KR100198199B1 - Decomposable resin composition - Google Patents

Abstract

The present invention consists of polyolefin resins, aliphatic polyesters, photodegradable derivatives, inorganic fillers and, optionally, compatibilizers, and synergistic action of the components to reinforce each other to provide excellent biodegradability and photodegradability as well as The present invention relates to a resin composition having excellent protection and air pollution prevention function, which is easy to decompose even if disposed of in any environment after use, and thus has a low burden on nature.

Description

Degradable Resin Composition

The present invention relates to a degradable resin composition. More specifically, the present invention consists of polyolefin resins, aliphatic polyesters, photodegradable derivatives, inorganic fillers and, optionally, compatibilizers, and synergistic action of the respective components to reinforce each other to provide excellent biodegradability and photodegradability, as well as The present invention relates to a resin composition having excellent protection against incineration and air pollution prevention.

Polyolefin resins, such as polyethylene and polypropylene, are one of the plastic raw materials used for general purposes. Since most of them are polymers composed of only carbon and hydrogen, they are used as shopping bags, packaging containers, or disposable products. It remains and causes environmental pollution problem. In order to solve this problem, researches on the development of degradable plastics and effective treatment of plastics have been conducted, and the above products must be incinerated without being degradable under natural conditions, that is, under biodegradable or photodegradable conditions. In view of the time, there is a demand for a technology that has favorable conditions even during incineration. Therefore, the aim of the present technology is to minimize the environmental impact of plastic products that can only be in various conditions.

As a final product, there are two methods for treating plastics that have been used: direct methods such as landfill, reclamation, and incineration, and degradable plastics that decompose in their natural state from the outset.

The method of embedding plastics can handle a large amount of waste plastic at once, but there is a problem of securing landfills, and recycling has its own difficulties in classifying plastics of the same kind.

The incineration method can reduce the pollution area due to waste plastic as much as possible by burning directly by incinerator without pretreatment process such as securing landfill and sorting, but it is inconvenient to collect and transport because of the large volume of waste plastic. There is a risk that the incinerator will be corroded or damaged, and especially plastics containing halogen atoms generate toxic gas when incinerated, so the treatment thereof becomes an important problem to be solved in connection with the pollution problem. Therefore, inorganic fillers are usually used for the removal of toxic gases and for the protection of incinerators.In particular, calcium carbonate, which is mainly used, removes sulfur compounds, hydrochloric acid, etc. generated during incineration. Pollution problems can be reduced and incinerators are protected by lowering the temperature of the incinerator.

Prior arts of applying calcium carbonate to polyolefins include, for example, Japanese Patent Laid-Open Nos. 62-218431, 50-17636, 50-23371, and the like.

On the other hand, there are largely biodegradation methods and photodegradation methods of plastics, and biodegradation methods include biodegradability by adding starch, microbial production polymers, and biosynthetic polymers. There is this.

Among the biodegradation methods, a method of preparing biodegradable plastics by adding starch to a polymer that is not degradable generally does not facilitate water treatment and particle size control of starch, which affects plastic formability and the final product. Compared to the product without starch, it has the disadvantages that the physical properties of the product are greatly degraded due to the effect of starch and that it takes considerable time to reach complete decomposition because of its disintegration.

Examples of the prior art in which the starch filling method is introduced include US Patent 4,337,181, PCT International Publication No. 90/10671, UK Patent 1,485,833, US Patent 4,016,117, 4,021,388, 4,218,350 and 4,337,181. And Korean Patent Publication No. 90-6336.

In addition, there is a method of synthesizing and using a microbial polymer, polyhydroxybutyrate (PHB), phlyhydroxyalkanoate (PHA) or derivatives thereof, and biodegradable synthetic polymers synthesized to be biodegradable. Although biodegradable, the price competitiveness is low due to expensive manufacturing equipment, etc., and thus has a significant limitation in generalization. Examples of the prior art using biodegradable synthetic polymers include, for example, European Publication Nos. 572,256 and 569,144, US Patent Nos. 5,310,782, Japanese Laid-Open Patents No. 53-20326, No. 51-32572 and No. 51-05771. And PCT International Publication No. 93/06267.

