KR20220049824A - Composite Resin Composition with Excellent Gas Barrier Properties and Article Molded Therefrom - Google Patents

Abstract

The present invention relates to a composite resin composition having excellent oxygen and moisture barrier properties and a composite resin molded article prepared therefrom. The composite resin composition according to an embodiment of the present invention has excellent oxygen and moisture barrier properties and thus can be effectively used as a packaging film even when molded into a single-layer film.

Description

Composite Resin Composition with Excellent Gas Barrier Properties and Article Molded Therefrom

The present invention relates to a composite resin composition having excellent gas barrier properties and a molded article prepared therefrom. Specifically, the present invention relates to a composite resin composition having excellent oxygen and moisture barrier properties, and a composite resin molded article prepared therefrom, specifically, an injection molded article, an extrusion molded article, a blow molding molded article, or a casting molded article.

Polypropylene resin, a kind of general-purpose resin, is widely used as a material for automobile interior/exterior parts, electrical and home appliance parts, construction and industrial materials, etc.

In particular, the polypropylene-based resin is processed into a film and applied to various fields. One of them is food packaging. The material for food packaging serves to prevent deformation or deterioration of functions due to external environments, such as oxygen, humidity, carbon dioxide, heat, light and odor, until the food, which is the content, is delivered to the customer.

However, while the film for food packaging prepared from polypropylene resin has excellent moisture barrier properties, oxygen barrier properties are relatively poor.

Meanwhile, an ethylene-vinyl alcohol (EVOH) copolymer is known as a resin having excellent oxygen barrier properties. However, the ethylene vinyl alcohol copolymer has relatively poor moisture barrier properties.

As such, since gas barrier properties are different for each polymer material, it is difficult to implement satisfactory barrier properties against various gases with a molded article manufactured from one material. Therefore, when barrier properties are required for various substrates, multilayer molded articles obtained by laminating or molding molded articles manufactured from various materials are widely used.

However, since the multilayer molded article has disadvantages in that the manufacturing process is complicated, various materials are used, and the manufacturing cost is high, an attempt has been made to manufacture a film having excellent barrier properties against various gases using a single composite resin composition.

For example, Korean Patent Application Laid-Open No. 2001-0072562 discloses a resin composition in which a copolymer obtained by graft copolymerization of a styrene-based or acrylic monomer to a polypropylene-based resin is added. However, the oxygen barrier properties of the films prepared therefrom still need improvement.

Accordingly, there is a demand for the development of a composite resin composition having excellent barrier properties against both oxygen and moisture.

Korean Patent Application Publication No. 2001-0072562

An object of the present invention is to provide a composite resin composition excellent in both oxygen and moisture barrier properties.

Another object of the present invention is to provide a molded article prepared from this composite resin composition.

According to an embodiment of the present invention for achieving the above object, based on 100 parts by weight of the composite resin composition, (A) 20-50 parts by weight of a polypropylene-based resin; (B) 20-60 parts by weight of an ethylene-vinyl alcohol resin; (C) 0.1 to 15 parts by weight of a modified polyolefin resin; and (D) 0.1 to 6 parts by weight of cellulose fibers, wherein the polypropylene-based resin (A) is (A-1) a propylene homopolymer resin; (A-2) Ethylene-propylene block copolymer resin obtained by stepwise polymerization of propylene homopolymer, propylene-ethylene random copolymer or propylene-1-butene random copolymer and ethylene-propylene rubber copolymer in a reactor, and mixtures thereof A composite resin composition selected from the group consisting of and having a melt index of 0.1 to 30 g/10 min of the polypropylene-based resin (A) when measured at 230° C. under a load of 2.16 kg is provided.

In a specific embodiment, the polypropylene-based resin (A) may have an isotactic index according to stereoregularity of 95.0% or more, a solvent extract content of 15% by weight or less, and a melting temperature of 160°C or more.

In a specific embodiment, the ethylene content in the ethylene-vinyl alcohol resin (B) is 20 to 40 mol%.

In a specific embodiment, the melt index of the ethylene-vinyl alcohol resin (B) is 0.1 to 20 g/10 min when measured at 210° C. under a load of 2.16 kg.

In a specific embodiment, the modified polyolefin resin (C) is polypropylene or polyethylene grafted with maleic anhydride.

In a more specific embodiment, the content of maleic anhydride in the modified polyolefin resin (C) is 1.0 to 2.5 wt%.

