KR102261508B1 - 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 to which a lactate-based compound is added, and pellets for injection prepared therefrom, and specifically, coconut skin, wax, metal ion salt, organic oxidation initiator, organic acid, peroxide, room temperature thermal decomposition initiator , a redox initiator, an antioxidant, a UV absorber, a lactate-based compound, and ethyl lactyl retinoate (Ethyl Lactyl Retinoate) It relates to a room temperature composite decomposition additive composition and composite decomposition additive pellets. The composite decomposition additive pellets prepared in this way can be injection and molded to be used as disposable devices, packaging papers, fillers, and the like.

Description

Room temperature composite decomposition additive composition to which a lactate-based compound is added, and pellets for injection produced therefrom

The present invention relates to a room temperature complex decomposition additive composition to which a lactate-based compound is added, and pellets for injection prepared therefrom, and specifically, coconut skin, wax, metal ion salt, organic oxidation initiator, organic acid, peroxide, room temperature thermal decomposition initiator , a redox initiator, an antioxidant, a UV absorber, a lactate-based compound, and ethyl lactyl retinoate (Ethyl Lactyl Retinoate) It relates to a room temperature composite decomposition additive composition and composite decomposition additive pellets. The composite decomposition additive pellets prepared in this way can be injection and molded to be used as disposable devices, packaging papers, fillers, and the like.

UAE, Pakistan, France, Italy, and New York State in the United States have passed or are in the process of passing laws to distribute products using degradable plastics in packaging or products. As of January 1, 2014, the UAE has replaced all packaging materials in the UAE with oxidative biodegradable plastic, a type of degradable plastic, and a fine of about 8.5 million won is imposed for violation of this. The oxidative biodegradable plastic in UAE is UAE S 5009 based on ASTM D 6954, and the final decomposition period is set at 36 months. New York State, USA, enacted a law on January 1, 2015 to encourage the use of degradable plastics, with a grace period of 6 months. In the case of New York State, the decomposition period of degradable plastics is set within two years, and it is recommended to use degradable plastics with a decomposition period shorter than that of the UAE by 12 months.

In general, degradable plastics can be divided into biodegradation, oxidative biodegradation, photodegradation, or photodegradation according to the decomposition period. Among them, more than 90% of biodegradable plastics should be decomposed within 6 months compared to cellulose, a standard material, under industrial composting conditions, and oxidized biodegradable plastics should be decomposed more than 90% within 36 months. In the case of photodegradable and photodegradable plastics, they are excluded from the category of degradable plastics because it takes more than 50 years to completely decompose into water and carbon dioxide as well as lose their shape. Therefore, biodegradable plastics or oxidized biodegradable plastics must be used in order to meet the standards or product sales standards of foreign countries.

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

However, in order to biodegrade existing oxidative biodegradable plastics within two years, the amount of added additives is inevitably increased, and if the amount of additives is increased, physical properties may deteriorate, transparency may decrease, and the unit price of products may rise.

In order to solve this problem, the need for a room temperature complex decomposition additive capable of decomposing plastic materials discarded within 6 months by adding 1 to 5% by weight of a complex biodegradant to the non-degradable plastic (PE, PP, PS) this is required

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

Republic of Korea Patent No. 10-1785282

The present invention contains coconut skin biomass that can harmoniously implement mechanical properties such as carbon reduction function, excellent biodegradability, tensile strength and elongation, and is decomposable at room temperature, complex decomposition additive composition, complex decomposition additive pellets and injection molding It is a technical task to provide a room temperature composite 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 skin; 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-based 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 the remaining amount of the binder resin is added.

The lactate-based compound may include at least one of glyceryl lactate and stearyl lactate, preferably glyceryl lactate or stearyl lactate 1 It is characterized in that it is mixed in a weight part 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-fentanyl)phenyl]phosphite may be mixed in a weight ratio of 1:1.

More specifically, the wax is polyethylene wax, the metal ion salt is a mixture of ferric (III) formate and ferric (II) lactate in a weight ratio of 1:1, and the organic oxidation initiator is a mixture by weight of 1:1. It is a mixture of mixed alpha-linolenic acid and gamma-linolenic acid, the organic acid is maleic acid, the peroxide is benzoyl peroxide, the room temperature thermal decomposition 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, the 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 is the room temperature composite decomposition additive pellets; polymer resin; It is prepared by mixing a degradation aid accelerator.

