KR102462258B1 - Composite plasticizer and resin composition comprising same - Google Patents

Abstract

The present invention can provide a composite plasticizer composition that is environmentally friendly and harmless to the human body. A resin composition containing the composite plasticizer composition and a molded product containing the same have excellent elongation residual rate, volatility resistance, and breathability, and particularly have excellent heat resistance.

Description

Composite plasticizer composition and resin composition comprising same

The present invention relates to a composite plasticizer composition and a resin composition comprising the same, and more particularly, to a composite plasticizer composition including a citrate-based plasticizer, an epoxidized oil and a diketone-based compound, and a molded article made of a high heat resistance resin composition including the same is about

The plasticizer penetrates between the polymer chains to relieve the forces between molecules. In general, plasticizers are produced by esterification of alcohols with carboxylic acids such as adipic acid and phthalic acid, and there are adipate-based and phthalate-based plasticizers. Examples of commercialized primary plasticizers include di(2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, and di(2-ethylhexyl) phthalate, diisononyl phthalate and diisodecyl phthalate. There is this.

However, through many studies, some commercially available phthalate-based plasticizers have been found to disrupt the endocrine system as environmental hormones.

In addition, phthalate-based plasticizers were regulated by the National Environment Agency in 2010 for infants and adolescents such as baby products and children's toys. In 2012, wallpaper and flooring were applied, and the restrictions on commercial use were extended. The use of phthalate-based plasticizers is restricted due to regulations, and it is necessary to develop a plasticizer that can replace the physical properties of existing phthalate-based plasticizers.

Therefore, in order to solve the environmental problems and human harm of phthalate-based plasticizers, non-phthalate-based plasticizers are currently being replaced.

As a representative plasticizer to be replaced, a citrate-based plasticizer may be exemplified. The citrate-based plasticizer is synthesized by the esterification reaction of citric acid and alcohol, and can solve the above two problems, environmental problems and human harm.

However, a molded article made of a resin composition containing a citrate-based plasticizer may cause a problem of poor heat resistance. As a result, the use of citrate-based plasticizers may be limited in wire coatings, floor plates, building structures, or home appliance cases, which are often used in molded articles made of the plasticizer-added resin composition.

Therefore, a molded article made of a resin composition including a plasticizer should have constant heat resistance according to commercial purposes and uses. The citrate-based plasticizer can solve the environmental and human health problems of the phthalate-based plasticizer, but it is always necessary to develop a plasticizer composition having high heat resistance in a resin composition containing a citrate-based plasticizer and a molded article manufactured therefrom. to be.

Korea Patent Publication No. 2017-0049446

The present invention provides a composite plasticizer composition comprising a citrate-based plasticizer, an epoxidized oil, and a diketone compound.

In addition, the present invention is to provide a resin composition having improved heat resistance, including the composite plasticizer composition, and a molded article prepared therefrom.

The present invention provides a composite plasticizer composition comprising a citrate-based plasticizer, an epoxidized oil, and a diketone-based compound.

In one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterification of citric acid and an alcohol having 4 to 10 carbon atoms.

In one embodiment of the present invention, the composite plasticizer composition may contain 30 to 99 wt% of a citrate-based plasticizer, 0.99 to 50 wt% of an epoxidized oil, and 0.01 to 20 wt% of a diketone-based compound.

In one embodiment of the present invention, the epoxidized oil is an epoxidized soybean oil, an epoxidized pajama oil, an epoxidized linseed oil, an epoxidized palm oil, an epoxidized stearate, an epoxidized oleate, an epoxidized tall oil, and an epoxidized linoleate. It may be one or two selected from.

In one embodiment of the present invention, the diketone-based compound may be stearylbenzoylmethane, dibenzoylmethane, or a mixture thereof.

In one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying citric acid with one or more alcohols selected from 2-ethylhexanol, 2-octanol, and n-octanol.

