers thereof.

The amino acids including the amino group and carboxyl group include glycine, alanine, cysteine, serine, valine, methionine, proline, phenylalanine, tyrosine, aspartic acid, glutamic acid, proline, asparagine, glutamine, histidine, aminobutyric acid, and these Including at least one selected from the group consisting of isomers of, and the amino acid containing a hydroxy group or a sulfur group is at least one selected from the group consisting of hydroxylysine, homoserine, homocysteine, statins, and isomers thereof. Includes.

In this case, the amino acid does not necessarily contain one type of amino acid, and a mixture of two or more types of amino acids may be used. When two or more kinds of amino acids are mixed, hydrogen bonding between the two amino acids may help crystallization after reaction, and more stable compounds may be formed through hydrogen bonding.

Preferably, any one or more of the metal salt of glycine, the metal salt of alanine, and the metal salt of glutamic acid is preferably used.

The metal of the amino acid metal salt is not particularly limited, but magnesium (Mg), sodium (Na), cobalt (Co), nickel (Ni), iron (Fe), tin (Sn), manganese (Mn), zinc It is preferable to include at least one selected from the group consisting of (Zn), potassium (K), silver (Ag), gold (Au), and copper (Cu).

That is, amino acid metal salts are, for example, potassium glutamate, sodium glutamate, magnesium glutamate, manganese glutamate, silver glutamate, zinc glutamate, potassium glycinate, sodium glycinate, magnesium glycinate, manganese glycinate, silver glycine. And zincate, zinc glasinate, capaglycinate, and the like.

A method of preparing an amino acid metal salt includes a first step of preparing a solid amino acid metal salt, and a second step of removing unreacted amino acids and metal compounds and increasing the purity.

In the first step, after dissolving the amino acid in water or a solvent, the metal compound of the metal dissolved in water or a solvent is slowly added dropwise while stirring. After stirring, the temperature is gradually raised to 70 to 90°C and stirred for 4 to 6 hours. The metal salt is synthesized and the solvent used is distilled at room temperature or under reduced pressure to prepare a solid amino acid metal salt. In addition, the metal compound that does not directly react with the amino acid is dissolved in a solvent, and the obtained amino acid metal salt is dissolved by slowly stirring in water or a solvent, and then the metal compound dissolved in the solvent is gradually added to raise the temperature to 70 to 90°C, and 3 to 6 Stirring for hours to prepare a solid amino acid metal salt.

The metal compound is, for example, potassium hydroxide, potassium chloride, sodium hydroxide, sodium carbonate, magnesium hydroxide, magnesium chloride, magnesium sulfate, kappa hydroxide, kappa chloride, manganese Chloride, manganese sulfate, zinc hydroxide, zinc chloride, and the like can be used.

In the second step, unreacted amino acids and metal compounds are removed and recrystallized by a recrystallization method to increase purity, thereby preparing pure amino acid metal salts. Alternatively, as a preferred method other than the above recrystallization method, a pure amino acid metal salt may be prepared by a precipitation method using one or two alcohols having low solubility in the amino acid metal salt.

The solvent used in the precipitation method is preferably alcohol, and is an aliphatic or aromatic alcohol having 1 to 20 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, etc. It is preferable to use. The alcohol content is preferably 1 to 30 parts by weight based on 100 parts by weight of the amino acid metal salt. If it exceeds 30 parts by weight, there is a problem of precipitation of the added water-soluble metal salt, and if it is less than 1 part by weight, there is a problem of lowering the solubility.

The content of the catalyst may be 0.05% by weight to 5.0% by weight based on the total weight of the composition, preferably 0.1% by weight to 4.0% by weight, and more preferably 0.1% by weight to 3.0% by weight. . When the catalyst is contained in an amount of less than 0.05% by weight, the polyolefin-based resin is not sufficiently oxidized to the extent desired by the present invention, and thus the environmentally friendly material properties of the present invention cannot be achieved. On the other hand, if it is contained in an amount exceeding 5.0% by weight, the manufacturing cost of the oxidized biodegradable composition increases, and there is an instability that is unsuitable for use in industrial fields and in real life, and further, abrasion of the manufactured article is accelerated. Otherwise, there is a fear that the durability may be weakened.