In a specific embodiment, the average diameter of the cellulose fibers (D) is 50 μm or less and the average length is 1 mm or less.

In a specific embodiment, the composite resin composition may further include an additive (E) in an amount of 2 parts by weight or less based on 100 parts by weight of components (A) to (D). In this case, the additive (E) may be at least one selected from the group consisting of antioxidants, neutralizers, reinforcing materials, fillers, weathering stabilizers, antistatic agents, lubricants, slip agents, pigments and dyes.

In a more specific embodiment, additive (E) is pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 1,3,5-trimethyl-tris at least one antioxidant selected from the group consisting of (3,5-di-t-butyl-4-hydroxybenzene) and tris(2,4-di-t-butylphenyl)phosphite.

According to another embodiment of the present invention, a composite resin molded article manufactured by molding the above composite resin composition is provided.

In a specific embodiment, the composite resin molded article is an injection molded article, an extrusion molded article, a blow molded article, or a casting molded article.

In a specific embodiment, the composite resin molded article is a film, and has an oxygen permeability of less than 50 cm 3 /m 2 ·day·atm and a moisture permeability of less than 5 cm 3 /m 2 ·day·atm based on a thickness of 50 to 200 μm.

The composite resin composition according to an embodiment of the present invention has excellent oxygen and moisture barrier properties, so that it can be effectively used as a packaging film even when molded into a single-layer film.

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

According to an embodiment of the present invention, based on 100 parts by weight of the composite resin composition, (A) 20-50 parts by weight of a polypropylene-based resin; (B) 20-60 parts by weight of an ethylene-vinyl alcohol resin; (C) 0.1 to 15 parts by weight of a modified polyolefin resin; and (D) 0.1 to 6 parts by weight of cellulose fiber, wherein the polypropylene-based resin has a melt index of 0.1 to 30 g/10 min when measured at 230° C. under a load of 2.16 kg.

(A) polypropylene resin

The composite resin composition according to an embodiment of the present invention includes 20 to 50 parts by weight of the polypropylene-based resin (A) based on 100 parts by weight of the composite resin composition. When the content of the polypropylene-based resin (A) is less than 20 parts by weight, the moisture barrier property of a molded article prepared from the composite resin composition may be reduced, and if it exceeds 50 parts by weight, the oxygen barrier property of the molded article may be reduced. .

In a specific embodiment, the polypropylene-based resin (A) is (A-1) a propylene homopolymer resin; (A-2) Ethylene-propylene block copolymer resin obtained by stepwise polymerization of propylene homopolymer, propylene-ethylene random copolymer or propylene-1-butene random copolymer and ethylene-propylene rubber copolymer in a reactor, and mixtures thereof is selected from the group consisting of

Here, the propylene homopolymer resin (A-1) may be a polymer obtained by polymerization of a propylene monomer substantially alone.

There is no particular limitation on the method for preparing the propylene homopolymer resin (A-1), and the method for preparing the propylene homopolymer resin known in the art to which the present invention pertains may be used as it is or with appropriate modifications. For example, a bulk polymerization method, a solution polymerization method, a slurry polymerization method, a gas phase polymerization method, etc. can be used, and either a batch type or a continuous type is possible.

The ethylene-propylene block copolymer resin (A-2) may be obtained by stepwise polymerization of a propylene homopolymer, a propylene-ethylene random copolymer, or a propylene-1-butene random copolymer and an ethylene-propylene rubber copolymer in a reactor. there is.

There is no particular limitation on the method for preparing the ethylene-propylene block copolymer resin (A-2), and the method for preparing the ethylene-propylene block copolymer resin known in the art to which the present invention belongs can be used as it is or with appropriate modifications. . For example, one or more bulk reactors and one or more gas phase reactors are connected in series and are known to those skilled in the art using Mitsui's Hypol process, which can continuously polymerize. An ethylene-propylene block copolymer resin can be prepared by a polymerization method.

In an embodiment of the present invention, the polypropylene-based resin (A) has a melt index of 0.1 to 30 g/10 min when measured at 230° C. under a load of 2.16 kg. If the melt index of the polypropylene-based resin (A) is less than 0.1 g/10 min, the processability of the composite resin composition is lowered, and when it exceeds 30 g/10 min, the physical properties of a molded article manufactured from the composite resin composition may be reduced. there is.