For this reason, as with the principle of using starch, the recent trend is to mix waste materials with plastics which are not degradable and are used in waste plastics for decomposition. Examples of the prior art using biodegradable synthetic polymers in this manner include Canadian Patent Nos. 2,071,133, European Publication Nos. 518,003 and 435,435.

Next, among the methods of decomposing plastics, the photodegradation method includes a method of synthesizing and using a polymer having a carbonyl group in the main chain, a method of blending a similar polymer with a non-degradable polymer to induce degradability, a method of adding a photolysis accelerator to a base polymer, and There are methods for adding a photosensitive agent and a polymer having a functional group capable of reacting sensitively to ultraviolet rays.

Among these methods, a technique for synthesizing a polymer having a carbonyl group in the polymer main chain is a method of obtaining a copolymer containing a carbonyl group by reacting ethylene and carbon monoxide, and described in US Pat. Nos. 2,495,286, 3,676,401, 3,853,814 and the like. It is. The methods using the carbonyl group-containing polymer are photodegraded by the Norris-I, II decomposition mechanism when the carbonyl group-containing polyethylene film is exposed to ultraviolet rays. The resolution is excellent, but due to various devices and materials required for production. Due to the price increase factor, there is a problem that there is a limitation in the use as a final product.

On the other hand, the method of U.S. Patent No. 3,860,530 in which the ketone copolymer is blended with polyolefin such as polyethylene and polystyrene to induce photodegradability shows photodegradation when a carbonyl-containing copolymer is added to the polyolefin, and the film obtained by this method Compared with low resolution, it has a problem to be solved such as relatively high price.

In addition, a method of inducing photodegradability by adding a photolysis accelerator to a polyolefin is described in, for example, US Pat. Nos. 1,365,107, 3,880,752, 4,028,480, 4,519,161 and the like. These methods induce the photodegradability of polyolefins by using aromatic ketone compounds or substances acting as photosensitizers in transition metal compounds. In addition, there is a problem in that the color of the additive color on the film has a problem that can not guarantee the safety when the aromatic ketone compound is in contact with the food container.

Korean Patent Publication No. 94-11554 discloses photodegradability by simultaneously adding a polymer having a functional group capable of reacting sensitively to ultraviolet rays and a photosensitive agent.

On the other hand, Japanese Patent Laid-Open No. 51-6324 discloses a method for producing a plastic having both biodegradability and photodegradability using starch and a biodegradable synthetic polymer. This method has been pointed out that the photodegradability is relatively low compared to the excellent biodegradability, the price is also expensive to commercialize, and the physical properties as a product are low.

Accordingly, the object of the present invention is to improve each of the disadvantages of the prior art, to have a more active photodegradability, biodegradability and incineration function, the short decomposition time, the environmentally friendly rate of the final decomposition products, the conventional incineration In addition to the composition, the initial physical properties are further improved, and in addition to the removal of harmful gases in incineration, it not only reduces the amount of CO gas generated, but also reduces the heat of combustion, and is also inexpensive compared to conventional degradable products, and also has initial properties, processability, printability, and gloss. It is to provide a degradable resin composition capable of producing an excellent plastic product.

In order to achieve the above object, in the present invention, 1 to 50% by weight of aliphatic polyester, 0.01 to 10% by weight of photodegradable derivative compound, 10 to 60% by weight of inorganic filler, and optionally, 0.1 to 100 parts by weight of the total composition of the compatibilizer It provides a decomposable polyolefin resin composition comprising 12 parts by weight.

Hereinafter, the present invention will be described in more detail.

The photo-biodegradable and incinerated polyolefin resin composition of the present invention comprises a polyolefin resin, an aliphatic polyester, a photodegradable derivative, an inorganic filler, and optionally a compatibilizer.

