KR20210052703A - Room temperature complex decomposition additive having lactate-based compound and pellet for injection molding produced therefrom - Google Patents

Abstract

The present invention relates to a room-temperature complex decomposition additive composition including a lactate-based compound added thereto, and pellets for injection molding obtained therefrom. Particularly, the room-temperature complex decomposition additive composition includes coconut shells, wax, a metal ion salt, an organic oxidation initiator, an organic acid, a peroxide, a room-temperature thermal decomposition initiator, a redox initiator, an antioxidant, a UV-absorbing agent, a lactate-based compound and ethyl lactyl retinoate. The complex decomposition additive pellets obtained from the composition may be injection molded and used for disposable containers, packaging sheets, packing materials, or the like.

Description

ROOM TEMPERATURE COMPLEX DECOMPOSITION ADDITIVE HAVING LACTATE-BASED COMPOUND AND PELLET FOR INJECTION MOLDING PRODUCED THEREFROM}

The present invention relates to a room temperature composite decomposition additive composition to which a lactate-based compound is added, and to an injection pellet prepared therefrom, specifically, coconut blood, wax, metal ion salt, organic oxidation initiator, organic acid, peroxide, room temperature pyrolysis initiator , A redox initiator, an antioxidant, a UV absorber, a lactate-based compound, and a room temperature complex decomposition additive composition and a complex decomposition additive pellet prepared including ethyl lactyl retinoate. The composite decomposition additive pellet prepared in this way can be injected and molded to be used as a disposable device, a wrapping paper, a filler, and the like.

The UAE, Pakistan, France, Italy, and New York State in the US have passed or are promoting legislation to distribute products using degradable plastics in packaging or products. As of January 1, 2014, the UAE replaced all packaging materials in the UAE with oxidative biodegradable plastics, a type of degradable plastic, and imposed a fine of about 8.5 million won for violations. UAE's oxidative biodegradable plastic is UAE S 5009 based on ASTM D 6954, with a final decomposition period of 36 months. In New York State, USA, a law was enacted on January 1, 2015 to encourage the use of degradable plastics, with a grace period of 6 months. In New York State, the decomposition period of degradable plastics is set to within 2 years, and it is recommended to use degradable plastics, which have a decomposition period shorter than that of the UAE by 12 months.

In general, degradable plastics can be classified into biodegradation, oxidative biodegradation, photolysis, or photodegradation according to the decomposition period. Among these, biodegradable plastics must be decomposed at least 90% of cellulose, which is a standard material, within 6 months under industrial composting conditions, and oxidized biodegradable plastics must be decomposed at least 90% within 36 months. Photodegradation and photodegradation plastics are excluded from the category of degradable plastics because the product form disappears and it takes more than 50 years to be completely decomposed into water and carbon dioxide. Therefore, biodegradable plastics or oxidative biodegradable plastics must be used in order to meet the standards or product sales standards of overseas countries.

In the case of biodegradable plastics, the price is higher than that of general plastics, the range of use is limited, and biodegradable plastics, which are relatively inexpensive, have problems in physical properties. Oxidative biodegradable plastics are manufactured by adding a small amount of oxidative biodegradation additives to general polymers, so they are inexpensive and have no difference in physical properties from general polymers. In addition, the oxidative biodegradable plastic has the advantage of being able to control the decomposition period according to the ratio of additives to be added, the degree of concentration, and the amount of antioxidants added.

However, in order to biodegrade the existing oxidative biodegradable plastic within 2 years, the amount of added additives is inevitably increased, and if the amount of additives is increased, the physical properties or transparency may decrease, and the unit cost of the product may increase.

In order to solve this problem, there is a need for a room temperature complex decomposition additive that can decompose plastic materials that are discarded within 6 months by adding 1 to 5% by weight of a complex biodegradant to non-degradable plastics (PE, PP, PS). Is required.

In addition, composite biodegradable plastics using room temperature composite decomposition additives must be capable of responding to international environmental regulations.

Korean Patent Registration No. 10-1785282

The present invention contains coconut pea biomass that can harmonize mechanical properties such as carbon reduction function, excellent biodegradability and tensile strength and elongation, and is capable of decomposing at room temperature, complex decomposition additive composition, complex decomposition additive pellet and injection molding It is a technical problem to provide a room temperature complex decomposable composition.

