KR20190067320A - Eco-friendly biedegradable thermo plastic polymer resin composition and it's manufacturing film - Google Patents

Abstract

The present invention relates to a degradable polymer resin composition composed of a polymer resin, an oxidation promoter, a modified biodegradation agent, and the like, and a film manufactured using the same, wherein the present invention aims to manufacture a degradable material that promotes photodegradation and biodegradation of a polymer resin which is a hardly decomposable material, by decomposition using heat, light, microorganism or chemical reaction.

Description

TECHNICAL FIELD [0001] The present invention relates to an eco-degradable polymer resin composition and a film produced using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a biodegradable composition for improving the toughness and ductility of a conventional biodegradable fatty acid ester compound,

More particularly, the present invention relates to a polymer resin, an oxidizing accelerator, and a modified biodegradation material for producing a degradable material that promotes photodegradation and biodegradation of a polymer resin by decomposition action of heat, light, microorganism, And the like, and a film produced using the composition.

The polymer resin for film is applied to various fields such as polypropylene, polyethylene, polystyrene, PET, nylon, cellophane and polyacetate, various packaging materials such as advertising coating film, medicine packaging, food packaging and machine parts packaging, .

As the amount of polymer resin used increases, some recycled polymer resin products such as films, sheets, vials, foam structures and plastic containers are recycled and recycled. However, generation of environmental hormones due to incineration or landfill, Detection and incidence of air pollution due to incomplete combustion.

In particular, products made of a mixture of a polymer resin and a paper have been increasing in recent years, but most of them are incinerated, landfilled or non-reclaimed because it is difficult to separate the paper and the polymer resin.

In order to solve such a problem, studies on a degradable polymer resin composition for film and sheet have been progressing actively.

The degradable polymer resin is a polymer resin which can change its chemical structure due to a change in its chemical structure over time under specific environmental conditions such as light, heat, moisture and microorganisms, , And it is classified into a degradable polymer resin such as a biodegradable polymer resin and a photodegradable polymer resin.

The degradable polymer resins that have been researched and developed until now are partially commercialized as a biodegradable polymer resin composed of a composition such as starch, plant and aliphatic polyester, and a photodegradable polymer resin composed of a composition such as a vinyl ketone copolymer or an ethylene-carbon monoxide copolymer Has been used.

In recent years, there has been a need for a degradable polymer resin that complements the application and productivity of conventional biodegradable polymer resins, disadvantages of photolytic polymer resins, and disadvantages of expensive synthetic polymer products.

Conventional degradable polymer resin patents are disclosed in Korean Patent No. 10-1692873 (registered on Dec. 29, 2016), 'Environmentally friendly flexible PET-G resin composition with improved weatherability', 'Biodegradable resin composition, A biodegradable film produced therefrom "(Korean Registered Patent No. 10-1132382 (Registered Date: March 26, 2012))," Environmentally friendly biodegradable film composition "(Korean Patent No. 10-1249390 (A composition for preparing a breathable film containing a photodegradable agent and a breathable film using the same) (Korean Patent Laid-open Publication No. 10-2009-0055761 (published date: June 03, 2009)), (Korean Registered Patent No. 10-1195209 (registered on October 22, 2012)), a biodegradable film containing biomass, and a method for producing the same, (Korean Patent Laid- -0139421 (public date: December 07, 2016)), 'biodegradable water Composition and biodegradable film produced therefrom "(Korean Patent Registration No. 10-1784221 (registered on September 27, 2017))," biodegradable film of polylactic acid and polybutylene succinate adipate blend " 10-2012-0131961 (public date: December 05, 2012)), etc., conventional degradation products can not be completely decomposed because the degradable polymer resin has a single function such as biodegradability or photodegradability, And is composed of a composition of a large amount of additives. Thus, many problems arise in the commercialization of the composition at a high price and at the top of the manufacturing process, and also the mechanical properties such as toughness and ductility are not excellent.

Korean Registered Patent No. 10-1692873 (Registered Date: December 29, 2016) Korean Registered Patent No. 10-1132382 (Registered Date: March 26, 2012) Korean Registered Patent No. 10-1249390 (Registered Date: March 26, 2013) Korean Patent Publication No. 10-2009-0055761 (Published Date: June 03, 2009) Korean Registered Patent No. 10-1195209 (Registered Date: October 22, 2012) Korean Patent Publication No. 10-2016-0139421 (Publication date: December 07, 2016) Korean Registered Patent No. 10-1784221 (registered on September 27, 2017) Korean Patent Laid-Open No. 10-2012-0131961 (public date: December 05, 2012)

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the problems of conventional degradable polymer resin compositions and to satisfy the requirements of a product in which degradation of the polymer resin is promoted by decomposition action such as heat, light, microorganisms,

A degradable polymer resin composition composed of a polymer resin, an oxidation promoter, and a modified biodegradable agent is finally produced by dissolving water, carbon dioxide, biomass, and the like into a commercially available degradable polymer resin composition And to provide a film produced using the same.