Also, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying citric acid with one alcohol selected from 2-ethylhexanol, 2-octanol, and n-octanol.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterification of a mixed alcohol of 2-ethylhexanol and 2-octanol and citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying a mixed alcohol of 2-ethylhexanol and n-octanol with citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying a mixed alcohol of n-octanol and 2-octanol with citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterification of a mixed alcohol of 2-ethylhexanol, 2-octanol, and n-octanol with citric acid.

The present invention also provides a resin composition comprising the composite plasticizer composition and a polymer resin.

In one embodiment of the present invention, the polymer resin is polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, ethylene polymer, polypropylene resin, polyketone resin, polystyrene resin, polyurethane resin, natural It may be selected from the group consisting of rubber resins, synthetic rubbers and acrylic resins.

Alternatively, in one embodiment of the present invention, the composite plasticizer composition may include 5 to 150 parts by weight based on 100 parts by weight of the polymer resin.

In addition, in one embodiment of the present invention, the resin composition is any one or two selected from the group consisting of secondary plasticizers, fillers, lubricants, stabilizers, UV stabilizers, foaming agents, viscosity modifiers, processing aids, flame retardants, enhancers, pigments and dispersants More may be included.

The present invention also provides a molded article prepared from the resin composition.

The composite plasticizer including the citrate-based plasticizer, epoxidized oil, and diketone compound of the present invention is environmentally friendly and has the advantage of escaping the regulation of phthalate plasticizers.

In addition, the resin composition of the present invention includes a composite plasticizer composition, so that the molded article produced therefrom has an elongation rate and a residual elongation rate. It has excellent effects of volatility resistance, breathability and especially heat resistance.

1 is a view showing the thermal discoloration of Example 2 and Comparative Examples 1 to 6 of the present invention, and shows the color change for 1 day under the experimental condition of 100° C. for a total of 7 days.

The conventional resin composition and molded article including the citrate-based plasticizer may have high tensile strength, elongation, elongation residual rate, volatility resistance and breathability, but may have a disadvantage of poor thermal properties.

For this reason, the use of the resin composition including the citrate-based plasticizer may be limited in electric wire coatings, floor plates, building structures, or home appliance cases requiring heat resistance.

Therefore, in order to overcome these problems, the inventors of the present invention have found that the above problems can be solved by using a composite plasticizer composition comprising a citrate-based plasticizer, an epoxidized oil and a diketone-based compound, and completed the present invention.

The present invention provides a composite plasticizer composition comprising a citrate-based plasticizer, an epoxidized oil, and a diketone-based compound.

The citrate-based plasticizer according to an embodiment of the present invention may be prepared by esterifying citric acid with an alcohol having 4 to 10 carbon atoms.

The preferred alcohol may be an alcohol having 6 to 9 carbon atoms, more preferably an alcohol having 8 carbon atoms, but is not limited thereto.

More specifically, the composite plasticizer composition of the present invention is tris (2-ethylhexyl) citrate in which all three carboxylic acid groups of citric acid are branched chain alkyl having 8 carbon atoms, and specifically, all 2-ethylhexyl groups are introduced. A more improved effect can be obtained in combination with a ton-based compound, and it may be better in the case of a combination of tris(2-ethylhexyl)citrate, a diketone-based compound and an epoxidized oil.

In one embodiment of the present invention, the composite plasticizer composition may include 30 to 99 wt% of a citrate-based plasticizer, 0.99 to 50 wt% of an epoxidized oil, and 0.01 to 20 wt% of a diketone-based heat stabilizer.

Preferably, the composite plasticizer composition may contain 50 to 95 wt% of a citrate-based plasticizer, 2.99 to 40 wt% of an epoxidized oil, and 0.01 to 5 wt% of a diketone-based compound.

More preferably, the composite plasticizer composition may include 64.99 wt% to 95 wt% of a citrate-based plasticizer, 4.99 to 25.99 wt% of an epoxidized oil, and 0.01 to 2 wt% of a diketone-based compound.