The accelerator is characterized in that it contains a metal salt of hydroxy acids (Hydroxy acids). Hydroxy acid is a high-boiling fatty acid and has excellent biodegradability because it has one or more hydroxyl groups in the molecular chain. Even if the accelerator is added alone, it can induce oxidation of the polyolefin-based resin, but it is added together with the catalyst to help induce oxidation of the polyolefin-based resin, and thus, the desired biodegradation even if only a small amount of the catalyst is added. You will be able to achieve sex. It is preferable to add 1 to 50 parts by weight of the accelerator based on 100 parts by weight of the catalyst. If it exceeds 50 parts by weight, the effect of the catalyst may be reduced by combining with the catalyst, and if less than 1 part by weight is added, it cannot function as an accelerator.

The hydroxy acid metal salt is hydroxylinoleic acid (2-hydroxylinoleic acid), trans hydroxydekenoic acid (trans 10-hydroxydec-2-enoic acid), hydroxydekenoic acid (9-hydroxydec-2-enoic acid) , Hydroxy octadienoic acid (8-hydroxy-5,6-octadienoic acid), hydroxy icosenoic acid (14-hydroxy-11-eicosenoic acid), hydroxy octadecenoic acid (12-hydroxy-9) -octadecenoic acid), hydroxyoctadecadienoic acid (12-hydroxy-9,15-octadecadienoic acid) and hydroxyecosadienoic acid (14-hydroxy-11,17-eicosadienoic acid) selected from the group consisting of It contains at least one or more metal salts of any one or more hydroxy acids.

The metal of the hydroxy acid metal salt is not particularly limited, but magnesium (Mg), sodium (Na), cobalt (Co), nickel (Ni), iron (Fe), tin (Sn), manganese (Mn) , Zinc (Zn), potassium (K), silver (Ag), gold (Au) and copper (Cu) It is good to include at least one selected from the group consisting of.

That is, the hydroxy acid metal salt is, for example, potassium linoleate, sodium ricinoleate, silver ricinoleate, zinc ricinolate, potassium dihydroxystearate, magnesium ricinoleate, manganese ricinoleate, manganese hydride. Oxystearate, sodium dihydroxystearate, silverdihydroxystearate, zinc dihydroxystearate, and the like.

The method of preparing a metal salt of hydroxy acid is to put the above type of hydroxy acid in a solvent and heat it to 70 to 90°C to dissolve it, and then slowly drop the metal compound of the metal dissolved in water to 90 to 110°C for 4 to 6 hours. After heating and stirring at room temperature, it is cooled to room temperature, and the solvent and impurities are distilled under reduced pressure to prepare a metal hydroxy acid salt.

In addition, a photosensitizer for controlling a photochemical reaction may be further included as an additive, and an inorganic compound or an organic compound may be used as the photosensitizer. The inorganic compound system includes cadmium sulfide, cupric ions, ferric ions, ruthenium tribispyridyl, titanium dioxide, etc., preferably It is preferable to use a ketone-based photosensitizer, which is an organic compound type, specifically benzophenone, diphenylmethanone, butane-2,3-dione, 1- It may be one or more selected from the group consisting of phenyl-1,2-propanedione and camphorquinone.

The wavelength of light that induces decomposition of a film prepared using the oxidative biodegradation composition according to the present invention is not particularly limited, but due to the nature of the reaction in which oxidation is induced by light, light of a wavelength belonging to ultraviolet or near ultraviolet rays may induce the reaction. high portential. In addition, oxidation reactions may be caused by light in the visible region of a short wavelength close to ultraviolet rays.

The present invention facilitates oxidation by light, heat, etc. in a natural environment by adding amino acid metal salts, hydroxy acid metal salts, etc. as oxidation biodegradation additives to the olefin resin, thereby promoting biodegradation of products manufactured using this and reducing physical properties. It does not cause, and the biodegradation rate can be controlled, so it can be applied to various olefin resins.