In order to achieve the above object, the present invention is based on 100 parts by weight of the total room temperature composite decomposition additive composition, 5 to 15 parts by weight of coconut pea; 0.05 to 0.5 parts by weight of wax; 1.0 to 2.0 parts by weight of a metal ion salt; 0.5 to 2.0 parts by weight of an organic oxidation initiator; 1.0 to 5.0 parts by weight of an organic acid; 0.01 to 1.0 parts by weight of peroxide; 0.5 to 2.0 parts by weight of a room temperature pyrolysis initiator; 1.0 to 5.0 parts by weight of a redox initiator; 1.0 to 4.0 parts by weight of an antioxidant; 0.01 to 1.0 parts by weight of a UV absorber; 1.0 to 5.0 parts by weight of a lactate compound; 0.5 to 1.5 parts by weight of ethyl lactyl retinoate; And it provides a room temperature composite decomposition additive composition to which a lactate-based compound including a residual amount of a binder resin is added.

The lactate-based compound may include one or more of glyceryl lactate or stearyl lactate, preferably glyceryl lactate or stearyl lactate 1 It is characterized in that it is mixed in parts by weight of :1.

The antioxidant is a primary antioxidant (1,2-dioxyethylene) bis (iminoethylene) bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and As a secondary antioxidant, tris[2-(2,4,4-trimethyl-2-pentanyl)phenyl]phosphite may be mixed in a weight ratio of 1:1.

More specifically, the wax is polyethylene wax, and the metal ion salt is a mixture of ferric (III) formate and ferric (II) lactate mixed in a weight ratio of 1:1, and the organic oxidation initiator is a weight ratio of 1:1. It is a mixture of mixed alpha-linolenic acid and gammarinolenic acid, the organic acid is maleic acid, the peroxide is benzoyl peroxide, the room temperature pyrolysis initiator is naphthalene-2-azobenzene, and the redox initiator is Cumene hydroperoxide, and the UV absorber is benzophenone.

According to another embodiment of the present invention, room temperature composite decomposition additive pellets are prepared from the composite decomposition additive composition.

According to another embodiment of the present invention, the composition for injection molding comprises the room temperature composite decomposition additive pellet; Polymer resin; It is prepared by mixing a decomposition aid accelerator.

The room temperature composite decomposition plastic manufactured including the room temperature composite decomposition additive composition according to the present invention has a carbon reduction effect and can reduce the environmental burden by promoting the decomposition of the resin, and at the same time, it has the advantage of being able to cope with international environmental regulations. Have. In particular, the present invention contains a lactate-based compound, so it has a high biodegradation effect when used with polylactic acid (PLA), and the primary and secondary antioxidants included in the room temperature complex decomposition additive composition depend on their content. The period of oxidative biodegradation can be controlled, and yellowing and deterioration of physical properties of the oxidative biodegradable plastic material can be prevented.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are only illustratively presented to explain the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

In addition, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and in case of conflict, the present specification including definitions The description of will take precedence.

In order to clearly describe the invention proposed in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification. And when a part "includes" a certain component, it means that other components may be further included, not excluding other components unless otherwise stated. In addition, the "unit" described in the specification means one unit or block that performs a specific function.

Room temperature complex decomposition additive composition according to an embodiment of the present invention, based on 100 parts by weight of the total room temperature complex decomposition additive composition, 5 to 15 parts by weight of coconut pea; 0.05 to 0.5 parts by weight of wax; 1.0 to 2.0 parts by weight of a metal ion salt; 0.5 to 2.0 parts by weight of an organic oxidation initiator; 1.0 to 5.0 parts by weight of an organic acid; 0.01 to 1.0 parts by weight of peroxide; 0.5 to 2.0 parts by weight of a room temperature pyrolysis initiator; 1.0 to 5.0 parts by weight of a redox initiator; 1.0 to 4.0 parts by weight of an antioxidant; 0.01 to 1.0 parts by weight of a UV absorber; 1.0 to 5.0 parts by weight of a lactate compound; 0.5 to 1.5 parts by weight of ethyl lactyl retinoate; And a residual amount of a binder resin.