In order to achieve the above object,

The present invention relates to a resin composition comprising 40 to 90 wt% of a polymer resin; 0.1 to 15 wt% of an oxidation promoter; 9.5 to 50 wt% of a biodegradable product prepared by a cross-linking reaction of a fatty acid ester compound and an epoxidized vegetable oil.

And, it is produced by using the above-mentioned environmentally degradable polymer resin composition,

Wherein the green degradable polymer resin composition is formed into a film having a thickness of 20 to 40 탆 by using a film forming machine.

The eco-degradable polymer resin composition according to the present invention can improve the toughness and ductility of a mechanical property, which is a problem of a conventional fatty acid ester compound as a biodegradable agent, and can improve the toughness and ductility of a polymeric resin by decomposing action such as heat, light, microorganism, It is possible to complete decomposition with water, carbon dioxide and biomass in the final embedding and non-embedding state, and the manufacturing cost is low, so that it is highly possible to commercialize the degradable polymer resin composition. .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a comparison between a preliminary state (a) of a UV-curable film and a decomposed state (b) after irradiation with 300 h of UV, according to the film prepared using the degradable polymer resin composition according to Example 1 of the present invention.

Hereinafter, the above technical constitution will be specifically described.

As described above, in the degradable polymer resin composition according to the present invention,

40 to 90 wt% of a polymer resin,

0.1 to 15 wt% of an oxidation promoter,

And a mixture of 9.5 to 50 wt% of a biodegradable product prepared by a cross-linking reaction of a fatty acid ester compound and an epoxidized vegetable oil.

The polymer resin is one or more selected from among polypropylene, polyethylene, polystyrene, PET, nylon, cellophane, and polyacetate. The amount of the polymer resin is limited within a range of 40 to 90 wt% Preferably in the range of 60 to 90 wt%.

When the amount of the polymer resin is less than 40 wt%, the physical properties of the product deteriorate. When the amount of the polymer resin exceeds 90 wt%, the decomposition time becomes long. Therefore, the amount of the polymer resin is preferably 40 to 90 wt %. ≪ / RTI >

The oxidation promoter accelerates the decomposition of the polymer resin in an environment such as heat and light and is selected from metal carboxylates such as titanium stearate, iron stearate, copper stearate, cerium stearate or cobalt stearate At least one compound is used.

The amount of the oxidation promoting agent is limited within the range of 0.1 to 15 wt% with respect to the total amount of the composition, more preferably 1.0 to 10 wt%.

When the amount of the oxidation promoter is less than 0.1 wt%, the chemical oxidation reaction of the polymer resin can not be easily performed. When the amount of the oxidation promoter is more than 15 wt%, the physical properties of the resin may be deteriorated. Is preferably limited to a range of 0.1 to 15 wt%.

The modified biodegradable agent is used for increasing toughness and ductility, which is a problem of the mechanical properties of a fatty acid ester compound, which is a conventional biodegradable agent, and is produced by a cross-linking reaction between a fatty acid ester compound and an epoxidized vegetable oil.

The fatty acid ester compound may be any one selected from among polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polybutylene succinate (PBS), poly (butylenes adipate-co-terephthalate) Species or a mixture of the two. However, as long as it has the function of a biodegradation agent in addition to the biodegradation agents described above, it can be used without limitation.

Particularly, the fatty acid ester compound is hydrolyzed in addition to the biodegradation function, and is decomposed into an organic acid of a monomer. The decomposed organic acid acts as a catalyst of an oxidation promoter to accelerate the chemical decomposition of the polymer resin.

The epoxidized vegetable oil is one or more selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized milky oil and epoxidized grape oil. The epoxidized vegetable oil is prepared by reacting unsaturated fatty acid with hydrogen peroxide under acetic acid catalyst.

The amount of the modified biodegradable agent is limited within the range of 9.5 to 50 wt%, more preferably 20 to 40 wt%, based on the total amount of the composition.

If the amount of the modified biodegradable agent is less than 9.5 wt%, degradation of the biodegradation function and decomposition of the organic acid may not act as a catalyst for the chemical decomposition of the polymer resin. If the modified biodegradation agent is used in an amount exceeding 50 wt% And the physical properties of the resin may be deteriorated. Therefore, the amount of the modified biodegradable agent is preferably limited within the range of 9.5 to 50 wt%.

Hereinafter, the technical construction according to the present invention will be described in more detail with reference to examples.

<Preparation of modified biodegradation agent>

Specific production examples of the modified biodegradation agent include,

A mixed composition prepared by adding 0.2 wt% of catalyst catalyst methylimidazole (added in terms of the total weight of the mixture) to a mixture of 70 wt% of PLA resin and 30 wt% of epoxidized soybean oil (ESO 132, NAM YA Co.) Lt; 0 &gt; C to prepare pellets.