1 shows the decomposition result of a film according to an embodiment of the present invention after irradiation of ultraviolet rays for 300 hours.
2 shows the decomposition result after 3 months of outdoor exposure of a film according to an embodiment of the present invention.

Before describing the present invention in detail below, it is understood that the terms used in the present specification are for describing specific embodiments and are not intended to limit the scope of the present invention, which is limited only by the scope of the appended claims. shall.

Meanwhile, various embodiments of the present invention may be combined with any other embodiments unless there is a clear opposite point. Any feature indicated to be particularly preferred or advantageous may be combined with any other feature and features indicated to be preferred or advantageous. Hereinafter, embodiments of the present invention and effects thereof will be described with reference to the accompanying drawings.

<Production Example>

(1) Preparation Example 1-Preparation of amino acid metal salt (catalyst)

75 g of glycine was added to a mixed solvent of 500 ml of distilled water and 200 ml of ethanol, stirred at room temperature for 2 hours to completely dissolve, and then 59 g of sodium carbonate was dissolved in 100 ml of distilled water, and the solution in which glycine was dissolved was slowly added dropwise while stirring. Let it react for 3 hours. After the reaction, the temperature was lowered to room temperature and then reduced pressure (20mmHg) to obtain a solid sodium glycinate. After the solid sodium glycinate was added to a solvent prepared in a ratio of 8:2 of propanol and ethanol, it was completely dissolved by heating at 100°C. After that, it was gradually cooled to room temperature to obtain crystalline sodium glycinate, and filtered to prepare 92 g of pure sodium glycinate (yield about 95%). 90 g of sodium graicinate obtained above was added to 800 ml of distilled water and 200 ml of ethanol, stirred for 1 hour to dissolve, and then 135 g of copper chloride dissolved in distilled water was slowly added dropwise while stirring, followed by heating at about 80°C while stirring to react for 3 hours. A complex compound of capaglycinate was prepared.

(2) Preparation Example 2-Preparation of hydroxy acid metal salt (accelerator)

After 149 g of ricinoleic acid was added to 1000 ml of propanol, heated and stirred at 80° C. to dissolve, then 25 g of sodium hydroxide dissolved in 300 ml of water was slowly added dropwise, heated and stirred at 100° C. for 5 hours, cooled to room temperature, and mixed with a solvent. Impurities were distilled off under reduced pressure to remove 150 g of sodium ricinolate. 200 ml of triethanolamine, 800 ml of ethanol, and 200 ml of distilled water were added to 150 g of sodium ricinolate obtained above, heated and stirred for 2 hours, and then a solution in which 50 g of 200 ml of magnesium chloride was dissolved was slowly added dropwise and heated and stirred at 100° C. for 5 hours. Siumricinolate was prepared.

<Examples and Comparative Examples>

(1) Example 1

Low-density polyethylene (LDPE) (MFI=1g/10min) 97.0% by weight without antioxidants, 2.0% by weight of copper glycinate prepared in Preparation Example 1, and magnesium prepared in Preparation Example 2 Ricinolenite (Mgnecium ricinoleate) 1.0% by weight was compounded. For compounding, a 40 mm, L/D=40 DLS Twin Screw Extruder was used. At this time, the cylinder was heated to 180°C to 190°C, and the pressure was maintained at 30 kgf/cm2 to 32 kgf/cm2. The pellets prepared under these conditions were made of medium-colored pellets.

The prepared pellets were heated to 180°C to 190°C using a 50mm Blown Extruder, and a film having a thickness of 40-50 μm was formed under the conditions of Adapter/Die 190°C and screw 30 rpm.

(2) Example 2

A film was prepared in the same manner as in Example 1, except that magnesium glycinate prepared in Preparation Example 2 was used instead of capaglycinate as a catalyst.

(3) Example 3

A film was prepared in the same manner as in Example 1, except that the catalyst capaglycinate was changed to 3.0% by weight and the accelerator magnesium ricinolate was changed to 0.0% by weight.