The metal ion salt contained in the room temperature complex decomposition additive promotes a radical reaction by reacting with a redox initiator, an organic acid, and a hydro peroxide. The room temperature pyrolysis initiator included in the room temperature composite decomposition additive may control the biodegradability of a plastic product by using an azo compound having an appropriate temperature range according to temperature conditions such as processing and storage.

Coconut blood in the present invention may mean a mixture of a shell directly surrounding the pulp in a coconut fruit and a husk covering the inner shell, and a trace amount of coconut blood is unavoidably mixed in the process of collecting the coconut blood. It may mean that by-products are included. The palm oil contained in the coconut blood serves to protect the screw during the production of pellets, and the double bonds held by the coconut blood facilitate the radical reaction through redox and thus have favorable conditions for improving biodegradability. On the other hand, in the biomass, since the moisture content may cause carbonization in the process of processing or weaken the bonding force in the process of blending with other raw materials, it is advantageous to use a biomass having a low moisture content. Accordingly, it is preferable that the coconut pea has a low moisture content of about 10% or less. Coconut peel dried with a moisture content of 10% or less can be pulverized to a size of 100 to 400 mesh by any pulverizer known in the art so that it can be homogeneously blended with other raw materials, and in the present invention, to a size of 100 to 400 mesh. The crushed coconut blood is referred to as coconut blood powder. Coconut skin powder may be used in an amount of 5 parts by weight or more based on 100 parts by weight of the total room temperature complex decomposition additive composition for biodegradability of various products including pellets prepared from the additive composition according to the present invention, and in excess of 15 parts by weight. If so, it may cause a decrease in physical properties, and preferably 5 to 15 parts by weight may be used.

Wax can be used in a manner of coating the surface of the coconut blood to prevent moisture reabsorption of the dried coconut skin powder, preferably paraffin wax, liquid paraffin wax, beeswax, mold wax, emulsifying wax, candelilla Wax, polyethylene wax and polypropylene wax can be used. In addition, the wax may serve as an auxiliary agent for the lubricant, and may be advantageously used in the present invention by having an advantage of easy biodegradation due to a low molecular weight structure. Wax may be used in an amount of 0.05 parts by weight or more with respect to 100 parts by weight of the total room temperature composite decomposition additive composition for its coating function and role as a lubricant aid, and if it is used in excess of 0.5 parts by weight, it may generate debris on the die, so it is preferable. 0.05 to 0.5 parts by weight may be used.

The metal ion salt may use energy generated by a repeated redox reaction with a peroxide, which will be described later, to initiate a radical reaction. By this reaction, the polymer carbon chain is cleaved and oxidative decomposition occurs, so that the polymer can be made low molecular weight. The low-molecularized oxidized low-molecular cargo is finally digested and absorbed by microorganisms in the natural environment and converted into water and carbon dioxide, whereby decomposition can be completed. The metal ion salt according to the present invention is preferably Nickelous acetate, Nickel(II) acetate, Nickel(II) oxalate, Manganous acetate, Manganic acetate, Manganous oxalate, Cobaltous acetate, Cobaltic acetate Cobaltous oxalate, Ferric(III) formate and Ferric( Ⅱ) It may be one or more selected from the group consisting of lactate. If such a metal ion salt is used in an amount of less than 1.0 parts by weight based on 100 parts by weight of the total room temperature composite decomposition additive composition, the oxidative decomposition effect of the resin is insufficient, and when used in excess of 2.0 parts by weight, the manufacturing cost may increase. Preferably, it may be used in an amount of 1.0 to 2.0 parts by weight.

The organic oxidation initiator may be used to accelerate the decomposition reaction of the resin, and preferably a natural polyunsaturated fatty acid having an active methylene group may be used. The active methylene group formed in the polyunsaturated fatty acid is automatically oxidized by catalytic action such as light and heat, and then, by causing the deterioration of lipids, the oxidative decomposition of the resin can be accelerated. Such an organic oxidation initiator may be advantageous to have a low molecular structure in order to improve degradability, preferably C18-based alpha linolenic acid (α-Linolenic acid, ALA), gamma linolenic acid (γ-Linolenic acid, GLA), and mixtures thereof (For example, a weight ratio of 4:6 to 6:4, more specifically mixed in a weight ratio of 5:5 (1:1)) may be used. If the organic oxidation initiator is used in an amount of less than 0.5 parts by weight based on 100 parts by weight of the total room temperature complex decomposition additive composition, the decomposition effect will be insufficient, and if it is used in excess of 2.0 parts by weight, unnecessary manufacturing cost increases and excessive oxidation is accelerated. Since it may cause, it may be preferably used in an amount of 0.5 to 2.0 parts by weight.