In one embodiment of the present invention, the epoxidized oil is an epoxidized soybean oil, an epoxidized pajama oil, an epoxidized linseed oil, an epoxidized palm oil, an epoxidized stearate, an epoxidized oleate, an epoxidized tall oil, and an epoxidized linoleate. It may be one or two or more selected from.

Preferably, the epoxidized oil is epoxidized soybean oil and epoxidized palm oil, and may be an epoxidized oil containing a large amount of epoxy groups. More preferably, the epoxidized oil may be an epoxidized soybean oil.

As an embodiment of the present invention, although a citrate-based plasticizer and an epoxidized oil were included in the polyvinyl chloride resin, it can be confirmed that the polyvinyl chloride resin including the conventional phthalate-based plasticizer did not satisfy heat resistance.

Specifically, it can be seen that the initial thermal discoloration of the resin composition including the epoxidized oil and the citrate-based plasticizer and the molded article made of the resin composition is weak.

Therefore, in the present invention, a diketone-based compound is additionally used in a mixture of a citrate-based plasticizer and an epoxidized oil, and while maintaining the advantages of a citrate-based plasticizer, the resin composition and molded article containing the composite plasticizer composition of the present invention Heat resistance can be extremely improved.

In one embodiment of the present invention, the diketone-based compound may be used as stearylbenzoylmethane or dibenzoylmethane, and a mixture thereof.

In one embodiment of the present invention, the citrate-based plasticizer may be a citrate-based plasticizer obtained by reacting citric acid with one or more alcohols selected from 2-ethylhexanol, 2-octanol, and n-octanol.

In one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying citric acid with any one or two or more alcohols selected from 2-ethylhexanol, 2-octanol, and n-octanol.

In one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying citric acid with any one alcohol selected from 2-ethylhexanol, 2-octanol, and n-octanol.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying a mixed alcohol of 2-ethylhexanol and 2-octanol with citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying a mixed alcohol of 2-ethylhexanol and n-octanol with citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may provide a composite plasticizer composition prepared by esterification of a mixed alcohol of n-octanol and 2-octanol with citric acid.

Alternatively, in one embodiment of the present invention, the citrate-based plasticizer may be prepared by esterifying a mixed alcohol of 2-ethylhexanol, 2-octanol, and n-octanol with citric acid.

The present invention also provides a resin composition comprising the composite plasticizer composition and a polymer resin.

In one embodiment of the present invention, the composite plasticizer composition may contain 5 to 150 parts by weight based on 100 parts by weight of the polymer resin.

Preferably, the composite plasticizer composition may be included in an amount of 20 to 100 parts by weight, but the present invention is not limited thereto.

In one embodiment of the present invention, the polymer resin is polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, polyethylene resin, polypropylene resin, polyketone resin, polystyrene resin, polyurethane resin, natural It may be selected from the group consisting of rubber, synthetic rubber and acrylic resin.

Preferably, it may be a polyethylene resin, an ethylene vinyl acetate resin, a polyvinyl chloride resin, More preferably, it may be a polyvinyl chloride resin, but the present invention is not limited thereto.

In addition, in one aspect of the present invention, the resin composition is any one or two selected from the group consisting of secondary plasticizers, fillers, lubricants, stabilizers, UV stabilizers, foaming agents, viscosity modifiers, processing aids, flame retardants, enhancers, pigments and dispersants More may be included.

The filler is a ceramic and metal-based material, for example, calcium carbonate, silica, magnesium carbonate, calcium carbonate, talc, etc. may be used, and the filler is not limited as long as it can be used in the art, particularly polyvinyl chloride resin.

The present invention also provides a molded article prepared from the resin composition.

The process for manufacturing the molded article of the present invention includes a two-roll mill, an extrusion process, an injection process, a casting process, and the like, but the present invention may include all processes, and the process is not limited thereto.