In an embodiment of the present invention, the polypropylene-based resin (A) may have an isotactic index according to stereoregularity of 95.0% or more. It is preferable in terms of gas barrier properties that the isotactic index of the polypropylene-based resin (A) is 95.0% or more.

In an embodiment of the present invention, the polypropylene-based resin (A) may have a solvent extract content of 15% by weight or less. At this time, as a solvent, xylene is preferable. It is preferable in terms of gas barrier properties and rigidity that the solvent extract content of the polypropylene-based resin (A) is 15% by weight or less.

In an embodiment of the present invention, the polypropylene-based resin (A) may have a melting temperature of 160° C. or higher. It is preferable in terms of gas barrier properties and heat resistance that the melting temperature of the polypropylene-based resin (A) is 160° C. or higher.

In a preferred embodiment of the present invention, the polypropylene-based resin (A) has an isotactic index according to stereoregularity of 95.0% or more, a solvent extract content of 15% by weight or less, and a melting temperature of 160° C. or more. .

(B) Ethylene-vinyl alcohol resin

The composite resin composition according to an embodiment of the present invention includes 20 to 60 parts by weight of the ethylene-vinyl alcohol resin (B) based on 100 parts by weight of the composite resin composition. When the content of the ethylene-vinyl alcohol resin (B) is less than 20 parts by weight, the oxygen barrier property of a molded article prepared from the composite resin composition may be reduced, and if it exceeds 60 parts by weight, the moisture barrier property of the molded article may be lowered. there is.

The ethylene-vinyl alcohol resin (B) is a copolymer of ethylene and vinyl alcohol. Since the vinyl alcohol monomer mainly exists as acetaldehyde, which is a tautomer, ethylene-vinyl acetate (EVA) is obtained by copolymerizing ethylene and vinyl acetate, and then hydrolyzed to obtain a copolymer of ethylene and vinyl alcohol. get a synthesis

In a specific embodiment, the ethylene content in the ethylene-vinyl alcohol resin (B) may be 20 to 40 mol%. Preferably, the ethylene content in the ethylene-vinyl alcohol resin (B) may be 25 to 35 mol%. When the ethylene content in the ethylene-vinyl alcohol resin (B) is out of this range, the processability of the composite resin composition may be deteriorated, and the oxygen barrier property of a molded article manufactured therefrom may be reduced.

In a specific embodiment, the melt index of the ethylene-vinyl alcohol resin (B) when measured at 210° C. under a load of 2.16 kg may be 0.1 to 20 g/10 min. If the melt index of the ethylene-vinyl alcohol resin (B) is less than 0.1 g/10 min, the processability of the composite resin composition is reduced, and when it exceeds 20 g/10 min, miscibility with the polypropylene resin matrix (matrix) ) may be lowered.

(C) modified polyolefin resin

The composite resin composition according to an embodiment of the present invention includes 0.1 to 15 parts by weight of the modified polyolefin resin (C) based on 100 parts by weight of the composite resin composition. As the content of the modified polyolefin resin (C) increases, the compatibility between the polypropylene-based resin (A) and the ethylene-vinyl alcohol resin (B) improves, but when this content exceeds 15 parts by weight, the composite resin composition Mechanical properties of the manufactured molded article may be deteriorated.

In a specific embodiment, the modified polyolefin resin (C) is polypropylene or polyethylene grafted with maleic anhydride. In this case, the polypropylene or polyethylene grafted with maleic anhydride may be prepared by a solution method.

In a more specific embodiment, the content of maleic anhydride in the modified polyolefin resin (C) may be 1.0 to 2.5 wt%. When the graft rate of maleic anhydride is as high as 1.0 to 2.5 wt%, the effect of improving the adhesion to the polar substrate can be obtained. In an exemplary embodiment, the maleic anhydride grafted polypropylene included in the composite resin composition of the present invention may be prepared by graft polymerization of maleic anhydride to polypropylene having a melt index of 0.5 to 3 g/10 min.

(D) Cellulose fibers

The composite resin composition according to an embodiment of the present invention may include 0.1 to 6 parts by weight of cellulose fibers (D) based on 100 parts by weight of the composite resin composition. When the composite resin composition according to an embodiment of the present invention includes the cellulose fiber (D) in an amount of 0.1 to 6 parts by weight, the oxygen and moisture barrier properties of a molded article prepared from the composite resin composition can be further improved.