The organic acid may be used to induce crosslinking between the plasticized coconut skin powder and the binder polymer, and to react with metal ions to accelerate the decomposition of the polymer, and the organic acid according to the present invention is preferably propionic acid, paranitbenzoic acid, It may be one or more selected from the group consisting of citric acid, malic acid, and maleic acid. If the organic acid is used in an amount of less than 1.0 parts by weight based on 100 parts by weight of the total room temperature complex decomposition additive composition, the oxidative decomposition function of the resin may be poor, and if it is used in excess of 5.0 parts by weight, unnecessary manufacturing costs may increase. It can be used in an amount of 1.0 to 5.0 parts by weight.

The peroxide may be used to activate the radical reaction of the energy generated by the redox reaction with the metal ion salt, and may be additionally used to form a graft bond between the plasticized coconut skin powder and a binder polymer to be described later. . Peroxides are azo-bis-isobutylonitrile, tributyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-tributyl peroxide, 2,5 dimethyl-2,5 di(tibutylperoxy)hexane And it may be at least one selected from the group consisting of 1,3-bis (ti-butylperoxy-isopropyl) benzene. Peroxide may be used in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the total room temperature composite decomposition additive composition, and if it is used in an amount of less than 0.01 parts by weight, it is difficult to expect a graft bonding effect with a polymer due to less generation of resin polymer end groups. Since the biodegradation and oxidation effect of is reduced, the final biodegradation period may be prolonged, and if it is used in excess of 1.0 part by weight, it may be decomposed too early, and therefore, preferably 0.01 to 1.0 parts by weight may be used.

As the room temperature pyrolysis initiator, an aromatic azo compound may be preferably used. The aromatic azo compound undergoes a radical initiation reaction by forming two radicals by simultaneously decomposing both bonds of an azo group (-N=N-) at room temperature. Room temperature pyrolysis initiator is 2,2'-azobisisobutyronitrile (2,2-Azobisisobutyronitrile), naphthalene-2-azobenzene (Naphthalene-2-azobenzene), the following 3-methyl-1- (p-nitrophenyl) -5-pyrazolone-4-azo-3'-(4'-hydroxybenzamide)(3-Methyl-1-(p-nitrophenyl)-5-pyrazolone-4-azo-3'-(4'- hydroxybenzamide)), and at least one selected from the group consisting of anthracene-2-azoo-2'-naphthalene-7'-azobenzene (anthracene-2-azo-2'-naphthalene-7'-azobenzene) can be used. And, preferably, it may be used in an amount of 1.0 to 2.0 parts by weight based on 100 parts by weight of the total room temperature composite decomposition additive composition.

As the redox initiator, a persulfate-based initiator and a hydroperoxide-based initiator may be used. As the persulfate initiator, ammonium persulfate (APS), potassium persulfate (PPS), sodium persulfate (SPS), and Hydroxymethanesulfinic acid monosodium salt dihydrate may be used.In particular, ammonium persulfate (APS) may be used alone or It can be used in combination with a reducing agent such as ammonium bisulfite and sodium metabisulfite, and the hydroperoxide-based initiator is preferably tert-Butyl hydroperoxide, tert-Amyl peroxybenzoate, 2,2-di(tert-amyl peroxy) butane, 2,2-di(tert-butyl peroxy)butane and cumene hydroperoxide can be used. The redox initiator may be used in an amount of 1.0 to 5.0 parts by weight based on 100 parts by weight of the total room temperature composite decomposition additive composition.

Antioxidants include primary antioxidants and secondary antioxidants.