The room temperature composite decomposition plastic produced by 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 accelerating the decomposition of the resin, and at the same time, the advantage of responding to international environmental regulations have In particular, the present invention contains a lactate-based compound, which has a high biodegradation effect when used together with polylactic acid (PLA), and the primary antioxidant and secondary antioxidant included in the room temperature composite decomposition additive composition may vary depending on the content. The period of oxidative biodegradation can be controlled, and yellowing and deterioration of physical properties of oxidative biodegradable plastic materials can be prevented.

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

Further, 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 this invention belongs, and in case of conflict, this specification, including definitions description will take precedence.

In order to clearly explain 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, rather than excluding other components, unless otherwise stated. In addition, "unit" described in the specification means one unit or block that performs a specific function.

The room temperature composite decomposition additive composition according to an embodiment of the present invention, based on 100 parts by weight of the total room temperature composite decomposition additive composition, 5 to 15 parts by weight of coconut skin; 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-based compound; 0.5 to 1.5 parts by weight of Ethyl Lactyl Retinoate; and the remaining amount of the binder resin.

The metal ion salt contained in the room temperature complex decomposition additive reacts with the redox initiator, organic acid and hydroperoxide to promote radical reaction. The room temperature thermal decomposition initiator included in the room temperature composite decomposition additive may control the biodegradability of plastic products by using an azo compound having an appropriate temperature range according to temperature conditions such as processing and storage.

Coconut skin in the present invention may mean a mixture of the inner shell (shell) directly surrounding the pulp of the coconut fruit and the outer shell (husk) covering the inner shell, and a trace amount inevitably incorporated in the process of collecting coconut skin. It may mean that by-products are included. Palm oil contained in coconut skin serves to protect the screw during pellet production, and the double bond possessed by coconut skin has favorable conditions for improving biodegradability by facilitating radical reaction through redox. On the other hand, in the biomass, since the moisture content may cause carbonization in the processing process or weaken the binding force in the compounding process with other raw materials, it is advantageous to use a biomass having a low moisture content. Accordingly, it is preferable that coconut skin has a low moisture content of about 10% or less. Coconut skin dried to 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 pulverized coconut skin is called coconut skin powder. For the biodegradability of various products including pellets prepared from the additive composition according to the present invention, 5 parts by weight or more of the coconut skin powder may be used based on 100 parts by weight of the total room temperature composite decomposition additive composition, and used in excess of 15 parts by weight Since it may cause deterioration of physical properties, preferably 5 to 15 parts by weight may be used.

The wax may be used in a way that is coated on the surface of the coconut skin to prevent moisture reabsorption of the dried coconut skin powder, preferably paraffin wax, liquid paraffin wax, beeswax, molda wax, emulsifying wax, candelilla Waxes, polyethylene waxes and polypropylene waxes can be used. In addition, the wax can act as an auxiliary agent for a lubricant, and can be advantageously used in the present invention because it has the advantage of easy biodegradation due to its low molecular structure. For the coating function and the role as a lubricant auxiliary, 0.05 parts by weight or more may be used based on 100 parts by weight of the total room temperature composite decomposition additive composition, and when used in excess of 0.5 parts by weight, it may cause dregs on the dice, so it is preferable 0.05 to 0.5 parts by weight may be used.

The metal ion salt may use energy generated by repeated redox reactions with peroxides, 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 reduced in molecular weight. The low-molecular-oxidized low-molecular-weight product is finally digested and absorbed by microorganisms in the natural environment, and converted into water and carbon dioxide, so that 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. When such 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 complex decomposition additive composition, the oxidative decomposition effect of the resin is insignificant, and when used in excess of 2.0 parts by weight, it may cause an increase in manufacturing cost, Preferably 1.0 to 2.0 parts by weight may be used.

