KR102532715B1 - Carbon-neutral eco-friendly inorganic material-filled polyolefin resin composition and articles obtained therefrom - Google Patents

Abstract

The present invention may relate to a carbon-neutral and eco-friendly composition that is a polyolefin resin composition in which a polyolefin resin, a polyethylene-based ionomer, and a nucleating agent are contained in at least 30 wt% of an inorganic material or a cyclic olefin copolymer is additionally contained thereto. In the carbon-neutral and eco-friendly composition and articles obtained therefrom according to the present invention, the articles have excellent toughness and excellent recyclability upon disposal, and even if the articles are not recycled and incinerated, carbon dioxide emissions are reduced by the amount of inorganic materials filled, making it possible to achieve carbon neutrality.

Description

Carbon-neutral eco-friendly inorganic material-filled polyolefin resin composition and articles obtained therefrom}

The present invention may relate to a carbon-neutral, environmentally-friendly inorganic material-filled polyolefin resin composition and an article obtained therefrom.

More specifically, an eco-friendly inorganic-filled polyolefin resin composition that not only has excellent toughness, heat-sealability, and excellent recyclability when disposed of, but also can respond to carbon neutrality by reducing the amount of carbon dioxide generated by the content of the filled inorganic matter even if it is not recycled and incinerated, and the polyolefin resin composition obtained therefrom It could be about an item.

[National research and development project supporting this invention]
[Assignment identification number] D2222027
[Name of department] Gyeonggi Provincial Office
[Task management (professional) institution name] Gyeonggi Provincial Institute for Economics and Science Promotion
[Research project name] Gyeonggi-do technology development project
[Research Project Title] Development of carbon-neutral eco-friendly plastic bags for food delivery based on polyethylene composites filled with nano-inorganic particles
[Contribution rate] 1/1
[Name of project performing organization] Anychem Co., Ltd.
[Research period] 2022.07.01 ~ 2023.06.30
Despite the strengthening of related environmental regulations after the worldwide declaration of carbon neutrality due to the generation of carbon dioxide, the main culprit of global warming, shopping bags, delivery (courier) bags, air cap safety bags, ice pack bags, dry ice The market for disposable plastic products such as packaging bags, ziplock bags, roll bags, sanitary bags, wraps, clean bags, tablecloths, containers, cups, plates, spoons, forks, knives, toothbrush heads, razors, chopsticks, and toothpicks continues to grow. In particular, instead of a sharp decline in the offline market due to the impact of Corona 19, the online market, for example, where delivery to the desired place is activated only by ordering a mobile phone, and it is not shrinking but rather growing.

Most of the disposable plastic products are made of polyolefin resins such as polyethylene and polypropylene, because they have excellent economic efficiency such as being extremely inexpensive despite having excellent toughness.

In particular, since it is practically impossible to replace disposable polyolefin resin products used during delivery (transportation) with shopping carts, boxes, etc., their use cannot be avoided. Therefore, recognizing this fact, it is urgent and desperate to emerge a new carbon-neutral polyolefin material that is suitable for disposable products requiring excellent toughness, heat-sealability, and economy, and at the same time, can reduce the generation of carbon dioxide.

Polyolefin resin filled with inorganic materials such as calcium carbonate and talc has recently been discussed as a candidate for such a material. This material is a very promising solution because carbon dioxide generation is reduced by the amount of inorganic filling and it is judged to be very advantageous in terms of economic efficiency because inorganic materials such as calcium carbonate are usually very cheap. However, when 30% by weight, 50% by weight, 60% by weight or more, and 70% by weight or more of inorganic materials are filled in a large amount, especially in the case of products obtained as films and sheets, stiffness evaluated by tensile strength and toughness evaluated by elongation are severely deteriorated. Since there is a serious problem that sufficient carbon reduction effect cannot be imparted, it is urgent to develop a new eco-friendly carbon reduction polyolefin composition capable of maintaining sufficient rigidity or toughness even when a heavy inorganic filler is used.

In order to solve the above problems, the present inventors have reached the present invention as a result of repeated research.

That is, the present invention not only has relatively excellent toughness, heat-sealing synthesis and excellent recyclability at the time of disposal, even though it includes a high content of inorganic filler, for example, even when 70% by weight or more of inorganic filler is used, and even if it is not recycled and incinerated, filled It is an object of the present invention to provide an eco-friendly inorganic material-filled polyolefin resin composition capable of responding to carbon neutrality as the amount of carbon dioxide generated is reduced as much as the inorganic content, and an article obtained therefrom.