The primary antioxidant is Tetrakis[methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane of the following formula 1, Octadecyl 3-(3'5'-di-tert-butyl-4 of the following formula 2) '-hydroxyphenyl)propionate, Hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate of the following formula 3, (1,2-Dioxoethylene)bis(iminoethylene)bis(3) of the following formula 4 -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 3,5-DI-TERT-BUTYL-4-HYDROXY-HYDROCINNAMIC ACID TRIESTER OF 1,3,5-TRIS(2 It may be any one selected from -HYDROXYETHYL)-S-TRIAZINE-2,4,6-(1H,3H,5H)-TRIONE. The primary antioxidant plays a role in stabilizing the plastic by reacting with the radicals generated in the plastic to prevent the deterioration of the composite decomposition plastic product manufactured including the room temperature complex decomposition additive and prolong the oxidative biodegradation period.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

Secondary antioxidants are Tris(2,4-di-t-butyl phenyl)phosphite of the following formula 6, Tris[2-(2,4,4-trimethyl-2-pentanyl)phenyl] phosphite of the following formula 7, It may be any one selected from Tris (nonylphenyl) phosphite of Formula 8 and tris[4-(acetamido)phenyl] phosphite of Formula 9 below. Secondary antioxidants form decomposition reactions with peroxides to prevent yellowing of plastic products and to delay oxidative decomposition.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The first antioxidant and the second antioxidant are mixed in a weight ratio of 5:5 (1:1), and 1.0 to 4.0 parts by weight may be used based on 100 parts by weight of the total room temperature complex decomposition additive composition. It is adjusted according to the biodegradation period of the degradable plastic material

The UV-absorbing agent is at least one selected from the group of benzophenone, benzotriazole, benzylidene malonate, oxanilide, benzoaxazinone or triazine, and benzophenone and benzotriazole are preferred. The UV absorber may be used in an amount of 0.01 to 1.0 parts by weight based on 100 parts by weight of the total room temperature composite decomposition additive composition.

The lactate-based compound may be glyceryl lactate or stearyl lactate, and is preferably used by mixing in a weight ratio of 1:1, and 100 parts by weight of the total room temperature complex decomposition additive composition 1.0 to 5.0 parts by weight may be used, and the lactate-based compound exhibits a high biodegradation effect when used together with polylactic acid (PLA).

The ethyl lactyl retinoate (Ethyl Lactyl Retinoate) may be used in an amount of 1.0 to 3.0 parts by weight based on 100 parts by weight of the total room temperature complex decomposition additive composition, and ethyl lactyl retinoate has many double bonds as shown in the following [Formula 10]. It contains, and acts as a catalyst with unsaturated fatty acids to generate energy by breaking the double bond through the secondary oxidation reaction, and the energy thus generated breaks the bond of the polymer resin, accelerating decomposition and promoting pyrolysis and photolysis. It works.

[Formula 10]

Binder resins are polyethylene (PE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), high-density polyethylene (HDPE), ethylene vinyl acetate (EVA), polystyrene (PS), polyvinyl alcohol (PVA), and polypropylene (PP). ), polylactic acid (PLA), and polyhydroxybutyrate (PHB) may be one or more selected from the group consisting of, and the binder resin may be used in the range of the remaining amount of the component based on 100 parts by weight of the total additive composition.

In addition, in order to improve processability, product stability, product performance, etc., additives known in the art for manufacturing plastics may be used, preferably plasticizers, compatibilizers, lubricants, inorganic substances, and the like may be additionally added.

The room temperature composite decomposition additive composition may be prepared into composite decomposition additive pellets by a pelletizing method known in the art.

In order to prepare the room temperature composite decomposition additive pellet, the room temperature composite decomposition additive composition may be melt-kneaded by a melt-kneading apparatus known in the art such as a kneader or horizontal stirrer including a Banbari mixer, a single screw extruder or a twin screw compressor, , Preferably, a twin screw extruder may be used for the plasticization of the coconut skin powder and graft bonding between the plasticized coconut skin powder and the binder polymer. If the reaction temperature of the extruder is less than 100 ℃, mixing may be difficult as the added raw materials are not sufficiently melted. If the reaction temperature exceeds 300 ℃, carbonization may occur or the viscosity of the resin due to high temperature becomes excessively low. Since molding into a pellet shape may become impossible, the reaction temperature of the extruder may be preferably maintained in a temperature range of 100 to 300°C. In addition, the rotational speed of the screw can be 300 rpm or higher to prevent the decrease in productivity and facilitate mixing between raw materials. If it exceeds 800 rpm, the carbonization of coconut blood due to the increase in temperature due to the increase in the internal pressure of the screw is reduced. Since it may be generated, the rotational speed of the screw may preferably have a rotational speed range of 300 to 800 rpm. The composite decomposition additive composition melt-kneaded by the above method may be cooled by passing through an extruder and then cut into a predetermined size, thereby producing pellets of the composite decomposition additive at room temperature.