The polyolefin resin component in the composition may include polyethylene, polypropylene, and the like, and the amount thereof is 89 wt% or less based on the weight of the composition.

Preferably, the polyethylene has a melt flow index measured by the method of ASTM D-1238 of 0.01-40 g / 10 minutes, preferably 0.1-3 g / 10 minutes, and specific gravity measured by the method of ASTM D-1505D is 0.916-. 0.961g / cm ^3, preferably 0.919-0.951g / cm ^3, to have a 0-2 double bond in the main chain.

Polypropylene that can be used in the present invention has a melt flow index of 0.30-35g / 10min, the specific gravity is 0.890-0.910g / cm ³ measured by the method of ASTM D-1238 at 230 ℃, 2160g, ethylene and In the case of the copolymer of the average ethylene content is preferably 2.5 to 8.5% by weight.

The aliphatic polyester used in the present invention is a biodegradable synthetic polymer, which gives biodegradability to the base resin, and has a repeating unit represented by the following structural formula.

(Wherein a is an integer from 1 to 5 and b is 0 or 1).

Examples thereof include polycaprolactone, polylactide, polyglycolide, etc., wherein the aliphatic polyester is 1 to 50% by weight, preferably 3, based on the weight of the composition of the present invention. To 20% by weight. The aliphatic polyester component, as can be seen in its structure, is very rich in CO ₂ groups in the chain, so as not only biodegradable but also has a function of suppressing harmful CO gas generation and incineration heat upon incineration.

As the photodegradable derivative compound added to induce photodegradability in the composition of the present invention, one or more compounds selected from ionic modified polyethylene and polyolefin grafted with unsaturated ethylenic ring anhydride may be used, and these are also aliphatic polyesters. And a compatibilizer between polyolefin resin. Among these, the modified polyethylene having ionicity not only acts as a compatibilizer but also significantly improves physical properties and processability such as breaking strength and elongation, melt index (MI), and melt tension of the composition. Due to such physical property improvement effect, the composition of the present invention can be processed into various forms.

The modified polystyrene having ionicity is a modified polyethylene obtained by copolymerizing a carboxyl group-containing monomer in ethylene, and is added in an amount of 0.01 to 10% by weight, preferably 0.1 to 6% by weight based on the weight of the composition. The modified polyethylene having ionicity is partially ionized by substitution of metal ions such as sodium, zinc or lithium, and has a melt flow index of 1.0-2.6 g / 10 min, measured at 190 ° C. and 2160 g, with a specific gravity of 0.940-. It is preferable that the melting temperature measured by 0.950 g / cm ³ , thermal differential analysis (DTA) be 81-96 ° C. This component has a decisive influence on the photodegradation induction period, and has the advantage of excellent compatibility with the polyolefin and the like used in the present invention. The carboxyl group-containing monomers that can be used in the preparation of modified polyethylene include methacrylic acid, acrylic acid, and the like, and methacrylic acid is preferred.

Polyolefin grafted with unsaturated ethylenic ring anhydride is used in the composition of the present invention in an amount of 0.1 to 10% by weight, preferably 0.1 to 4% by weight, based on the weight of the composition, and melted at 230 ° C. and 2160 g. The flow index is preferably 1-1300 g / 10 min, specific gravity 0.757-0.965 g / cm ³ and graft% 0.01-10.0%. This component acts as a radical source to generate radicals that can cleave the polyolefin backbone when the film is exposed to ultraviolet light and the polyolefins that can be used for its preparation are polyethylene, polypropylene, etc., and unsaturated ethylenic ring anhydrides are maleic anhydride and Its derivatives.