(4) Example 4

A film was prepared in the same manner as in Example 1, except that capaglycinate as a catalyst was not added (changed to 0.0% by weight) and magnesium ricinolate as an accelerator was changed to 3.0% by weight.

(5) Example 5

A film was prepared in the same manner as in Example 1, except that the accelerator magnesium ricinolate was changed to 0.9% by weight, and 0.1% by weight of benzophenone was further added.

(6) Example 6

A film was prepared in the same manner as in Example 1 by adding 1.0% by weight of potassium glutamate instead of capaglycinate as a catalyst.

(7) Example 7

A film was prepared in the same manner as in Example 1 by adding 1.0% by weight of silver dihydroxystearate instead of magnesium ricinolate as an accelerator.

(8) Example 8

A film was prepared in the same manner as in Example 1 by adding 1.0% by weight of capaglycinate as a catalyst and 2.0% by weight of magnesium ricinolate as an accelerator.

(9) Comparative Example 1

Only low-density polyethylene (LDPE) (M.F.I.=1 g/10min) without antioxidant was compounded under the same conditions as in Example 1 to prepare pellets, and then a film was prepared.

(wt%) Suzy Catalyst accelerant Photosensitizer ingredient content ingredient content ingredient content ingredient content Example 1 LDPE 97.0 copper glycinate 2.0 magnesium recinoleate 1.0 - - Example 2 LDPE 97.0 magnesium glycinate 2.0 magnesium recinoleate 1.0 - - Example 3 LDPE 97.0 copper glycinate 3.0 - - - - Example 4 LDPE 97.0 - - magnesium recinoleate 3.0 - - Example 5 LDPE 97.0 magnesium glycinate 2.0 magnesium recinoleate 0.9 benzo-
phenone 0.1 Example 6 LDPE 97.0 potassium glutamate 1.0 magnesium recinoleate 1.0 - - Example 7 LDPE 97.0 copper glycinate 2.0 silver dihydroxy stearate 1.0 - - Example 8 LDPE 97.0 copper glycinate 1.0 magnesium recinoleate 2.0 - - Comparative Example 1 LDPE 100.0 - - - - - -

<Experimental Example>

(1) Experimental Example 1

The films prepared in Examples and Comparative Examples were irradiated with ultraviolet rays for 300 hours using a UV lamp aging tester according to ASTM D 15 ultraviolet treatment test method, and then time with a universal testing machine (UTM). The elongation rate according to the elongation was measured, and the results are shown in Table 2 below. In addition, a photograph of the film before/after UV decomposition of Example 3 is shown in FIG. 1.

UV irradiation time (hr) Elongation (%) 0 100 200 300 Example 1 26.32 15.67 3.87 1.54 Example 2 26.02 13.72 2.78 0.68 Example 3 25.98 10.58 1.25 -* Example 4 26.47 21.56 18.33 12.54 Example 5 26.34 12.23 3.02 0.89 Example 6 26.55 16.32 4.07 1.97 Example 7 26.25 14.24 3.27 1.24 Example 8 25.57 18.67 7.86 4.46 Comparative Example 1 26.57 25.54 23.78 22.92 * Disassembled and cannot be measured

The elongation rate has a lower value as more decomposition by oxidation occurs. From the results of Table 2 above, when comparing the elongation values of Example 1 with the oxidizing biodegradant and Example 4 without the oxidizing biodegradant and Comparative Example 1, Example 1 with the oxidizing biodegradant shows a remarkably low value. It can be determined that it happened. Comparing Example 1 and Example 2, it was confirmed that the decomposition was faster when magnesium glycinate was used than the capaglycinate as a catalyst, and the decomposition was faster than that of Example 5 with the photosensitizer added. Can be confirmed In addition, in the case of Example 3 to which a catalyst was added, it could be confirmed that the decomposition rate was faster than in other examples, and the results of Examples 1 and 7 showed that when the silver metal salt as an accelerator was added, the decomposition rate slightly increased. Although there was a trend, the impact is judged to be insignificant when considering economic feasibility. Comparing Example 8 and Example 1, when the content of the catalyst of Example 8 was lowered and the content of the accelerator was increased, it was confirmed that the decomposition rate was slow, and thus the content of the catalyst was found to have more influence upon decomposition. These results confirm that the decomposition rate of the plastic resin can be controlled by controlling the content of the catalyst and the content of the accelerator.

