KR100961729B1 - Cellulosic polymer composites and low carbon environment-friendly mouldings produced therefrom - Google Patents

Abstract

PURPOSE: A cellulosic polymer composite and a low carbon environment-friendly molded product manufactured therefrom are provided to reduce the pyrolysis by inducing the dispersion between a cellulose material and a synthetic resin. CONSTITUTION: A cellulosic polymer composite contains 20~80wt% of cellulose based powder, 20~80wt% of polyolefin resin, 0.1~10wt% of ethylene glycidyl methacrylate copolymer, and 0.0001~0.1wt% of quaternary ammonium salt or quaternary phosphonium salt. The ethylene glycidylmethacrylate copolymer contains 3~50wt% of glycidyl methacrylate. The quaternary phosphonium salt is selected from the group consisting of tetrabutyl phosphonium bromide, ethyltriphenylphosphonium bromide, methyltributylphosphonium chloride and benzyltriphenyl chloride.

Description

Cellulose-based resin composites and low carbon environmentally-friendly moldings produced therefrom {Cellulosic polymer composites and low carbon environment-friendly mouldings produced therefrom}

The present invention relates to a cellulose-based resin composite and a low carbon environmentally friendly molded article prepared therefrom. More specifically, the present invention relates to a novel resin composite having a cellulose-based powder and a polyolefin-based resin as main ingredients and having excellent environmental properties by reducing carbon dioxide (greenhouse gas) while maintaining excellent mechanical properties.

The Kyoto Protocol, concluded in 1997 to overcome severe global warming caused by excessive carbon dioxide emissions, imposes the obligation on 38 advanced countries to reduce greenhouse gas emissions while giving them the right to emit carbon dioxide to induce new implementation. Introduced a carbon trading scheme to buy and sell. At the end of 2007, the Bali Roadmap, which was followed by the Kyoto Protocol, was adopted, which is evaluated positively in that 180 member countries should reduce CO2 regardless of developed and developing countries. It is taking steps to create a low carbon green growth industry. As a result, a new market for so-called carbon dioxide-reducing new materials suitable for the low-carbon green growth industry is being opened.

As the most promising material as a carbon dioxide-reducing new material, a bio material obtained from plants, specifically a cellulose-based material, has been highlighted. Conventionally, synthetic resins, which are used as raw materials for various molded products, are manufactured with starting oil, which is gradually depleted of resources, and have a structure that emits greenhouse gas when incinerated after disposal, while cellulose such as wood flour, rice hull, hemp, kenaf, pulp, etc. System materials are made from plants that grow by photosynthesis by absorbing carbon dioxide in the atmosphere, and the overall cycle results in a reduction of carbon dioxide. Therefore, the cellulose-based resin composites and the molded products prepared from the cellulose-based composites and synthetic resins are being re-evaluated from the viewpoint of so-called low-carbon eco-friendly materials and products that reduce carbon dioxide, and the demand thereof is greatly increased.

In other words, conventional cellulose resin composites are emphasized in terms of recycling using waste resources such as sawdust and rice hulls, or resin composites containing more than 50% by weight of powdered wood are classified as synthetic wood and possess wood texture while reinforcing the disadvantages of wood. In recent years, it is being reexamined from the viewpoint of so-called low carbon eco-friendly materials and products that reduce carbon dioxide.

Therefore, in the case of cellulose-based resin composites, the higher the cellulose content, the higher the cellulose content, while the higher the cellulose content, the greater the low-carbon eco-friendly effect and the lower the cellulose-based material compared to the synthetic resin. As a result, the economic gain is also increased proportionally, and there is an urgent need for the development of a new resin composite having a high cellulose content.

By the way, the cellulose-based material acts as a kind of organic filler in the cellulose-based resin composite, which is very difficult to disperse the synthetic resin. In other words, while cellulose-based materials have a large amount of hydrophilic functional groups such as hydroxyl groups, general-purpose synthetic resins such as polyethylene, polypropylene, and polystyrene have lipophilic properties, which are extremely difficult to disperse and are easily decomposed by heat during the dispersion process. It is difficult to cause not only dropping, but also discoloration due to carbonization, and high content of water, which adversely affects the molding processability.