The composition for injection molding according to the present invention may be prepared by mixing the room temperature composite decomposition additive pellet, a polymer resin, a decomposition aid accelerator, and a biodegradable polymer.

The room temperature composite decomposition additive pellet may be added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total injection molding composition. When the composite decomposition additive pellet is used in an amount of less than 1 part by weight, the carbon reduction effect and biodegradability effect according to the biomass added to the injection molding composition is insufficient, and when used in excess of 10 parts by weight, a sheet manufactured from the composition for injection molding Since there is a problem in that physical properties such as tensile strength of are deteriorated, preferably 1 to 10 parts by weight may be used, and more preferably 1 to 5 parts by weight may be used.

The polymer resin can be a thermoplastic resin known in the art, and polystyrene (PS), polypropylene (PP), polylactic acid (PLA), polyethylene terephthalate (PET), polyethylene (PE), linear low-density polyethylene (LLDPE) , Low-density polyethylene (LDPE), high-density polyethylene (HDPE), ethylene vinyl acetate (EVA), polyvinyl alcohol (PVA) and polyhydroxybutyrate (PHB). The polymer resin according to the present invention may be the same resin as the binder resin used in the composite decomposition additive pellet in order to improve the bonding between raw materials, and preferably, a mixture of high-density polyethylene (HDPE) and polypropylene (PP) (for example, Mixed in a weight ratio of 1:1 to 1:10) can be used. The polymer resin may be used in an amount of 25 to 75 parts by weight based on 100 parts by weight of the total injection molding composition in order to improve the physical properties of the biodegradable sheet prepared from the composition for injection molding.

An inorganic material may be used as a decomposition aid accelerator, and such an inorganic material may contribute to improving the durability of the biodegradable sheet according to the present invention. As the decomposition aid accelerator according to the present invention, a mixture of calcium carbonate and talc (for example, mixed in a weight ratio of 1:6 to 6:1) may be used. If less than 5 parts by weight of the decomposition aid accelerator is used with respect to 100 parts by weight of the total injection molding composition, the durability of the biodegradable sheet may be reduced, and if it is used in excess of 65 parts by weight, the blending ratio of other raw materials to be added decreases. Preferably 5 to 65 parts by weight may be used.

The biodegradable polymer is 1 selected from the group consisting of polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyhydroxybutyrate (PHB), (PHV), thermoplastic starch (TPS), and polycaprolactone (PCL). It may be more than a species, preferably 1 to 35 parts by weight based on 100 parts by weight of the total injection molding composition may be used. When used in an amount of less than 1 part by weight, the biodegradation effect may be insufficient, and when used in an amount of 35 parts by weight or more, durability may be deteriorated.

The composition for injection molding can be manufactured in a sheet shape by a molding method known in the art, and the biodegradable sheet thus prepared is not only disposable products such as cups, tableware, chopsticks, lunch containers, disposable containers, etc. It can be applied to various industrial fields such as packaging materials, industrial films, and automobile interior materials.

Hereinafter, the configuration of the present invention and effects thereof will be described in more detail through specific examples and comparative examples. However, the present examples are for explaining the present invention more specifically, and the scope of the present invention is not limited to these examples.

[Example 1]

(1) Preparation of room temperature complex decomposition additive composition

Based on 100 parts by weight of the total composite decomposition additive composition, 10 parts by weight of coconut pea; 0.25 parts by weight of polyethylene wax; 1.2 parts by weight of ferric (III) formate and ferric (II) lactate mixed in a weight ratio of 5:5 (1:1); 1 part by weight of a mixture of alpha linolenic acid and gamma linolenic acid mixed in a weight ratio of 5:5 (1:1); 1.5 parts by weight of maleic acid; 0.05 parts by weight of benzoyl peroxide; 1.5 parts by weight of naphthalene-2-azobenzene; 2.5 parts by weight of cumene hydroperoxide; 1.0 part by weight of (1,2-Dioxoethylene)bis(iminoethylene)bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) as a primary antioxidant; 1.0 part by weight of Tris[2-(2,4,4-trimethyl-2-pentanyl)phenyl] phosphite as a secondary antioxidant; 1 part by weight of benzophenone; After adding 4 parts by weight of Glyceryl lactate stearyl lactate and 75 parts by weight of polylactic acid (PLA) to a supermixer at a weight ratio of 5:5 (1:1) Mixing at temperature for 12 minutes to prepare a room temperature composite decomposition additive composition.