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 or heat, and then causes the deterioration of the lipid, thereby promoting the oxidative decomposition of the resin. 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 (GLA), and mixtures thereof. (For example, a mixture in a weight ratio of 4:6 to 6:4, more specifically, a mixture in a weight ratio of 5:5 (1:1)) may be used. When 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 composite decomposition additive composition, the decomposing effect is insignificant, and when used in excess of 2.0 parts by weight, unnecessary increase in manufacturing cost and excessive oxidation are 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 shell powder and the binder polymer, and to promote the decomposition of the polymer by reacting with metal ions, and the organic acid according to the present invention is preferably propionic acid, paranitrile benzoic acid, It may be at least one selected from the group consisting of citric acid, malic acid and maleic acid. When 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 when used in excess of 5.0 parts by weight, it may cause an unnecessary increase in manufacturing cost. 1.0 to 5.0 parts by weight may be used.

The peroxide may be used to activate a radical reaction using the energy generated by the redox reaction with the metal ion salt, and may additionally be used to form a graft bond between the plasticized coconut shell powder and the binder polymer to be described later. . Peroxides are azo-bis-isobutylonitrile, tributyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, di-tributylperoxide, 2,5 dimethyl-2,5-di(tibutylperoxy)hexane and 1,3-bis(t-butylperoxy-isopropyl)benzene. The 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 when used in an amount of less than 0.01 parts by weight, it is difficult to expect a graft bonding effect with the polymer, or Since the biodegradation and oxidative effect of the biodegradation and oxidative effects may be reduced, and the final biodegradation period may be prolonged, if used in excess of 1.0 part by weight, it may be decomposed too early, so 0.01 to 1.0 part by weight may be preferably used.

As the room temperature thermal decomposition initiator, an aromatic azo compound may be preferably used. Aromatic azo compounds undergo radical initiation by forming two radicals by simultaneously decomposing both bonds of an azo group (-N=N-) at room temperature. Room temperature thermal decomposition 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-azo-2'-naphthalene-7'-azobenzene (anthracene-2-azo-2'-naphthalene-7'-azobenzene) may be used. and preferably 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. Ammonium persulfate (APS), potassium persulfate (PPS), sodium persulfate (SPS) and Hydroxymethanesulfinic acid monosodium salt dihydrate may be used as the persulfate-based initiator. 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 may 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 Formula 1 below, Octadecyl 3-(3'5'-di-tert-butyl-4 of Formula 2) '-hydroxyphenyl)propionate, Hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate of Formula 3 below, (1,2-Dioxoethylene)bis(iminoethylene)bis(3) of 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 prevents the deterioration of the composite decomposition plastic product manufactured including the room temperature composite decomposition additive, and acts to stabilize the plastic by reacting with radicals generated in the plastic so that the oxidative biodegradation period can be extended.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

The secondary antioxidant is Tris(2,4-di-t-butyl phenyl)phosphite of Formula 6, Tris[2-(2,4,4-trimethyl-2-pentanyl)phenyl] phosphite of 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 a decomposition reaction with peroxide to prevent yellowing of plastic products and delay oxidative decomposition.

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

As the antioxidant, the primary antioxidant and the secondary 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 composite decomposition additive composition, and the amount used is the room temperature complex It is controlled 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 preferable. 0.01 to 1.0 parts by weight of the UV absorber may be used 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, preferably mixed in a weight ratio of 1:1, and used in 100 parts by weight of the total room temperature composite 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 catalyzes with unsaturated fatty acids to generate energy by breaking double bonds through secondary oxidation reactions, and the energy generated in this way breaks the bonds of polymer resins, accelerating decomposition and promoting thermal decomposition and photolysis. It works.

[Formula 10]

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

In addition, additives for manufacturing plastics known in the art may be used to improve processability, product stability, product performance, etc., and preferably, a plasticizer, a compatibilizer, a lubricant, and an inorganic material 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 room temperature composite decomposition additive pellets, 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, and , A twin-screw extruder may be preferably used for plasticizing coconut shell powder and graft bonding between the plasticized coconut shell powder and the binder polymer. If the reaction temperature of the extruder is less than 100 ℃, there may be difficulties in mixing because the added raw materials are not sufficiently melted. If it exceeds 300 ℃, carbonization occurs 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 rotation speed of the screw can be 300 rpm or more to prevent a decrease in productivity and facilitate mixing between raw materials, and when it exceeds 800 rpm, carbonization of coconut skin due to the temperature increase due to the increase in the internal pressure of the screw increases. can be generated, the rotation speed of the screw may preferably have a rotation speed range of 300 to 800 rpm. The composite decomposition additive composition melt-kneaded by the above method may be cooled through an extruder and then cut into a predetermined size to be manufactured into room temperature composite decomposition additive pellets.