In order to overcome such difficulties, maleic anhydride, phthalic anhydride, and silane-based compounds are used as coupling agents to increase the compatibility by reaction with hydroxyl groups of cellulose, as in Korean Patent Application No. 1999-33055, or Korean Patent Registration Maleic anhydride graft polypropylene is used as the reactive compatibilizer as in 928702, or carboxylic acid or anhydrous carboxylic acid graft polyolefin is used as the reactive compatibilizer as in Korean Patent Registration No. 848219 and the basics such as CaO, ZnO Reactive fillers have been prescribed to minimize moisture loss of cellulose and thermal decomposition of the composites, but have not yet produced satisfactory results.

As described above, the reactive compatibilizer introduced into the cellulose-based resin composite is insufficient in expression of compatibility due to the reaction, and when the dispersion time is sufficiently increased to increase the compatibility, the thermal decomposition of cellulose is promoted to cause discoloration and deterioration of mechanical properties. Such serious problems are urgently required to take drastic improvements. In other words, the emergence of new materials and molded products made from these materials exhibits a low-carbon eco-friendly effect due to the cellulose contained while maintaining excellent mechanical properties while minimizing thermal decomposition by inducing high dispersion of cellulose materials and synthetic resins in a short time. It is becoming.

In order to solve the above problems, the present inventors have led to the present invention as a result of intensive studies. That is, the present invention is to provide a cellulose-based resin composite and a low carbon environmentally friendly molded article prepared from them.

In order to solve the above problems, the present invention is 20 to 80% by weight of cellulose-based powder; 20 to 80% by weight of polyolefin resin; It provides a cellulose-based resin composite and low-carbon environmentally friendly molded article prepared therefrom, including 0.1 to 10% by weight of an epoxy group-containing polyolefin resin; and 0.0001 to 0.1% by weight of a quaternary ammonium salt or a quaternary phosphonium salt.

In the present invention, the cellulose-based material powder is a pulverized material containing various types of cellulose such as cellulose, hemicellulose, lignocellulose, ie, cellulose-based materials, and the cellulose-based materials may be generally obtained from various plants. . Specific examples include wood such as conifers such as pine, spruce, fir, hardwood such as maple, poplar, and aspen, grains such as rice, wheat, oats, barley, corn, peanut, kenaf, bamboo, jute, hemp, It can be obtained from various types of plants, such as crops such as ramie, flax and the like, and any form of fruit, stem, leaves, roots, bark, etc. of the plant can be used in the present invention. These plants play a very important role in absorbing carbon dioxide in the atmosphere and growing through photosynthesis to express the so-called low carbon eco-friendly effect of reducing carbon dioxide on the planet.

In addition, the cellulose-based material powder of the present invention is obtained by intentionally pulverizing a plant containing the cellulose, or by pulverizing by-products or wastes such as rice hulls, straw, sawdust, etc. generated through harvesting, plate processing, etc. Powders obtained by processing the cellulose-based materials, such as pulp or paper, and the like, are pulverized. The cellulose-based materials may be spherical or fibrous.

The size of the cellulose-based powder is suitably having an average particle size of 0.01 to 50 mm, in particular 0.1 to 5 mm. When the cellulose-based powder is fibrous, it can be represented by a long axis and a short axis. The cellulose-based powder is preferably 20 to 80% by weight of the cellulose-based resin composite, and preferably 30 to 60% by weight based on the total weight. If less than 20% by weight, low-carbon environmental effects due to the cellulose-based materials contained are insignificant, if more than 80% by weight is excellent in low-carbon eco-friendly effects, but there is a fear that the mechanical properties significantly decrease.

The polyolefin resin in the present invention is one or more selected from polyethylene, polypropylene, polybutylene, or copolymers thereof.

Examples of the polyolefin resin include low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, copolymers based on ethylene, polypropylene, copolymers based on propylene, polybutene, and the like. It may be prepared by a polymerization method using a Ziegler-based catalyst, a chromium-based catalyst, a metalocene catalyst, and the like, the copolymer may be in the form of a random copolymer or a block copolymer, and the molecular structure is atactic, isotactic or synth. Any of the atactic may be used, and the polymerization method may be any of a low pressure method, a medium pressure method, and a high pressure method. It is possible to mix | blend additives, such as a heat stabilizer, a ultraviolet absorber, an antistatic agent, a fluorescent agent, with such polyolefin resin by a well-known method.

The polyolefin-based resin is suitably 20 to 80% by weight, preferably 30 to 60% by weight, based on the total weight of the total cellulose-based resin composite. If it is less than 20% by weight, the low-carbon eco-friendly effect is excellent, but there is a possibility that the mechanical properties are significantly lowered, if it exceeds 80% by weight, the low-carbon eco-friendly effect by the contained cellulose-based material is minimal.