(2) Preparation of composite decomposition additive pellets

After melt-kneading the prepared composite decomposition additive composition using a twin-screw extruder, the reaction temperature is 100 to 300 °C, the screw is cooled through a twin-screw extruder having a rotation speed of 300 to 800 RPM, and then cut into a predetermined size. Composite decomposition additive pellets were prepared.

(3) Preparation of injection molding composition and biodegradable sheet

5 parts by weight of the composite decomposition additive pellet prepared above based on 100 parts by weight of the total injection molding composition; 20 parts by weight of high-density polyethylene (HDPE); 25 parts by weight of polypropylene (PP); 15 parts by weight of calcium carbonate; A composition for injection molding was prepared by mixing 15 parts by weight of talc and 20 parts by weight of polylactic acid (PLA), and then a biodegradable sheet was prepared using a sheet manufacturing facility known in the art.

[Example 2]

A biodegradable sheet was prepared in the same manner as in Example 1 by adding 1 part by weight of ethyl lactyl retinoate instead of 1 part by weight of polylactic acid (PLA) in the manufacturing step of the room temperature complex decomposition additive composition of Example 1. .

[Comparative Example 1]

In the manufacturing step of the room temperature composite decomposition additive composition of Example 1, a biodegradable sheet was prepared in the same manner as in Example 1 by using polyethylene instead of polylactic acid (PLA).

[Comparative Example 2]

Propionic acid in place of maleic acid in the manufacturing step of the room temperature complex decomposition additive composition of Example 1; 1,3-bis(ti-butylperoxy-isopropyl)benzene in place of benzoyl peroxide; 2,2'-azobisisobutyronitrile in place of naphthalene-2-azobenzene; A biodegradable sheet was prepared in the same manner as in Example 1 by using polyethylene instead of polylactic acid (PLA).

For the sheet samples according to the Examples and Comparative Examples prepared as described above, molecular weight reduction evaluation and biodegradability evaluation were performed.

[Experimental Example]

(1) molecular weight reduction evaluation

Changes in molecular weight of the sheet samples according to Examples 1 and 2 and Comparative Examples 1 and 2 were measured. Countries that have certification standards for degradable films worldwide include the United States, Sweden, United Kingdom, Korea, Singapore, and the UAE. Among the countries that have the above certification criteria, except for the UK, which conducts sensory testing, other countries perform molecular weight evaluation, biodegradation evaluation, gel residue test, physical property degradation, and heavy metal test according to the method of ASTM D 6954. For the molecular weight of Sweden and Singapore, a molecular weight of 10,000 Da or less is the evaluation reference point according to the method of ASTM D 6954 Tier 1, and in Korea and the UAE, a molecular weight of 5,000 Da or less is the evaluation reference point according to the method of ASTM D 6954 Tier 1. Molecular weight evaluation was carried out for 300 hours and 400 hours at an irradiance of 340 nm and a temperature of 50° C. according to the method of ASTM D 6954 Tier 1 at the Korea Apparel Testing Institute, and the results are shown in Table 1 below.

Time(hr) Example 1 Example 2 Comparative Example 1 Comparative Example 2 300 3,854 Da 3,626 Da 4,176 Da 4,375 Da 400 2,938 Da 2,701 Da 3,513 Da 3,798 Da

As a result of the experiment, Example 1 and Example 2 both entered the molecular weight of the 3,000 Da range after 300 hours, and entered the molecular weight of the 2,000 Da range after 400 hours.

Comparing Examples 1 and 2 with Comparative Example 2, propionic acid, 1,3-bis(thi-butylperoxy-isopropyl)benzene, 2,2'-azobisiso Excellent biodegradation with lactate compounds in the case of preparing a room temperature complex decomposition additive composition with a combination of maleic acid, benzoyl peroxide, naphthalene-2-azobenzene, and polylactic acid (PLA) rather than using butyronitryl and polyethylene. It can be seen that the effect is shown.