Cellulose fibers (D) refer to those obtained by pulverizing fibers derived from plants by mechanical treatment or the like. Since wood or non-wood biomass, which is a raw material for cellulose fiber (D), forms a rigid structure by combining materials such as hemicellulose and lignin in addition to cellulose, a grinder or a high-pressure homogenizer ), etc., can be used to efficiently crush these structures to manufacture cellulose fibers (D).

Cellulose fiber (D) has a coefficient of linear thermal expansion at the level of glass fiber and a higher elastic modulus than glass fiber, and is derived from plants, so it is eco-friendly and easy to recycle.

In a specific embodiment, the average diameter of the cellulose fibers (D) may be 50 μm or less and the average length may be 1 mm or less. When the average diameter and average length of the cellulose fibers (D) are within this range, the composite resin composition can be easily molded, and the oxygen barrier properties of the molded article manufactured therefrom can be further improved.

In an embodiment of the present invention, cellulosic fibers may be used in the form of a master batch. Here, the masterbatch may consist of about 60% by weight of cellulose fibers and about 40% by weight of a polypropylene-based resin, but is not particularly limited to this configuration. In addition, the polypropylene-based resin in the masterbatch may be the same as the above-mentioned resin, but is not particularly limited thereto.

(E) additives

The composite resin composition according to an embodiment of the present invention may further include an additive (E) in an amount of 2 parts by weight or less based on 100 parts by weight of components (A) to (D).

In a specific embodiment, the additive (E) may be, for example, at least one selected from the group consisting of antioxidants, neutralizers, reinforcing materials, fillers, weathering stabilizers, antistatic agents, lubricants, slip agents, pigments and dyes, but with this It is not limited.

In one exemplary embodiment, additive (E) is pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 1,3,5-trimethyl-tris at least one antioxidant selected from the group consisting of (3,5-di-t-butyl-4-hydroxybenzene) and tris(2,4-di-t-butylphenyl)phosphite.

In this case, the antioxidant may be included in an amount of 0.01 to 1 parts by weight, preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the composite resin composition. If the content of the antioxidant is less than 0.01 part by weight, it is difficult to secure the antioxidant effect of the composite resin composition, and if it exceeds 1 part by weight, the increase in the antioxidant effect is insignificant and the cost-effectiveness of the composite resin composition may be lowered. not.

There is no particular limitation on the method for preparing the composite resin composition of the present invention, and the method for producing the composite resin composition known in the art to which the present invention belongs can be used as it is or with appropriate modifications, and each resin component described above is limited in a special order Without this, you can freely select and mix in any order you want. Specifically, for example, each of the above-mentioned resins and additives is added to a kneader, a roll, a kneader such as a Banbury mixer, or a single screw/two screw extruder in the required amount, etc. The composite resin composition of the present invention can be prepared by a method of blending the input raw materials using these devices.

Preferably, each of the above-mentioned resins and additives are melt-blended in a twin screw extruder at a temperature of 180 to 250° C. to pelletize.

According to another embodiment of the present invention, there is provided a composite resin molded article manufactured by molding the composite resin composition of the present invention.

There is no particular limitation on a method for manufacturing a molded article from the composite resin composition according to an embodiment of the present invention, and a method known in the art to which the present invention pertains may be used. For example, a composite resin molded article may be manufactured by molding the composite resin composition according to an embodiment of the present invention by a conventional method such as injection molding, extrusion molding, blow molding molding, or casting molding.

In a specific embodiment, the composite resin molded article is an injection molded article, an extrusion molded article, a blow molding molded article, or a casting molded article. More specifically, the composite resin molded article is a film, and more specifically, the composite resin molded article is a packaging film.

In a specific embodiment, the above film has an oxygen transmittance of less than 50 cm 3 /m 2 ·day · atm based on a thickness of 50 to 200 μm. Preferably, the above film has an oxygen permeability of less than 48 cm 3 /m 2 ·day·atm based on a thickness of 50 to 200 μm. More preferably, the above film has an oxygen permeability of less than 46 cm 3 /m 2 ·day·atm based on a thickness of 50 to 200 μm.

In addition, the above film has a moisture permeability of less than 5 ㎤ / m 2 ·day · atm based on a thickness of 50 ~ 200㎛. Preferably, the above film has a moisture permeability of less than 4.5 cm 3 /m 2 ·day · atm based on a thickness of 50 to 200 μm. More preferably, the above film has a moisture permeability of less than 4.0 cm 3 /m 2 ·day·atm based on a thickness of 50 to 200 μm.