The epoxy group-containing polyolefin resin in the present invention is a copolymer prepared mainly from an olefin monomer and an epoxy group-containing comonomer, wherein the epoxy group-containing polyolefin resin has a content of an epoxy group-containing comonomer of 3% by weight to 50% by weight. It is characterized by that. If the content of the comonomer is less than 3% by weight, the compatibility by the reaction with a hydrophilic functional group such as a hydroxyl group of the cellulose-based material is difficult to express as desired.

The reason for introducing such epoxy group-containing polyolefin resin in the resin composite of cellulose-based material and polyolefin resin is that the main chain is polyolefin-based resin, so that it is naturally compatible with polyolefin-based resin. It is focused on the fact that the reaction can be made into a so-called excellent reactive compatibilizer that is well expressed by reaction with a hydrophilic functional group such as a hydroxyl group.

More preferred examples include ethylene-glycidyl methacrylate (GMA) copolymer, ethylene-butyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate-glycidyl methacrylate copolymer, and the like. Likewise, there may be mentioned a copolymer prepared based on ethylene and glycidyl methacrylate as a main component.

Examples of more specific epoxy group-containing polyolefin resins include Igetabond 2C (GMA content 6 wt%, manufactured by Sumitomo Chemical), Lotader AX8840 (GMA content 8 wt%, manufactured by Arkema), Igetabond E (GMA content 12 wt%, manufactured by Sumitomo Chemical), and the like. Ethylene-glycidyl methacrylate copolymer, Ethylene-butyl acrylate-glycidyl methacrylate copolymer, such as Elvaloy PTW (GMA content 5% by weight, DuPont), Lotader AX8900 (GMA content 8% by weight, And ethylene-methylacrylate-glycidyl methacrylate copolymers such as those manufactured by Arkema.

More preferably, the epoxy group-containing polyolefin resin is a copolymer containing ethylene and glycidyl methacrylate as main components.

The epoxy group-containing polyolefin resin is preferably 0.1 to 10% by weight of the cellulose-based resin composite, and preferably 0.5 to 5% by weight based on the total weight. If less than 0.1% by weight does not exhibit compatibility due to reaction with hydrophilic functional groups such as hydroxyl groups of the cellulose-based material is poor mechanical properties and there is a high possibility of discoloration due to carbonization of cellulose-based material and exceeds 10% by weight It is excellent in compatibility and somewhat better in terms of mechanical properties, but there is a limit to the improvement, and because the epoxy group-containing polyolefin resin itself is very expensive, it is not preferable because of poor economic efficiency.

As described above, the epoxy group-containing polyolefin resin according to the present invention was introduced as a kind of reactive compatibilizer in the resin composite of the cellulose-based material and the polyolefin resin, but the amount thereof was increased. This phenomenon has been aggravated when the cellulose-based material content is increased in the resin composite to reach a certain limit level, and in particular, to maximize the low-carbon eco-friendly effect. In addition, increasing the dispersion reaction time to improve this, as shown in the prior art, due to the carbonization of some cellulose-based materials, discoloration and deterioration of the phenomena also occur, something new attempts are urgently needed. Therefore, by adding a small amount of quaternary ammonium salt or quaternary phosphonium salt in addition to the epoxy group-containing polyolefin resin, the mechanical properties are improved by the excellent compatibility between the cellulose-based material and the polyolefin-based resin in a very short time while minimizing the additional cost burden. It has been completed the present invention that the effect is surprisingly expressed.

The quaternary ammonium salts are tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentyl ammonium bromide, tetrahexyl ammonium bromide, tetramethylammonium chloride, tetraethyl Ammonium Chloride, Tetrapropyl Ammonium Chloride, Tetrabutyl Ammonium Chloride, Tetrabutyl Ammonium Chloride Iodide, Tetrabutyl Ammonium Hydrogen Sulfate, Tetrabutyl Ammonium Hydrochloride, Benzyl Trimethyl Ammonium Chloride, Benzyl Triethyl Ammonium Chloride One or more selected from the group consisting of can be selected.

The quaternary phosphonium salt is characterized in that at least one selected from the group consisting of tetrabutyl phosphonium bromide, ethyl triphenyl phosphonium bromide, methyl tributyl phosphonium chloride, benzyl triphenyl chloride.