One aspect of the present invention to solve the above problem is to use 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, 70% to 85% by weight of an inorganic filler, or between these values The above problems may be solved by providing a polyolefin resin composition including polyolefin resin, polyethylene ionomer, and nucleating agent, even though inorganic fillers are used. Another aspect of the present invention provides a polyolefin resin composition comprising, for example, 30% to 85% by weight of an inorganic material based on the total composition, and including a polyolefin resin, a polyethylene-based ionomer, a nucleating agent and a cyclic olefin copolymer, It may have solved the problem.

In one embodiment, the polyolefin resin is carbon-neutral at least one selected from the group consisting of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene homopolymer, polypropylene random copolymer, polypropylene block copolymer, and polybutene. It may relate to an eco-friendly resin composition.

In one embodiment, the inorganic material is calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, barium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos powder It may relate to a carbon-neutral eco-friendly resin composition that is at least one selected from zeolites, silicate clay, and mixtures thereof.

In one embodiment, the polyethylene-based ionomer may relate to a carbon-neutral eco-friendly resin composition that is a polyethylene-based copolymer containing a carboxylic acid group neutralized with metal ions.

In one embodiment, the polyethylene-based ionomer may relate to a carbon-neutral eco-friendly resin composition in which 10 to 80% by weight of the carboxylic acid group of the polyethylene-based copolymer containing a carboxylic acid group is neutralized with metal ions.

In one embodiment, the metal may relate to a carbon-neutral eco-friendly resin composition of at least one selected from the group consisting of alkali metals, alkaline earth metals, and transition metals.

In one embodiment, the polyethylene-based copolymer containing a carboxylic acid group may relate to a carbon-neutral environmentally friendly resin composition that is a polyethylene-based copolymer containing methacrylic acid or acrylic acid.

In one embodiment, the carboxylic acid group-containing polyethylene-based copolymer may relate to a carbon-neutral eco-friendly resin composition having a carboxylic acid content of 3 to 50% by weight.

In one embodiment, the content of the polyethylene-based ionomer may be about 3 to 20% by weight of a carbon-neutral eco-friendly resin composition.

In one embodiment, the nucleating agent may be an organic nucleating agent or an organometallic nucleating agent, which is a carbon-neutral, environmentally friendly resin composition.

In one embodiment, the organic nucleating agent may relate to a carbon-neutral, environmentally-friendly resin composition that is at least one selected from the group consisting of a sorbitol-based nucleating agent, a nonitol-based nucleating agent, and a benzotrisamide-based nucleating agent.

In one embodiment, the organometallic nucleating agent may relate to a carbon-neutral, environmentally friendly resin composition that is at least one selected from the group consisting of aluminum para-tertiary butyl benzoic acid, sodium benzoic acid, and calcium benzoic acid.

In one embodiment, the nucleating agent content may be about 0.01 to 2.0% by weight of a carbon-neutral eco-friendly resin composition.

In one embodiment, the cyclic olefin copolymer may relate to an ethylene-norbornene copolymer, a carbon-neutral, environmentally friendly resin composition.

In one embodiment, the content of the cyclic olefin copolymer may be about 1 to 10% by weight of a carbon-neutral eco-friendly resin composition.

In one embodiment, it may relate to an article obtained from the carbon-neutral eco-friendly resin composition.

In one embodiment, the article may relate to a film, sheet, or foam sheet obtained by extrusion of the carbon-neutral, eco-friendly resin composition.

In one embodiment, the film may relate to a packaging film or an agricultural mulching film.

In one embodiment, the product is a shopping bag obtained from the film, a delivery (courier) bag, an air cap safety bag, an ice pack bag, a dry ice packaging bag, a zipper bag, a rollback bag, a sanitary bag, a wrap, a clean bag, or a tablecloth. it may be about

In one embodiment, the foam sheet may relate to a sheet formed by extrusion foaming by containing a foaming agent in the carbon-neutral eco-friendly resin composition.

In one embodiment, the article may relate to an article obtained by a method selected from pressure molding, pressure vacuum molding, or vacuum molding of the sheet or foam sheet.

In one embodiment, the article may relate to an article that is a container, cup or plate.

In one embodiment, the article may relate to an article that is an injection product obtained by injection molding of the carbon-neutral eco-friendly resin composition.