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

The room temperature composite decomposition additive pellets may be added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total composition for injection molding. When the composite decomposition additive pellet is used in less than 1 part by weight, the carbon reduction effect and biodegradability effect due to the biomass added to the composition for injection molding are insignificant, and when used in excess of 10 parts by weight, a sheet prepared from the composition for injection molding Since the problem of deterioration of physical properties such as tensile strength of the , 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 may be a thermoplastic resin known in the art, and polystyrene (PS), polypropylene (PP), polylactic acid (PLA), polyethylene terephthalate (PET), polyethylene (PE), linear low-polyethylene (LLDPE) , low-density polyethylene (LDPE), high-density polyethylene (HDPE), ethylene vinyl acetate (EVA), polyvinyl alcohol (PVA) and may be at least one selected from the group consisting of polyhydroxybutyrate (PHB). For the polymer resin according to the present invention, the same resin as the binder resin used in the composite decomposition additive pellet may be used in order to improve the bonding force between raw materials, and preferably a mixture of high-density polyethylene (HDPE) and polypropylene (PP) (eg, mixed in a weight ratio of 1:1 to 1:10) may be used. 25 to 75 parts by weight of the polymer resin may be used based on 100 parts by weight of the total composition for injection molding 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 auxiliary accelerator, and such an inorganic material may contribute to the improvement of durability of the biodegradable sheet according to the present invention. As the decomposition auxiliary accelerator according to the present invention, preferably a mixture of calcium carbonate and talc (eg, mixed in a weight ratio of 1:6 to 6:1) may be used. When less than 5 parts by weight of the decomposition auxiliary accelerator is used with respect to 100 parts by weight of the total composition for injection molding, the durability of the biodegradable sheet may decrease, and when used in excess of 65 parts by weight, the blending ratio of other raw materials added is reduced, Preferably 5 to 65 parts by weight may be used.

The biodegradable polymer is 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 one species, and preferably 1 to 35 parts by weight based on 100 parts by weight of the total composition for injection molding may be used. When used in an amount of less than 1 part by weight, the biodegradation effect may be insignificant, and when used in an amount of 35 parts by weight or more, durability may be reduced.

The composition for injection molding may 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, and disposables, but also other food products. 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 its effects will be described in more detail through specific examples and comparative examples. However, these examples are for explaining the present invention in more detail, and the scope of the present invention is not limited to these examples.

[Example 1]

(1) Preparation of room temperature composite decomposition additive composition

Based on 100 parts by weight of the total composite decomposition additive composition, 10 parts by weight of coconut skin; 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; benzoyl peroxide 0.05 parts by weight; 1.5 parts by weight of naphthalene-2-azobenzene; 2.5 parts by weight of cumene hydroperoxide; 1.0 parts by weight of primary antioxidant (1,2-Dioxoethylene)bis(iminoethylene)bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate); 1.0 parts 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, 4 parts by weight of stearyl lactate and 75 parts by weight of polylactic acid (PLA) mixed in a weight ratio of 5:5 (1:1) to a supermixer, a temperature of 130 to 160° C. By mixing at a temperature for 12 minutes, a room temperature composite decomposition additive composition was prepared.

(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., and the screw is cooled by passing through a twin-screw extruder having a rotation speed of 300 to 800 RPM, and then cut to a predetermined size. Composite decomposition additive pellets were prepared.

(3) Preparation of composition for injection molding and biodegradable sheet

Based on 100 parts by weight of the total composition for injection molding, 5 parts by weight of the composite decomposition additive pellet prepared above; 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 composite decomposition additive composition of Example 1 .

[Comparative Example 1]

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

[Comparative Example 2]

Propionic acid instead of maleic acid in the preparation step of the room temperature composite decomposition additive composition of Example 1; 1,3-bis(t-butylperoxy-isopropyl)benzene instead of benzoylperoxide; 2,2'-azobisisobutyronitrile instead of naphthalene-2-azobenzene; A biodegradable sheet was prepared in the same manner as in Example 1 using polyethylene instead of polylactic acid (PLA).