The molded article provides excellent physical properties in elongation rate, elongation residual rate, volatility resistance, and breathability, and by additionally including an epoxidized oil and a diketone-based compound, high heat resistance can be extremely improved.

Example

In order to describe the present invention in detail, it will be described in detail with reference to examples. However, the scope of the present invention is not limited to the examples.

<Test item>

1. Heat resistance measurement

Each measurement sample is placed in an oven and heated to 100 °C. The degree of discoloration was checked on a daily basis, and the degree of discoloration was confirmed for a total of 5 days. Check the color change with the naked eye and use a colorimeter to L ^* , a ^* , The b ^* value was measured and the result value of b ^* corresponding to the yellow value was compared.

Preparation Example 1: Preparation of TEHC (Tris 2-ethylhexyl citrate) citrate-based plasticizer

Citric acid (1 mol) and 2-ethylhexanol (3 mol) were put into a reactor, and in the presence of a PTSA (paratoluenesulfonic acid) (0.006 mol) catalyst, the temperature was increased to about 160° C. and the direct esterification reaction was carried out. During the direct esterification reaction, 2-ethylhexanol (0.9 mol) was additionally added to the reactor. After completion of the reaction, the reaction product was purified. And the obtained compound was analyzed by GC-Mass to confirm the prepared citrate-based plasticizer.

Preparation Example 2: Preparation of plasticizer composition

A plasticizer composition comprising 95 wt% of TEHC, which is a citrate-based plasticizer prepared in Preparation Example 1, and 5 wt% of epoxidized soybean oil (ESO) was prepared.

Preparation Example 3: Preparation of plasticizer composition

A plasticizer composition comprising 90 wt% of TEHC, which is a citrate-based plasticizer prepared in Preparation Example 1, and 10 wt% of ESO (epoxidized soybean oil) was prepared.

Preparation Example 4: Preparation of plasticizer composition

A plasticizer composition comprising 99.7 wt% of TEHC, which is a citrate-based plasticizer prepared in Preparation Example 1, and 0.3 wt% of SBM (Stearoyl Benzoly methane) was prepared.

Preparation Example 5: Preparation of plasticizer composition

A plasticizer composition comprising 99.5 wt% of TEHC, which is a citrate-based plasticizer prepared in Preparation Example 1, and 0.5 wt% of SBM (Stearoyl Benzoly methane) was prepared.

Example 1: Preparation of Composite Plasticizer Composition

A composite plasticizer composition was prepared by mixing 89.5 wt% of TEHC, which is a citrate-based plasticizer prepared in Preparation Example 1, 10 wt% of epoxidized soybean oil (ESO), and 0.5 wt% of SBM (Stearoyl Benzoly methane).

Example 2: Preparation of polyvinyl chloride resin containing composite plasticizer composition.

70 parts by weight of the composite plasticizer composition prepared in Example 1, and a stabilizer (CZ-400 (Ca-Zn Organics, Songwon Industries) 2.5 parts by weight was added, and using this as a two-roll mill equipment, it was trained for 5 minutes at 170° C. Then, a pressure of 15 Mpa was applied at 175° C. for 3 minutes using a hot press, cooled to 90° C. or less, and then the thickness After that, the color changed by the heat resistance measurement of the test item is shown in Fig. 1, and the color difference meter b ^* value of the discolored color is shown in Table 1.

Comparative Example 1: Preparation of a resin composition

It was prepared in the same manner as in Example 2, except that the citrate-based plasticizer prepared in Preparation Example 1 was used instead of the composite plasticizer composition in Example 2. Thereafter, the color changed by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

Comparative Example 2: Preparation of a resin composition

It was prepared in the same manner as in Example 2, except that the temporary agent composition prepared in Preparation Example 2 was used instead of the composite plasticizer composition in Example 2. Thereafter, the color changed by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

Comparative Example 3: Preparation of a resin composition

It was prepared in the same manner as in Example 2, except that the plasticizer composition prepared in Preparation Example 3 was used instead of the composite plasticizer composition in Example 2. Thereafter, the color changed by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