In the present invention, the amount of quaternary ammonium salt or quaternary phosphonium salt added is preferably 0.0001 to 0.1% by weight, preferably 0.001 to 0.05% by weight, and 0.005 to 0.01% by weight, based on the total weight of the cellulose resin composite. % Is more preferred. According to the results of our analysis, the quaternary ammonium salt or quaternary phosphonium salt according to the present invention acts as an excellent catalyst in the reaction of hydrophilic functional groups such as hydroxyl groups of cellulose materials and epoxy groups of epoxy group-containing polyolefin resins. It was estimated that the mechanical properties were achieved by maximizing reactive compatibility without discoloration due to carbonization of cellulose-based materials in a short time. When the content of quaternary ammonium salt or quaternary phosphonium salt is less than 0.0001% by weight, it is difficult to obtain excellent mechanical properties due to the insignificant reactive catalysis effect. When the content of quaternary ammonium or quaternary phosphonium salt is more than 0.1% by weight It is very expensive, so it is unfavorable because of poor economics.

In the present invention, the cellulose-based resin composites include conventional additives such as antioxidants, heat stabilizers, ultraviolet stabilizers, lubricants, processing aids, desiccants, pigments, dyes, foaming agents, flame retardants and the like that do not impair the object of the present invention. It can mix | blend in the range.

The present invention provides a low carbon eco-friendly molded article made of the cellulose-based resin composite according to the present invention. More specifically, the present invention provides a low-carbon eco-friendly molded article for film, sheet, plate, horn, rod, tray, bottle or profile.

The cellulose-based resin composite of the present invention having the above-described constitution is a single-screwed composition comprising a cellulose-based powder, a polyolefin-based resin, an epoxy group-containing polyolefin-based resin, a quaternary ammonium salt or a quaternary phosphonium salt in an appropriate ratio. It can be obtained by kneading and dispersing with an extruder, a twin screw extruder, a mixing roll, a balm mixer, a kneader or the like to produce a compound pellet.

Particularly, powdered polyolefin resins, not pellets, are used to mix cellulose-based powders, epoxy group-containing polyolefin resins, quaternary ammonium salts or quaternary phosphonium salts in an appropriate ratio, and put them in a high speed stirrer maintained at a constant temperature. When a high speed stirring is performed for a predetermined time, a small amount of water contained in the cellulose-based powder is volatilized and removed, thereby achieving uniform mixing. The compound thus obtained is subjected to the single screw extruder, the twin screw extruder, the mixing roll, the balamba mixer, By kneading and dispersing with a kneader or the like to form a compound pellet, it is possible to obtain cellulose-based resin composite pellets which are more effectively dispersed while minimizing moisture content which may adversely affect the manufacture of molded articles.

In addition, the cellulose-based resin composite pellets thus obtained are formed into films, sheets, plates, squares, rods, trays, bottles, and profiles by conventional plastic molding methods such as extrusion, injection, blow, vacuum, and compression molding. And various types of molded articles can be produced. In addition, at least one or more layers of the cellulose-based resin composite according to the present invention may be used in a multi-layer molding machine, and the remaining layers may be manufactured using a composite multi-layered molded article having a conventional synthetic resin.

The cellulose-based resin composites and the molded articles prepared therefrom according to the present invention thus obtained are highly carbon-friendly due to the cellulose contained while maintaining excellent mechanical properties while minimizing thermal decomposition by causing high dispersion of cellulose materials and synthetic resins within a short time. It is amazing that the effect is realized.The interior and exterior materials for building such as door frames, doors, windows, floors, ceilings, moldings, decorates, stairs, railings, benches, desks, chairs, bookshelves, cabinets, sinks, hangers, cupboards, and cabinets It can be usefully used as a molded article such as a packaging tray, a packaging sheet, a packaging film, a packaging bottle suitable for a furniture, food, household goods, medicine, electronic products, communication products, machinery parts packaging.

Cellulose-based resin composites and molded articles prepared therefrom according to the present invention cause high dispersion of the cellulose material and the synthetic resin within a short time to minimize thermal decomposition while maintaining excellent mechanical properties while having a low carbon eco-friendly effect due to the contained cellulose It is expected to be very useful in various fields as a molded article such as building interior and exterior materials, furniture, packaging trays, packaging sheets, packaging films, packaging bottles, etc.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

Tensile strength, flexural strength, flexural modulus, impact strength and appearance of the molded articles manufactured according to the following Examples and Comparative Examples were measured as follows.

(The tensile strength)

Tensile strength (MPa) of the sample was evaluated according to KS M 3006.