(2) Experimental Example 2

In order to confirm that the film of Example 1 was decomposed in the actual natural environment, an outdoor exposure test was conducted for 3 months at the Seosan outdoor exposure test site of Korea Living Environment Testing Research Institute, and the exposure period was 3 months, exposure angle 45ㅀ, temperature up to 33.4℃. , A minimum of 14 ℃, a relative humidity of 96%, a minimum of 11%, an average of 66%, and a total amount of ultraviolet rays of 315-400nm (89.01 mJ/m ² ). The results are shown in FIG. 2. As shown in FIG. 2, it can be seen that the film decomposed and fell off after 3 months in natural light.

(3) Experimental Example 3

After 300 hours of irradiation with ultraviolet rays of Examples 3 and 5, the sample was requested to measure the molecular weight reduction, and the condition was measured using GPC (gel permeation chromatography), and the column was Olexis Column 1 (7.5mmx300mm). The detector used a Refractive index (RI), and the results are shown in Table 3.

Condition Example 5 Example 3 Mn
(dalton) Mw
(dalton) Mw/Mn Mn
(dalton) Mw
(dalton) Mw/Mn 50h 10,117 112,124 11.08 10,566 85,679 8.11 100h 11,837 82,945 7.01 6,144 34,981 5.69 150h 4,696 23,928 5.09 3,495 16,772 4.80 200h 3,827 14,775 3.86 4,561 14,678 4.12 250h 3,366 12,093 3.59 2,489 9,171 3.68 300h 2,763 9,189 3.32 2,184 6,901 3.16 350h 2,253 7,055 3.13 1,648 4,625 3.26

As shown in Table 3, it was confirmed that the molecular weight decreased with the UV irradiation time, and the weight average molecular weight (Mw) showed a sharp decrease up to 150 hours, and the number average molecular weight (Mn) showed a somewhat slower decrease than this. This result confirms that the molecular weight decreases due to the progress of oxidative biodegradation. This is a result confirming that decomposition is possible to less than oligomer when irradiated with ultraviolet rays for a longer period of time, and that plastic can ultimately be decomposed.

The features, structures, effects, and the like illustrated in each of the above-described embodiments may be combined or modified for other embodiments by a person having ordinary knowledge in the field to which the embodiments belong. Accordingly, contents related to such combinations and modifications should be interpreted as being included in the scope of the present invention.

Claims (11)