Comparative Example 4: Preparation of a resin composition

Instead of the composite plasticizer composition prepared in Example 1 in Example 2, it was prepared in the same manner as in Example 2, except that the plasticizer composition of Preparation Example 4 was used. Thereafter, the changed color of the sample measured by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

Comparative Example 5: Preparation of resin composition

Instead of the composite plasticizer composition prepared in Example 1 in Example 2, it was prepared in the same manner as in Example 2, except that the plasticizer composition of Preparation Example 5 was used. Thereafter, the changed color of the sample measured by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

Comparative Example 6: Preparation of resin composition

It was prepared in the same manner as in Example 2, except that Di isodecyl phthalate (DIDP), a phthalate-based plasticizer, was used instead of the composite plasticizer composition in Example 2. Thereafter, the changed color of the sample measured by the heat resistance measurement of the test item is shown in FIG. 1 , and the color difference value of the discolored color is shown in Table 1.

colorimeter b ^* value Early 1 day 2 days 3 days 4 days 5 days Example 2 -3.42 -1.29 0.49 1.78 4.32 6.64 Comparative Example 1 -3.03 6.52 31.91 47.78 X X Comparative Example 2 -2.76 7.68 10.24 17.58 31.58 42.61 Comparative Example 3 -2.62 7.54 10.11 16.24 30.15 35.42 Comparative Example 4 -3.53 -0.77 2.93 8.87 28.16 X Comparative Example 5 -3.51 -1.92 1.17 8.10 25.06 X Comparative Example 6 -3.63 -0.85 1.90 3.27 5.89 7.96

The color difference system b ^* value is a + value based on 0, meaning that a yellow color (yellowing) appears strongly when the value is increased.

In Table 1, x means that a large amount of discoloration (carbonization) proceeds and thus measurement is impossible.

Referring to FIG. 1 and Comparative Example 1 of Table 1, it can be seen that the sample containing only the tris 2-ethylhexyl citrate (TEHC) plasticizer, that is, the sample containing only the citrate-based plasticizer, exhibited significant discoloration. This means that the heat resistance of Comparative Example 1 is inferior. Therefore, the thermal weakness of the citrate-based plasticizer is clearly revealed.

Referring to Comparative Example 2 of FIG. 1 , it can be seen that the degree of discoloration is significantly reduced compared to Comparative Example 1. Comparative Example 2 includes the epoxidized oil, and it can be seen that the degree of discoloration is reduced compared to Comparative Example 1.

Comparing Comparative Example 1 and Comparative Example 2 of Table 1, after 1 day, the color difference system b ^* of Comparative Example 1 was 6.52 and the color difference system b ^* of Comparative Example 2 was 7.68, which does not cause much difference. However, from the 2nd day, it can be seen that the color difference system b ^* value of Comparative Example 2 is smaller than the color difference system b ^* value of Comparative Example 1.

Therefore, it can be seen that Comparative Example 1 or Comparative Example 2 undergoes discoloration after 1 day, and in Comparative Example 2, less discoloration proceeds after 2 days.

In the case of Comparative Example 3, there is no difference from Comparative Example 2, but when compared with Table 1, the color difference meter b ^* value shows a difference at 5 days.

Therefore, the plasticizer composition including the Tris 2-ethylhexyl citrate (TEHC) plasticizer and Epoxidized soybean oil (ESO) can impart the late heat resistance of the resin composition including the plasticizer composition, but it can be confirmed that the initial heat resistance is not good.

In the case of Comparative Example 4 or Comparative Example 5, it can be seen that the color change of the sample to which a constant heat is applied in FIG. 1 is significantly changed in 4 to 5 days.

As for the above results, when the color difference meter b ^* value of Comparative Examples 4 and 5 is checked in Table 1, it can be confirmed that the color is not measured due to severe discoloration and carbonization in X.