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

[Experimental example]

(1) Evaluation of molecular weight reduction

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, the United Kingdom, Korea, Singapore, and the UAE. Among the countries that have the above certification standards, other countries, except for the UK, which conduct the sensory test, conduct molecular weight evaluation, biodegradation evaluation, gel residue test, physical property degradation, and heavy metal test according to the method of ASTM D 6954. As for the double molecular weight, in Sweden and Singapore, a molecular weight of 10,000 Da or less according to the method of ASTM D 6954 Tier 1 is an evaluation reference point, and in Korea and the UAE, a molecular weight of 5,000 Da or less according to the method of ASTM D 6954 Tier 1 is an evaluation reference point. Molecular weight evaluation was carried out at the Korea Apparel Testing and Research Institute according to the method of ASTM D 6954 Tier 1 at an irradiance of 340 nm and a temperature of 50° C. for 300 hours and 400 hours, 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 3,000 Da after 300 hours, and entered the molecular weight of 2,000 Da after 400 hours.

Comparing Examples 1 and 2 with Comparative Example 2, propionic acid, 1,3-bis(t-butylperoxy-isopropyl)benzene, 2,2'-azobisiso in the manufacturing step of the compound decomposition additive composition at room temperature Better biodegradation with a lactate compound in the case of preparing a compound decomposition additive composition at room temperature with a combination of maleic acid, benzoyl peroxide, naphthalene-2-azobenzene, and polylactic acid (PLA) rather than using butyronitrile and polyethylene It can be seen that the effect is shown.

Also, comparing Examples 1 and 2, it can be seen that Ethyl Lactyl Retinoate improves the biodegradation effect, and the lactate-based compound improves the biodegradation effect especially when used together with polylactic acid (PLA). was confirmed (Comparative Example 1).

(2) Room temperature biodegradability evaluation

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

division Average biodegradability calculated by CO _{2 emissions} standard 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, as in the molecular weight reduction evaluation, Example 2 containing ethyl lactyl retinoate showed the highest degree of biodegradation, and the biodegradation effect was increased when the lactate-based compound and polylactic acid were used together. could confirm that

The above description is merely illustrative of the technical idea of the present invention, and various modifications and variations will be possible without departing from the essential characteristics of the present invention by those skilled in the art to which the present invention pertains. Therefore, the embodiments disclosed in the present invention are intended to explain, not to limit the technical idea of the present invention, and the protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent range are 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 composite decomposition additive composition,
5 to 15 parts by weight of coconut skin; 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 thermal decomposition 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-based compound; 0.5 to 1.5 parts by weight of Ethyl Lactyl Retinoate; and the remaining amount of the binder resin, wherein the lactate-based compound contains at least one of Glyceryl lactate or Stearyl Lactate. A room temperature complex decomposition additive composition to which a lactate-based compound is added.
delete According to claim 1,
The lactate compound is glyceryl lactate (Glyceryl lactate) or stearyl lactate (Stearyl Lactate) is mixed in a weight part of 1:1.
According to claim 1,
The antioxidant is a primary antioxidant (1,2-dioxyethylene)bis(iminoethylene)bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and A room temperature composite decomposition additive to which a lactate compound is added, characterized in that tris[2-(2,4,4-trimethyl-2-fentanyl)phenyl]phosphite is mixed as a secondary antioxidant in a weight ratio of 1:1 composition.
According to claim 1,
The wax is polyethylene wax, 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 a mixture of linolenic acid and gamma-linolenic acid, the organic acid is maleic acid, the peroxide is benzoyl peroxide, the room temperature thermal decomposition initiator is naphthalene-2-azobenzene, and the redox initiator is cumene hydroperoxide. Oxide, and the UV absorber is a lactate compound is added, characterized in that benzophenone compound decomposition additive composition at room temperature.
A room temperature composite decomposition additive pellet prepared from the room temperature composite decomposition additive composition of any one of claims 1 and 3 to 5.
The room temperature composite decomposition additive pellet according to claim 6; polymer resin; decomposition auxiliary accelerators; And a composition for injection molding prepared by mixing a biodegradable polymer.