The photodegradable inducing compounds described above also show a photodegradation effect on polyolefins by themselves, but when used together with a trace amount of a photosensitizer, they exhibit better photodegradability by synergy. In addition, matrix destruction due to the above photolysis effect promotes biodegradation because it provides a place where microorganisms can inhabit. Therefore, in the present invention, a photosensitive agent may optionally be included in the resin composition in order to improve the photodegradability of the photodegradable inducing compound. As the photosensitizer, an iron-based compound may be used, and specific examples thereof include ferric acetylacetonate, ferric diethyl dithiocarbamate, ferric stearate, and ferric palmitate. These compounds may be used alone or in combination of two or more, and are added in an amount of 0.001 to 0.1 parts by weight, preferably 0.005 to 0.05 parts by weight, based on 100 parts by weight of the polyolefin composition.

On the other hand, in the present invention, an inorganic filler is used to give the resin composition a function of reducing air pollution and protecting the incineration apparatus during incineration of plastics. For example, calcium carbonate may be used as the inorganic filler. The inorganic filler is used in an amount of 10 to 60% by weight, preferably 20 to 40% by weight of the composition.

In the case of calcium carbonate in the inorganic filler, the 325 mesh residue is preferably 0.02% or less, the average particle diameter is 10 μm or less, and the water content is 0.2% or less.

In addition, the composition of the present invention may further comprise a compatibilizer to further increase the compatibility of the polyolefin and aliphatic polyester, the compatibilizer is a polyolefin grafted or copolymerized with an epoxy compound, unsaturated ethylenic ring anhydride and epoxy One or more compounds selected from polyolefins grafted or terpolymerized, unsaturated ethylenic ring anhydrides and acrylates grafted or terpolymerized and acrylate grafted or copolymerized polyolefins may be used, as mentioned above. Modified polyolefins having ionicity can be used as compatibilizers. The amount of these to be used is preferably 0.1 to 12 parts by weight per 100 parts by weight of the composition.

Mixing of the resin composition according to the present invention may be carried out by dry blending each of the above-mentioned components at room temperature with a mixer such as Henschel mixer, for example, by melt mixing with a single screw or twin screw extruder, or by mixing using a barrel mixer such as a kneader. Can be.

In the present invention, a 5-1000 μm thick film and a 0.1-10 cm thick plate were molded by a single screw compressor with a film die and an extruder with a site die using the resin composition obtained as described above. Several types of products were molded.

The following examples are intended to illustrate the invention in more detail, but the scope of the invention is not limited thereto. The contents of all compositions in the examples are by weight unless otherwise indicated and used polyethylene, polypropylene, modified polyethylene with ionicity, polyolefins grafted with unsaturated ethylenic ring anhydrides, aliphatic polyesters, photosensitizers, calcium carbonates and Physical properties of the compatibilizers are as follows.

end. Polyethylene resin

Density 0.953 g / cm ³ and melt flow index 0.04 g / 10 min.

I. Polypropylene resin

Homopolypropylene resin with a density of 0.910 g / cm ³ and a melt flow index of 2.5 g / 10 min.

All. Modified Polyethylene with Ionicity

Ethylene and methacrylic acid were copolymerized to have an acid content of 15% and then reacted with sodium ions to have a neutralization degree of 34%. The melting temperature was 92 ° C., the density was 0.950 g / cm ³ , and the melting was performed. The flow index is 2.6 g / 10 min.

la. Polyolefin Grafted with Unsaturated Ethylene Ring Anhydride

A graft% of an unsaturated ethylenic ring anhydride is 5.0, a density is 0.807 g / cm ³ , and a melt flow index is 950 g / 10 min, prepared by solution polymerization of maleic anhydride and polypropylene.

hemp. Aliphatic polyester

(1) The repeating unit of [-(CH ₂ ) ₅ -COO-] having a number average molecular weight of 80,000, a melt flow index of 44 psi at 125 ° C. of 1.0 g / 10 min, and a density of 1.145 at 23 ° C. Polyester having.