Including a polyolefin-based resin and an additive that helps the oxidation biodegradation of the polyolefin-based resin,
The additive includes a catalyst comprising an amino acid metal salt,
The amino acid metal salt includes at least one or more metal salts of any one or more amino acids selected from the group consisting of amino acids including amino groups and carboxyl groups, amino acids including hydroxy groups or sulfur groups, and isomers thereof,
The amino acid containing a hydroxy group or a sulfur group is an oxidative biodegradable composition comprising at least one selected from the group consisting of hydroxylysine, homoserine, homocysteine, statins, and isomers thereof.
The method of claim 1,
The additive is an oxidative biodegradable composition, characterized in that it contains 0.5% to 20% by weight based on the total weight of the composition.
The method of claim 1,
The amino acids including the amino group and carboxyl group include glycine, alanine, cysteine, serine, valine, methionine, proline, phenylalanine, tyrosine, aspartic acid, glutamic acid, proline, asparagine, glutamine, histidine, aminobutyric acid, and these Oxidative biodegradable composition comprising any one or more selected from the group consisting of isomers of.
The method of claim 1,
The amino acid metal salts are magnesium (Mg), sodium (Na), cobalt (Co), nickel (Ni), iron (Fe), tin (Sn), manganese (Mn), zinc (Zn), potassium (K), and silver. Oxidative biodegradable composition comprising at least one selected from the group consisting of (Ag), gold (Au) and copper (Cu).
The method of claim 1,
The amino acid metal salts are potassium glutamate, sodium glutamate, magnesium glutamate, manganese glutamate, silver glutamate, zinc glutamate, potassium glycinate, sodium glycinate, magnesium glycinate, manganese glycinate, silver glycinate, zinc glycine. Oxidative biodegradation composition comprising any one or more selected from the group consisting of nate and capaglycinate.
Including a polyolefin-based resin and an additive that helps the oxidation biodegradation of the polyolefin-based resin,
The additive includes an accelerator containing a metal hydroxy acid salt,
The hydroxy acid metal salt is hydroxylinoleic acid (2-hydroxylinoleic acid), trans hydroxydekenoic acid (trans 10-hydroxydec-2-enoic acid), hydroxydekenoic acid (9-hydroxydec-2-enoic acid) , Hydroxy octadienoic acid (8-hydroxy-5,6-octadienoic acid), hydroxy icosenoic acid (14-hydroxy-11-eicosenoic acid), hydroxy octadecenoic acid (12-hydroxy-9) -octadecenoic acid), hydroxyoctadecadienoic acid (12-hydroxy-9,15-octadecadienoic acid) and hydroxyecosadienoic acid (14-hydroxy-11,17-eicosadienoic acid) selected from the group consisting of An oxidation biodegradable composition comprising at least one or more metal salts of any one or more hydroxy acids.
The method of claim 6,
The hydroxy acid metal salt is magnesium (Mg), sodium (Na), cobalt (Co), nickel (Ni), iron (Fe), tin (Sn), manganese (Mn), zinc (Zn), potassium (K) , Silver (Ag), gold (Au), and oxidized biodegradable composition comprising at least one selected from the group consisting of copper (Cu).
The method of claim 6,
The additive is an oxidative biodegradable composition, characterized in that it contains 0.5% to 20% by weight based on the total weight of the composition.
Including a polyolefin-based resin and an additive that helps the oxidation biodegradation of the polyolefin-based resin,
The additive includes a catalyst including an amino acid metal salt and an accelerator including a hydroxy acid metal salt,
It contains 1 to 50 parts by weight of the accelerator based on 100 parts by weight of the catalyst,
The amino acid metal salt includes at least one or more metal salts of any one or more amino acids selected from the group consisting of amino acids including amino groups and carboxyl groups, amino acids including hydroxy groups or sulfur groups, and isomers thereof,
The amino acid containing a hydroxy group or a sulfur group includes any one or more selected from the group consisting of hydroxylysine, homoserine, homocysteine, statins, and isomers thereof,
The hydroxy acid metal salt is hydroxylinoleic acid (2-hydroxylinoleic acid), trans hydroxydekenoic acid (trans 10-hydroxydec-2-enoic acid), hydroxydekenoic acid (9-hydroxydec-2-enoic acid) , Hydroxy octadienoic acid (8-hydroxy-5,6-octadienoic acid), hydroxy icosenoic acid (14-hydroxy-11-eicosenoic acid), hydroxy octadecenoic acid (12-hydroxy-9) -octadecenoic acid), hydroxyoctadecadienoic acid (12-hydroxy-9,15-octadecadienoic acid) and hydroxyecosadienoic acid (14-hydroxy-11,17-eicosadienoic acid) selected from the group consisting of An oxidation biodegradable composition comprising at least one or more metal salts of any one or more hydroxy acids.
The method according to any one of claims 1 to 9,
The additive further comprises a ketone-based photosensitizer,
The ketone-based photosensitizers are diphenylmethanone, butane-2,3-dione, 1-phenyl-1,2-propanedione ,2-propanedione) and camphor quinone (camphorquinone), characterized in that it comprises any one or more selected from the group consisting of an oxidative biodegradable composition.
A film prepared using the oxidized biodegradable composition of any one of claims 1 to 9.

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