Flexural strength

The flexural strength (MPa) of the sample was evaluated according to KS M ISO 178.

Flexural Modulus

The flexural modulus (GPa) of the sample was evaluated according to KS M ISO 178.

(Impact strength)

Izod impact strength (KJ / m ² ) of the sample was evaluated according to KS M 3055.

(Exterior)

The color of the cellulose-based powder used and the color of the molded article obtained through the manufacturing and molding of the cellulose-based resin composite were compared with each other to visually evaluate the degree of discoloration. (◎ Excellent, Good, △ Normal, X Bad)

Example 1

First, as a cellulose-based powder, an average size of 0.05mm fine wood powder (cellulose-based material A) was prepared. As a polyolefin-based resin, polypropylene-based polypropylene (polyolefin-based) having a melt index (230 ° C., 2.16 Kg) of 8.0 g / 10 minutes and a density of 0.91 was obtained. Resin A) was prepared. In addition, Lotader AX8840 (8 wt% GMA content, manufactured by Arkema, Epoxy group-containing resin A) was prepared as an epoxy group-containing polyolefin resin, and tetramethylammonium bromide (manufactured by Aldrich Chemical, quaternary ammonium salt A) was prepared as a quaternary ammonium salt. . 30% by weight of cellulose-based material A, 67.999% by weight of polyolefin-based resin A, 2% by weight of epoxy group-containing resin A, and 0.001% by weight of quaternary ammonium salt A in a high speed stirrer maintained at 100 ° C (see Table 1). ) Was added to a twin screw extruder and kneaded and dispersed to prepare a cellulose resin composite in pellet form. The obtained cellulose-based resin composite was introduced into an extruder hopper, extruded at 190 ° C., cooled, and cut to prepare a plate-shaped molded product sample having a width of 150 mm and a thickness of 10 mm. The physical properties of the obtained molded product samples were evaluated and shown in Table 1.

[Example 2]

50% by weight of cellulose-based material A, 44.995% by weight of polyolefin-based resin A, 5% by weight of epoxy group-containing resin A, and 0.005% by weight of quaternary ammonium salt A using a cellulose-based resin composite The same procedure as in Example 1 was followed. The physical properties of the obtained molded product samples were evaluated and shown in Table 1.

Example 3

Cellulose-based resin composite according to the blending ratio (see Table 1) of 70% by weight of cellulose-based material A, 21.99% by weight of polyolefin-based resin A, 8% by weight of epoxy group-containing resin A, and 0.01% by weight of quaternary ammonium salt A It carried out similarly to Example 1 except having used. The physical properties of the obtained molded product samples were evaluated and shown in Table 1.

Comparative Example 1

It carried out similarly to Example 1 except having used the cellulose-type resin composite by the compounding ratio (refer Table 1) of 50 weight% of cellulose-type raw materials A, 45 weight% of polyolefin resin A, and 5 weight% of epoxy group containing resin A. . The physical properties of the obtained molded product samples were evaluated and shown in Table 1.

TABLE 1 Property evaluation results of the molded article obtained according to Examples 1 to 3 and Comparative Example 1

Example 4

First, as a polyolefin resin, a polypropylene block copolymer (polyolefin resin B) having a powdery melt index (230 ° C., 2.16 Kg) of 1.0 g / 10 minutes and a density of 0.91 was prepared, and Igetabond 2C (GMA content) was used as an epoxy group-containing polyolefin resin. 6% by weight, manufactured by Sumitomo Chemical, epoxy group-containing resin B), and ethyltriphenyl phosphonium bromide (made by Aldrich Chemical, quaternary phosphonium salt A) were prepared as quaternary phosphonium salts. 40% by weight of cellulose-based material A, 54.996% by weight of polyolefin-based resin B, 6% by weight of epoxy group-containing resin B, and 0.004% by weight of quaternary phosphonium salt A were added to a high speed stirrer maintained at 100 ° C. The composition obtained by high-speed stirring for 20 minutes was introduced into a twin screw extruder and kneaded and dispersed to prepare a cellulose resin composite in pellet form. The obtained cellulose-based resin composite was extruded at 200 ° C. using an extrusion machine to prepare a sheet having a thickness of 0.7 mm. The resulting sheet was vacuum molded at 180 ° C. to prepare a tray molded product sample for packaging. The physical properties of the obtained molded article samples were evaluated and shown in Table 2.