In an exemplary embodiment, the film according to an embodiment of the present invention has an oxygen permeability of less than 50 cm 3 /m 2 ·day · atm and a moisture permeability of less than 5 cm 3 /m 2 ·day · atm, based on a thickness of 50 to 200 μm. have

Example

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

In Examples and Comparative Examples, the following resins and compounds were used in the amounts (unit: parts by weight) shown in Table 1.

A1: ethylene-propylene block copolymer (melt index 0.5 g/10 min, xylene extract content 12 wt%, Tm 165 °C, isotactic index 96.4%)

A2: propylene homopolymer (melting index 1.5 g/10 min, xylene extract content 1.3 wt%, Tm 165 ° C, isotactic index 96.9%)

A3: ethylene-propylene block copolymer (melt index 5 g/10 min, xylene extract content 10 wt%, Tm 165 °C, isotactic index 96.6%)

A4: propylene homopolymer (melt index 20 g/10 min, xylene extract content 1.5 wt%, Tm 165 ° C, isotactic index 97.1%)

A5: ethylene-propylene block copolymer (melt index 100 g/10 min, xylene extract content 13 wt%, Tm 165 ° C, isotactic index 95.4%)

A6: propylene homopolymer (melting index 10 g/10 min, xylene extract content 2.1 wt%, Tm 165 ° C, isotactic index 94.2%))

A7: ethylene-propylene block copolymer (melt index 40 g/10 min, xylene extract content 24 wt%, Tm 163 °C, isotactic index 95.9%))

B1: Ethylene-vinyl alcohol resin (melt index 9 g/10 min, ethylene content 27 mol%)

B2: Ethylene-vinyl alcohol resin (melt index 4 g/10 min, ethylene content 32 mol%)

C1: Maleic anhydride graft polypropylene resin (maleic anhydride content 1.2%)

D1: Cellulose fiber masterbatch (40% by weight of cellulose fibers, average diameter 20 μm, average length 500 μm)

D2: talc (average particle size of 5 µm)

Example comparative example One 2 3 One 2 3 4 A1 - 40 - - - - - A2 - - 35 - - - - A3 - - - 85 - - - A4 44 - - - 80 - - A5 - - - - - 50 - A6 - - - - - - 30 A7 - - - - - - 35 B1 50 - 55 15 - 15 15 B2 - 42 - - 10 - 5 C1 5 10 5 - 5 10 5 D1 One 8 5 - - 25 10 D2 - - - - 5 - -

Experimental example

The physical properties of the resins used in Examples and Comparative Examples were measured in the following manner.

(1) Melt index

Melt index was measured at 230°C under a load of 2.16 kg according to ASTM D1238.

(2) isotactic index

In the xylene insoluble fraction in the polypropylene molecule measured using ¹³ C-NMR, isotacticity was measured by the content of mmmm Pendard units.

(3) content of solvent extract (xylene extract; xylene soluble)

The polypropylene resin was dissolved in xylene at a concentration of 1% at 135° C. for 1 hour and 30 minutes, extracted after 30 minutes at room temperature, and the weight was measured and expressed as a percentage of the total weight of the polypropylene resin. .

(4) Melting temperature

Using TA Instrument Q2000 differential scanning calorimetry (DSC), the sample was maintained isothermal at 200°C for 10 minutes to remove the thermal history, and then cooled from 200°C to 30°C at 10°C per minute and crystallized to obtain the same thermal history. After the temperature was maintained isothermal at 30 ° C. for 10 minutes, the temperature was raised by 10 ° C. per minute again, and the melting temperature (Tm) was obtained from the peak temperature.

After melt-blending the resins and additives of the content (unit: parts by weight) as shown in Table 1 at a temperature of 200° C. in a twin-screw extruder to pelletize, the die casting molding method using Thermo Scientific HAAKE A film was prepared by At this time, the processing temperature was 200 ~ 230 ℃, the film thickness was 50 ~ 200㎛.

The properties of the specimens obtained in each Example and Comparative Example were measured in the following manner.

(5) transmittance

Oxygen permeability was measured according to ASTM D3985, and moisture permeability was measured according to ASTM F1249. The results are shown in Table 2.