&Lt; Preparation of degradable polymer film >

Masterbatches were prepared in consideration of uniformity and extrudability because a polypropylene resin (Lotte Chemical, SFO-130A) and modified biodegradants prepared above were used and the oxidation promoter was a solid phase powder, 2, and the films were formed into films having a thickness of 30 占 퐉 using a blown film molding machine.

In order to measure the degree of decomposition of the thus formed polypropylene films, the change in the average molecular weight distribution of the polymer resin specified in ASTM D5247 standard was examined, and the average molecular weight was measured using a high temperature GPC instrument.

The films formed by kneading with each composition were subjected to UV irradiation according to KS M ISO 4892-3: 2002, and the average molecular weight of the films decomposed according to the irradiation time was measured and compared. UV irradiation was carried out by repeating 4 hours of UV irradiation at 60 ° C and 4 hours of contact with water, and the UV irradiation amount was 0.76 W / m 2 at 340 nm.

The degradable polymer resin composition (Example 1-4) prepared by using a polypropylene resin (Lotte Chemical, SFO-130A) as a polymer resin and the composition of Comparative Example 1-3 were used in Table 1, The results of measurement of the average molecular weight after UV irradiation for 300 hours with the films formed into a thickness of 30 mu m using a molding machine are shown.

Molecular weight distribution after UV irradiation weight% Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 PP 65 80 67 82 70 70 100 Modified PLA 30 15 30 15 - 30 - Cerium stearate 5 5 3 3 - - - PLA - - - - 30 - - Average molecular weight
(300h) 5,052 5,521 7,845 8,024 200,862 196,648 240, 412

As shown in Table 1, the average molecular weight of the PP film before UV irradiation of Comparative Example 3 was 240,412, and Comparative Examples 1 and 2 were the compositions to which the PP resin and the modified PLA and the PLA resin were added. The average molecular weight was 200,862 and 196,648, And there is almost no change.

However, in Example 1-4, the addition of cerium stearate, which is an oxidation promoter, shows a large decrease in average molecular weight.

This is because it accelerates the oxidation reaction of PP resin by the catalytic reaction of cerium stearate under UV.

FIG. 1 shows a comparison between a pre-UV state (a) of a film prepared using the degradable polymer resin composition according to Example 1 of the present invention and a decomposed state (b) after irradiation with 300 h of UV light, Is completely decomposed into a powder form.

In order to measure the biodegradability of the degradable polymer film, the biodegradability was tested in accordance with KS M 3100-1 standard test. The tensile strength and tensile elongation of the mechanical properties were tested in accordance with KS M 3503 standard test, and are shown in Table 2.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 The tensile strength
(MPa) 34.7 36.2 35.3 37.8 30.6 32.5 35.2 Tensile elongation
(%) 165.5 185.2. 175.3 190.1 140.4 170.4 178.5 Biodegradability
(45 days, compared to standard,
%)
81.2
75.3
78.8
76.4
65.7
78.1
5.5

As shown in Table 2, Example 1-4 shows tensile strength and tensile elongation similar to those of PP resin, and Comparative Example 1 shows a lower value than PP. In the biodegradability test, the films produced from the decomposition polymer composition show excellent biodegradability.

As described above, the degradable polymer resin composition according to the present invention has excellent mechanical properties such as toughness and ductility, and can be completely decomposed by water, carbon dioxide, biomass, etc., and is low in manufacturing cost, .

Claims (7)

40 to 90 wt% of a polymer resin,
0.1 to 15 wt% of an oxidation promoter,
And a mixture of 9.5 to 50 wt% of a biodegradable material prepared by a cross-linking reaction of a fatty acid ester compound and an epoxidized vegetable oil.
The method according to claim 1,
Wherein the polymer resin is one or more selected from the group consisting of polypropylene, polyethylene, polystyrene, PET, nylon, cellophane, and polyacetate.
The method according to claim 1,
Wherein the oxidation accelerator is one or more compounds selected from the group consisting of titanium stearate, iron stearate, copper stearate, cerium stearate or metal carboxylate of cobalt stearate.
The method according to claim 1,
The modified biodegradation agent,
60 to 80 wt% of a fatty acid ester compound,
Wherein the composition is prepared by extruding a composition prepared by adding a catalyst to a mixture of 20 to 40 wt% of an epoxidized vegetable oil at a temperature of 170 to 180 캜 to produce pellets.
The method of claim 4,
The fatty acid ester compound may be selected from among polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polybutylene succinate (PBS), poly (butylenes adipate-co-terephthalate) Or a mixture of two of them.
The method of claim 4,
Wherein the epoxidized vegetable oil is a mixture of one or two selected from the group consisting of epoxidized soybean oil, epoxidized castor oil, epoxidized oil, and epoxidized grape oil.
A film produced by using the environmentally degradable polymer resin composition according to any one of claims 1 to 6, which is molded into a film having a thickness of 20 to 40 탆 by using a film forming machine.

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