Example 5

Cellulose-based resin composite according to the compounding ratio (see Table 2) of 60% by weight of cellulose-based material A, 33.992% by weight of polyolefin-based resin B, 6% by weight of epoxy group-containing resin B, and 0.02% by weight of quaternary phosphonium salt A It carried out similarly to Example 4 except having used. The physical properties of the obtained molded article samples were evaluated and shown in Table 2.

Example 6

In addition to the cellulose-based material A, a fibrous kenaf (cellulose-based material B) having a long axis of 30 mm and a short axis of 0.03 mm was prepared as the cellulose base material powder. 40% by weight of cellulose-based material A, 20% by weight of cellulose-based material B, 33.95% by weight of polyolefin-based resin B, 6% by weight of epoxy group-containing resin B, 0.05% by weight of quaternary phosphonium salt A (see Table 2) It carried out similarly to Example 4 except having used the cellulose-type resin composite by). The physical properties of the obtained molded article samples were evaluated and shown in Table 2.

Comparative Example 2

40% by weight of cellulose-based material A, 20% by weight of cellulose-based material B, 34% by weight of polyolefin-based resin B, and 6% by weight of epoxy group-containing resin B except for using the cellulose-based resin composite according to the compounding ratio (see Table 2). It carried out similarly to Example 4. The physical properties of the obtained molded article samples were evaluated and shown in Table 2.

TABLE 2 Molded article physical property evaluation results obtained according to Examples 4 to 6 and Comparative Example 2

First, in Examples 1 to 3, as the content of the cellulose-based material in the composition increases, the tensile strength, flexural strength, flexural modulus is excellent, and the shot strength and appearance (discoloration resistance due to processing) are somewhat decreased, but the overall excellent physical properties On the other hand, the cellulose-based material content in the composition is the same, but compared to Example 2, which contains the quaternary ammonium salt and Comparative Example 1, which does not contain the quaternary ammonium salt, the physical and appearance differences are apparent.

This is because the quaternary ammonium salt according to the present invention acts as an excellent catalyst in the reaction of hydrophilic functional groups such as hydroxyl groups of cellulose-based materials with epoxy groups of polyolefin-based resins containing epoxy groups, thereby causing discoloration due to carbonization of cellulose-based materials in a short time. It is inferred to achieve amazing mechanical properties by maximizing reactive compatibility without generation.

In addition, looking at Examples 4 to 6, it can be seen that even if the polyolefin-based resin or the cellulose-based material is changed, the physical properties and appearance of the cellulose-based resin composite according to the present invention and the molded article prepared therefrom are very excellent. Particularly, the phenomena shown in Example 2 and Comparative Example 1 were compared with those of Example 6 containing the same cellulose-based material but not containing quaternary phosphonium salt in the composition. Similarly, it can be seen that the difference in physical properties and appearance is apparent.

Claims (8)

20 to 80% by weight of cellulose-based powder; 20 to 80% by weight of polyolefin resin; 0.1 to 10 wt% of an ethylene-glycidyl methacrylate copolymer; and 0.0001 to 0.1 wt% of a quaternary ammonium salt or quaternary phosphonium salt; wherein the ethylene-glycidyl methacrylate copolymer is A cellulose resin composite comprising 3% by weight to 50% by weight of glycidyl methacrylate. The method of claim 1, The quaternary ammonium salts are tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentyl ammonium bromide, tetrahexyl ammonium bromide, tetramethylammonium chloride, tetraethyl Ammonium Chloride, Tetrapropyl Ammonium Chloride, Tetrabutyl Ammonium Chloride, Tetrabutyl Ammonium Chloride Iodide, Tetrabutyl Ammonium Hydrogen Sulfate, Tetrabutyl Ammonium Hydrochloride, Benzyl Trimethyl Ammonium Chloride, Benzyl Triethyl Ammonium Chloride One or more cellulose-based resin composites selected from the group consisting of. The method of claim 1, The quaternary phosphonium salt is at least one selected from the group consisting of tetrabutyl phosphonium bromide, ethyl triphenyl phosphonium bromide, methyl tributyl phosphonium chloride, and benzyl triphenyl chloride. Compound. delete delete The method of claim 1, Wherein said polyolefin resin is at least one selected from polyethylene, polypropylene, polybutylene, or copolymers thereof. A low carbon eco-friendly molded article made of the cellulose-based resin composite according to any one of claims 1 to 3 and 6. The method of claim 7, wherein The low carbon eco-friendly molded article is a low-carbon eco-friendly molded article for film, sheet, plate, square material, rod, tray, bottle or profile.