Example comparative example One 2 3 One 2 3 4 Film thickness (㎛) 100 50 200 200 30 150 150 oxygen permeability
(㎤/㎡·day·atm) 46 38 33 750 1,300 1,000 650 water permeability
(㎤/㎡·day·atm) 3.36 3.88 3.15 4.69 5.71 3.86 5.07

As can be seen from Tables 1 and 2 above, the films prepared from the composite resin compositions of Examples within the scope of the present invention exhibited low values of both oxygen and moisture permeability.

On the other hand, in Comparative Example 1, which contained a small amount of ethylene-vinyl alcohol resin and did not contain a modified polyolefin resin, both oxygen and moisture permeability were high, and in particular, oxygen permeability was very high.

In Comparative Example 2 in which the content of the ethylene-vinyl alcohol resin was small and talc was used, both oxygen and moisture permeability were high, and in particular, oxygen permeability was very high.

In Comparative Example 3 with a small content of ethylene-vinyl alcohol resin and a high content of cellulose fibers, the moisture permeability was good, but the oxygen permeability was very high.

In Comparative Example 4 using a high content of a polypropylene-based resin having a large solvent extract content and a low isotactic index, both oxygen and moisture permeability were high.

Therefore, since the composite resin composition according to an embodiment within the scope of the present invention is excellent in both oxygen and moisture barrier properties, a molded article manufactured therefrom, specifically a film, can be effectively used as a food packaging.

Claims (13)

Based on 100 parts by weight of the composite resin composition, (A) 20-50 parts by weight of a polypropylene-based resin; (B) 20-60 parts by weight of an ethylene-vinyl alcohol resin; (C) 0.1 to 15 parts by weight of a modified polyolefin resin; and (D) 0.1 to 6 parts by weight of cellulose fibers, wherein the polypropylene-based resin (A) is (A-1) a propylene homopolymer resin; (A-2) Ethylene-propylene block copolymer resin obtained by stepwise polymerization of propylene homopolymer, propylene-ethylene random copolymer or propylene-1-butene random copolymer and ethylene-propylene rubber copolymer in a reactor, and mixtures thereof A composite resin composition selected from the group consisting of, and having a melt index of 0.1 to 30 g/10 min of the polypropylene-based resin (A) when measured at 230° C. under a load of 2.16 kg.
The composite resin composition of claim 1, wherein the polypropylene-based resin (A) has an isotactic index of 95.0% or more, a solvent extract content of 15% by weight or less, and a melting temperature of 160°C or more according to stereoregularity. .
The composite resin composition according to claim 1, wherein the ethylene content in the ethylene-vinyl alcohol resin (B) is 20 to 40 mol%.
The composite resin composition of claim 1, wherein the melt index of the ethylene-vinyl alcohol resin (B) is 0.1 to 20 g/10 min when measured at 210° C. under a load of 2.16 kg.
The composite resin composition according to claim 1, wherein the modified polyolefin resin (C) is polypropylene or polyethylene grafted with maleic anhydride.
The composite resin composition according to claim 5, wherein the content of maleic anhydride in the modified polyolefin resin (C) is 1.0 to 2.5 wt%.
The composite resin composition according to claim 1, wherein the cellulose nanofibers (D) have an average diameter of 50 µm or less and an average length of 1 mm or less.
The composite resin composition according to claim 1, further comprising an additive (E) in an amount of 2 parts by weight or less based on 100 parts by weight of components (A) to (D).
The composite resin composition according to claim 8, wherein the additive (E) is at least one selected from the group consisting of antioxidants, neutralizers, reinforcing materials, fillers, weathering stabilizers, antistatic agents, lubricants, slip agents, pigments and dyes.
10. The method according to claim 9, wherein the additive (E) is pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate), 1,3,5-trimethyl-tris( 3,5-di-t-butyl-4-hydroxybenzene) and tris(2,4-di-t-butylphenyl)phosphite at least one antioxidant selected from the group consisting of.
A composite resin molded article manufactured by molding the composite resin composition of claims 1 to 10.
The composite resin molded article according to claim 11, which is an injection molded article, an extrusion molded article, a blow molding molded article, or a casting molded article.
The composite according to claim 12, wherein the composite resin molded article is a film, and has an oxygen permeability of less than 50 cm 3 /m 2 ·day · atm and a moisture permeability of less than 5 cm 3 /m 2 ·day · atm based on a thickness of 50 to 200 μm. resin molded product.