(2) Repeating unit of [-(CH ₂ ) ₃ -COO-] having a number average molecular weight of 80,000, a melt flow index of 44 g / s at 125 ° C. of 4.0 g / 10 min, and a density of 1.150 at 23 ° C. Polyester having.

bar. Calcium carbonate

The average particle diameter is 1.30㎛ and the apparent specific gravity is 0.37g / cm ³ with a whiteness of 98%.

four. Photosensitizer

Ferric Stearate.

Ah. Compatibilizer

Acrylic polymer, maleic anhydride, ethylene is a terpolymer copolymer, the content of the acrylic ester and maleic anhydride is 32%, the melt flow index is 7g / 10 minutes, the melting point is 65 ℃.

Reference Example: Mixing of Compositions and Preparation of Specimens

[(Step 1) Kneading of Composition]

The kneading of the composition was weighed as described in the following table and then mixed in a dry mixer (Hensel mixer) at room temperature, followed by melt mixing using a twin screw extruder. The barrel of the twin screw extruder has 11 parts to control the temperature. The temperature range is 180 ~ 210 ℃, and the screw rotation speed is 200rpm. The mixture of extruded resin was cooled and then cut in a cooling water bath to prepare a pellet.

[(Step 2) Specimen Preparation]

The resin pellets prepared in (Step 1) were each formed into a film having a thickness of 10-100 μm by a uniaxial hollow film molding machine (manufacturer: Brabender, L / D: 19/25) whose temperature was controlled at 170 to 200 ° C. Prepared.

Example 1 and Comparative Example 1

Effect of improving the compatibility of the composition by the photodegradable derivative or compatibilizer

In order to confirm the effect of modified polyethylene or compatibilizer having ionicity as a photodegradable compound, on the processability and physical properties of the high density polyethylene (HDPE) composition containing calcium carbonate and aliphatic polyester, as shown in Table 1 below, Was prepared to test the processability and physical properties, the results are shown in Table 1 below.

Using the same experiment as described above using a polypropylene instead of polyethylene as a base resin as a result shown in Table 2 below.

As can be seen from Tables 1 and 2, the composition consisting of only calcium carbonate and aliphatic polyester without a compatibilizer cannot be used as a packaging material because the physical properties are significantly lower than the tensile strength of 170. This phenomenon is due to poor compatibility between the polyolefin and the polyester, and it can be seen that the tensile strength of the fracture decreases as the content of the polyester increases. On the contrary, the addition of ionic modified polyethylene or compatibilizer to the composition shows excellent processability regardless of the content of polyester, enabling the production of blown films, and greatly improving tensile strength and elongation.

Example 2 and Comparative Example 2

Physical property improvement effect by photodegradable compound

When high density polyethylene (HDPE) is used as a base resin and modified polyethylene having ionicity as a photodegradable compound is used when the composition ratio of calcium carbonate is 0%, 105, 30% (B, C; Examples) Melt tension of the case (A; comparative example) was compared. In general, the melt tension can predict the processability of the blown film. That is, film processing is impossible when the measured value of melt tension is too small (usually 3 or less).

The measurement method of melt tension is as follows. That is, the melt tension of the resin composition manufactured under the conditions of a piston speed of 10 mm / min, a draw speed of 10 m / min, and a temperature of 190 ° C. was measured using a capillary type rheometer (Toyoseiki, Japan).

In the absence of ionic modified polyethylene, the melt tension decreases with increasing polyester content and this tendency increases with increasing calcium carbonate content. As a result, as the polyester content increases, the processability of the blown film greatly decreases or molding becomes impossible. On the contrary, in the case of using the modified polyethylene having ionicity, it can be seen that the melt tension is 3.0 or more regardless of the polyester content, and it is further improved as the content of the modified polyethylene having ionicity increases. In addition, when calcium carbonate is not used, the melt tension decreases when the content of the modified polyethylene having ionicity is increased, but when the calcium carbonate is used in 10% and 30%, respectively, the content of the modified polyether having ionicity is used. As this increased, it improved greatly from 3.0 to 6.05. Therefore, it can be seen that the modified polyethylene having ionicity not only performs a photolysis function but also a compatibilizer function, thereby improving the physical properties of the composition of the present invention to enable blow molding film processing.