Comparing Comparative Example 2 and Comparative Example 4 in Table 1, the color difference system b ^* value of Comparative Example 2 was 7.68 after 1 day, and the color difference system b ^* value of Comparative Example 4 was -0.77. Therefore, the initial color difference system b ^* values of Comparative Example 2 and Comparative Example 4 are significantly different.

Therefore, it can be confirmed that the sample using the plasticizer composition including TEHC (Tris 2-ethylhexyl citrate) and SBM (Stearoyl Benzoly methane) has poor late heat resistance.

Comparing Example 2 of FIG. 1 with Comparative Example 6, the degree of discoloration at 100 ° C. for each day is similar, but in Table 1, the color difference b ^* value is more overall compared to the DIDP plasticizer of Comparative Example 6 in Example 2 low can be seen.

As confirmed through the examples, it can be confirmed that the heat resistance of the resin composition including the composite plasticizer composition of the present invention is equal to or superior to that of the resin composition including the DIDP (Di isodecyl phthalate) plasticizer.

Therefore, the resin composition including the composite plasticizer composition including the citrate-based plasticizer, the epoxidized oil, and the diketone-based compound of the present invention and a molded article manufactured using the same may have high heat resistance.

In conclusion, the resin composition and molded article including the composite plasticizer composition of the present invention may be used in various fields requiring heat resistance.

Claims (16)

A composite plasticizer composition comprising a citrate-based plasticizer, an epoxidized oil and a diketone-based compound, the composition comprising:
The composite plasticizer composition comprises 30 to 99 wt% of a citrate-based plasticizer, 0.99 to 50 wt% of an epoxidized oil, and 0.01 to 20 wt% of a diketone-based compound. The method of claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by ester reaction with citric acid and an alcohol having 4 to 10 carbon atoms. delete The method of claim 1,
The epoxidized oil is at least one selected from the group consisting of epoxidized soybean oil, epoxidized pajama oil, epoxidized linseed oil, epoxidized palm oil, epoxidized stearate, epoxidized oleate, epoxidized tall oil and epoxidized linoleate. Composite plasticizer composition. The method of claim 1,
The diketone-based compound is a composite plasticizer composition of stearylbenzoylmethane, dibenzoylmethane, or a mixture thereof. According to claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterifying citric acid with one or more alcohols selected from 2-ethylhexanol, 2-octanol and n-octanol. According to claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterifying citric acid with one alcohol selected from 2-ethylhexanol, 2-octanol, or n-octanol. The method of claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterification of a mixed alcohol of 2-ethylhexanol and 2-octanol and citric acid. The method of claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterification of a mixed alcohol of 2-ethylhexanol and n-octanol and citric acid. The method of claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterifying n-octanol and 2-octanol mixed alcohol with citric acid. The method of claim 1,
The citrate-based plasticizer is a composite plasticizer composition prepared by esterifying a mixed alcohol of 2-ethyl hexanol, 2-octanol and n-octanol with citric acid. [Claim 1] A resin composition comprising the composite plasticizer composition of any one of claims 1, 2 and 4 to 10, and a polymer resin. 13. The method of claim 12,
The polymer resin is polyvinyl chloride resin, polyolefin resin, polyester resin, ABS resin, ethylene vinyl acetate copolymer, polyethylene resin, polypropylene resin, polyketone resin, polystyrene resin, polyurethane resin, natural rubber, synthetic rubber and acrylic resin. One or two or more resin compositions selected from the group consisting of resins. 13. The method of claim 12,
The composite plasticizer composition is a resin composition comprising 5 to 150 parts by weight based on 100 parts by weight of the polymer resin. 13. The method of claim 12,
The resin composition may further include any one or two or more selected from the group consisting of secondary plasticizers, fillers, lubricants, stabilizers, UV stabilizers, foaming agents, viscosity modifiers, processing aids, flame retardants, enhancers, pigments and dispersants. resin composition. A molded article manufactured from the resin composition of claim 12 .

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