In addition, when comparing Examples 1 and 2, it can be seen that ethyl lactyl retinoate improves the biodegradation effect, and when the lactate-based compound is used together with polylactic acid (PLA), the biodegradation effect is particularly improved. It was confirmed to be made (Comparative Example 1).

(2) Room temperature biodegradability evaluation

In order to evaluate the biodegradability of the standard cellulose and the sheets prepared from Examples 1 and 2 and Comparative Examples 1 and 2, a test was conducted according to ASTM D6954-04. Degradability evaluation can be divided into three stages. In the first stage, chemical decomposition is performed by treating with UVA 340nm for 100 hours by ASTM D5208-01 CYCLE A method, and then the biodegradability of the UV-treated sample is determined by the method of KSM-3100-1. It was measured as. The results of the biodegradability test for 45 days according to the ASTM D6954-04 method are shown in Table 2 below.

division Average biodegradability calculated by CO _{2 emissions} Standard material Example 1 Example 2 Comparative Example 1 Comparative Example 2 unit(%) 74.2 60.2 63.1 55.8 53.2

As a result of the experiment, in the same manner as in the molecular weight reduction evaluation, the highest biodegradability was shown in Example 2 containing ethyl lactyl retinoate. I was able to confirm that.

The above description is merely illustrative of the technical idea of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications and variations without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are not intended to limit the technical idea of the present invention, but to explain, and the protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the scope equivalent thereto It should be construed as being included in the scope of the invention.

Claims (7)

Based on 100 parts by weight of the total room temperature complex decomposition additive composition,
5 to 15 parts by weight of coconut pea; 0.05 to 0.5 parts by weight of wax; 1.0 to 2.0 parts by weight of a metal ion salt; 0.5 to 2.0 parts by weight of an organic oxidation initiator; 1.0 to 5.0 parts by weight of an organic acid; 0.01 to 1.0 parts by weight of peroxide; 0.5 to 2.0 parts by weight of a room temperature pyrolysis initiator; 1.0 to 5.0 parts by weight of a redox initiator; 1.0 to 4.0 parts by weight of an antioxidant; 0.01 to 1.0 parts by weight of a UV absorber; 1.0 to 5.0 parts by weight of a lactate compound; Ethyl Lactyl Retinoate (Ethyl Lactyl Retinoate) 0.5 to 1.5 parts by weight; And room temperature complex decomposition additive composition to which a lactate-based compound including a residual amount of a binder resin is added.
The method of claim 1,
The lactate-based compound is a room temperature complex decomposition additive composition containing a lactate-based compound, characterized in that it contains at least one of glyceryl lactate or stearyl lactate.
The method of claim 1,
The lactate-based compound is a room temperature complex decomposition additive composition to which a lactate-based compound is added, characterized in that glyceryl lactate or stearyl lactate is mixed in an amount of 1:1 by weight.
The method of claim 1,
The antioxidant is a primary antioxidant (1,2-dioxyethylene) bis (iminoethylene) bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) and Room temperature complex decomposition additive with lactate compound, characterized in that tris[2-(2,4,4-trimethyl-2-pentanyl)phenyl]phosphite as a secondary antioxidant is mixed in a weight ratio of 1:1 Composition.
The method of claim 1,
The wax is polyethylene wax, and the metal ion salt is a mixture of ferric (III) formate and ferric (II) lactate mixed in a weight ratio of 1:1, and the organic oxidation initiator is alpha mixed in a weight ratio of 1:1. It is a mixture of linolenic acid and gammarinolenic acid, the organic acid is maleic acid, the peroxide is benzoyl peroxide, the room temperature pyrolysis initiator is naphthalene-2-azobenzene, and the redox initiator is cumene hydroper A room temperature complex decomposition additive composition to which a lactate-based compound is added, which is an oxide, and the UV absorber is benzophenone.
A room temperature complex decomposition additive pellet prepared from the room temperature complex decomposition additive composition of any one of claims 1 to 5.
Room temperature composite decomposition additive pellet according to claim 6; Polymer resin; Decomposition aid accelerators; And a composition for injection molding prepared by mixing a biodegradable polymer.