Example 3 and Comparative Example 3

Photodegradability Improvement by Interaction of Calcium Carbonate with Aliphatic Polyester Photodegradable Compound

Films each having a thickness of 10-100 μm by a uniaxial hollow film molding machine (manufacturer: Brabender, L / D: 19/25) whose temperature was controlled to 170-200 ° C. in the resin composition having the composition shown in Tables 4 and 5 were used. After the preparation, photodegradation was measured by UV-CON (manufactured by ATLAS), which is an exposure apparatus using an ultraviolet lamp, in accordance with the methods of ASTM D-4329, ASTM D-1435, and ASTM D-882.

In the photolysis furnace measurement method, the photodegradation measurement condition of the film by the ultraviolet lamp is irradiated with ultraviolet rays for 4 hours at 60 ℃, for 4 hours at 40 ℃ to achieve a cycle to wet the surface of the film by condensation of moisture. As the elongation value is lowered within a short time, the decomposition of the film is greater. Photodegradation was measured while changing the content of aliphatic polyester and calcium carbonate, and the results are reported in Tables 4 and 5.

Through the measurement results of Tables 4 and 5, the photolysis rate increases as the content of calcium carbonate or aliphatic polyester increases, but it is difficult to decompose under actual natural conditions because all of them are 130 hours or more. That is, the two materials cannot work with polyethylene, respectively, to degrade the composition.

Meanwhile, different compositions of CaCO and aliphatic polyester were used in compositions containing 200 ppm and 1% of ethylene-modified polyethylene and polyolefin grafted with unsaturated olefin ring anhydride, which are photodegradable inducing compounds, respectively. Using the respective compositions of Table 6 prepared by the addition of the same, the change of photodegradation degree according to the exposure by the ultraviolet lamp and the outdoor exposure was measured as described above.

In Table 6, the compositions kneaded with the present technology show very fast resolution. That is, when the light, biodegradation and incineration materials are kneaded together, it can be seen that as the content of calcium carbonate and polyester increases, the resolution is greatly improved, and in particular, the effect is enhanced by calcium carbonate. This phenomenon is the effect of degradation activity by the co-action of four compositions.

Example 4

Biodegradation and photodegradation measurement

Photodegradation degree in the same manner as in Example 3 using a composition in which 30% calcium carbonate was added to the polyethylene-based resin and the content of the aliphatic polyester and the photodegradable derivative compound was changed as shown in Table 7 below. After measuring the biodegradation was measured as follows. In this example, the biodegradability of the strain was measured according to ASTM G21-70 and ASTM D4300-93, and propagation of the specimen-covered strain after about 30 days of culture experiment using the five strains indicated by ASTM regulations. According to the degree, according to ASTM G21-70 evaluation criteria classified into 1 ~ 4 stages and the weight loss compared to the initial weight was measured. The results are shown in Table 7.

Except for using a composition containing a polypropylene (calcium carbonate content 30%) instead of polyethylene as a base resin was carried out the same experiment as above to obtain the results shown in Table 8.

As can be seen in Tables 07 and 8, the composition of the present invention comprising a polyethylene or polypropylene resin as a base resin and containing all of calcium carbonate, a photodegradable derivative compound, and an aliphatic polyester has a high photodegradation time in UV-CON measurement. The photodegradation time was less than 24 hours and less than 60 days in outdoor exposure. The biodegradability measured by ASTM G21-70 showed more than three. That is, it can be seen that the results of photodegradation illustrated in Example 3 are shown in the polyolefin or polypropylene composition, and the biodegradation is improved by photolysis.

Example 5 and Comparative Example 4

Calorific Value and Limited Oxygen Volume in Incineration

Experimental results of comparing the calorific value during incineration of the polyolefin composition containing only calcium carbonate and the composition of the present invention are shown in Table 9 below. The calorific value was measured using a thermal time difference analyzer (DTA, DuPont, USA).

The greater the amount of heat generated during incineration, the shorter the life of the incinerator, so the lower the amount of heat generated, the better the air demand. As can be seen from Table 9, it can be seen that the greater the amount of aliphatic polyester (1) used, the less the calorific value and the air demand.

As seen from the above, the composition of the present invention is significantly improved in processability and physical properties, compared to the previous composition, the light resolution and biodegradation is superior due to the synergistic effect of the interaction, the heat generation and the air consumption is much reduced when incinerated It may be referred to as an affinity composition.

Claims (19)

1 to 50% by weight of an aliphatic polyester, 0.01 to 10% by weight of a photodegradable derivative compound, 10 to 60% by weight of an inorganic filler, and, optionally, 0.1 to 12 parts by weight of a compatibilizer with respect to 100 parts by weight of the total composition. Composition. The composition of claim 1 wherein said polyolefin resin is a resin comprising a polyethylene or polypropylene component. The composition of claim 2 wherein the polyethylene has a melt flow index of 0.01 to 40 g / 10 minutes and a specific gravity of 0.916 to 0.961 g / cm ³ . The composition of claim 2 wherein the polypropylene has a melt flow index of 0.3 to 35 g / 10 minutes and a specific gravity of 0.890 to 0.910 g / cm ³ . 5. The composition of claim 4, wherein said polypropylene is a copolymer with ethylene having an average ethylene content of 2.5 to 8.5 wt%. The composition of claim 1 wherein the aliphatic polyester is a compound consisting of repeating units having the structure: (Wherein a is an integer from 1 to 5 and b is 0 or 1). The composition of claim 1, wherein the photodegradable inducing compound is at least one compound selected from modified polyethylenes having ionicity and unsaturated ethylenic ring anhydrides grafted polyolefins. The composition according to claim 7, wherein the content of the modified polyethylene having ionicity is 0.01 to 10% by weight based on the total weight of the composition. The composition according to claim 8, wherein the melt polyethylene having a ionic property has a melt flow index of 1.0 to 2.6 g / 10 min and a specific gravity of 0.940 to 0.950 g / cm ³ . The composition of claim 8, wherein the modified polyethylene having ionicity has sodium, zinc or lithium ions. 8. The composition of claim 7, wherein the content of the polyolefin grafted with the unsaturated ethylenic ring anhydride is 0.1 to 10.0 wt%. The polyolefin grafted with the unsaturated ethylenic ring anhydride according to claim 11, wherein the polyolefin grafted with unsaturated ethylenic ring anhydride has a graft% of unsaturated ethylenic ring anhydride of 0.01 to 10%, a melt flow index of 1 to 1,300 g / 10 minutes, and a specific gravity of 0.757 to 12. 0.965 g / cm ³ composition. The composition of claim 1 further comprising a photosensitizer. The composition of claim 13, wherein the photosensitizer comprises 0.001 to 0.1 parts by weight based on 100 parts by weight of the polyolefin composition. The composition of claim 13, wherein the photosensitizer is an iron compound. The composition of claim 15, wherein the iron-based compound is at least one compound selected from ferric acetylacetonate, ferric diethyldithiocarbamate, ferric stearate, and ferric palmitate. The composition of claim 1 wherein said inorganic filler is calcium carbonate. The composition according to claim 17, wherein the calcium carbonate has a 325 mesh residue of 0.02% or less, an average particle diameter of 10 µm or less, and a water content of 0.2% or less. According to claim 1, wherein the compatibilizer is a polyolefin grafted or copolymerized epoxy compounds, unsaturated ethylene ring anhydride and an epoxy compound grafted or terpolymer polyolefin, unsaturated ethylene ring anhydride and acrylate grafted or terpolymerized Wherein the polyolefin and acrylate are at least one compound selected from grafted or copolymerized polyolefins.