In one embodiment, the injection product may be a spoon, fork, knife, toothbrush handle, razor, chopsticks, or toothpick.

An object of the present invention is to have excellent toughness and excellent recyclability at the time of disposal despite having an excessive amount of inorganic filler, and even if it is not recycled and incinerated, the amount of carbon dioxide generated is reduced as much as the amount of the filled inorganic material, so that it can respond to carbon neutrality. It is intended to obtain a polyolefin resin composition and an article obtained therefrom.

An important point of focus of the present invention is a shopping bag, a delivery (courier) bag, an air cap safety bag, an ice pack bag, a dry ice packaging bag, a zipper bag, a rollback bag, a sanitary bag, a wrap, a clean bag, a tablecloth, a container, a cup, a plate, and a cutlery. , Forks, knives, toothbrush heads, razors, chopsticks, and toothpicks, etc., are intended to drastically reduce the amount of carbon dioxide generated proportionally by dramatically reducing the content of combustible synthetic resins such as polyolefin resins in items such as disposable polyolefin resin products. In addition, as the content of polyolefin resin is reduced, it is intended to improve economic feasibility by introducing inorganic materials that are very inexpensive compared to polyolefin resin.

However, when the content of the inorganic filler is 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, and 70% to 85% by weight of the inorganic filler, the desired toughness cannot be secured. ran into difficulties.

In order to solve this problem, focusing on the fact that inorganic materials usually have hydrophilic surface properties, maleic anhydride group-containing polyolefins such as ethylene-vinyl acetate copolymers and maleic anhydride grafted polyolefin copolymers, and glycidyl methacrylate grafted polyethylenes, have been developed. As a result of introducing a polyolefin resin containing a hydrophilic group, such as polyolefin containing an epoxy group, the dispersibility of inorganic substances was improved and the toughness was slightly improved, but it failed to secure the desired level of toughness.

In addition, it is a polyethylene-based ionomer that is expected to improve toughness through the expression of a similar network structure in molded products such as films, sheets, and injection molding products, as well as excellent dispersibility to inorganic substances by strong secondary bonding forces such as hydrogen bonds and ion-dipole bonds. As a result of introducing a new hydrophilic group-containing polyolefin resin, more improved toughness was obtained compared to the case of the hydrophilic group-containing polyolefin resin, but unfortunately, the desired level of toughness was not reached.

As a result of repeated studies, the present inventors have found that 30 wt% to 30 wt% or more, 40 wt% or more, 50 wt% or more, 60 wt% or more, and 70 wt% to 85 wt% of an inorganic filler, polyolefin resin, polyethylene As a result of introducing a novel polyolefin resin composition containing a based ionomer and a nucleating agent at the same time, the desired excellent toughness and heat-sealability are secured, and it has excellent recyclability when discarded. As the amount of carbon dioxide decreases, it is found that the amount of carbon dioxide generated is drastically reduced, making it possible to respond to carbon neutrality, and the present invention was completed.

In addition, the present inventors found that 30% by weight or more, 40% by weight or more, 50% by weight or more, 60% by weight or more, and 70% to 85% by weight of inorganic layering agent particles and the polyolefin resin, polyethylene-based ionomer and nucleating agent as well as cyclic As a result of introducing a new polyolefin resin composition additionally containing an olefin copolymer, more excellent toughness and heat-sealability are secured, and it has excellent recyclability when discarded. If not recycled, the amount of flammable polyolefin resin contained when incinerated is reduced As a result, it was found that the amount of carbon dioxide generated was remarkably low, making it possible to respond to carbon neutrality, and the present invention was completed.

In one embodiment, the polyolefin resin is one or more selected from low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene homopolymer, polypropylene random copolymer, polypropylene block copolymer, and polybutene.

In one embodiment, the inorganic material is calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, barium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, ass It may be at least one selected from besto powder, zeolite, silicate clay, and mixtures thereof. Inorganic materials may be spherical, plate-shaped, needle-shaped, etc., but spherical ones with good dispersibility in polypropylene resin are preferable, and untreated inorganic materials are also good, but those surface-treated with compounds such as stearic acid are preferable because of good dispersibility. If the amount of inorganic substances added is less than 30% by weight, the carbon neutral effect due to the reduction of carbon dioxide generation during incineration due to the decrease in the content of synthetic resin is small, and if it exceeds 85% by weight, the carbon neutral effect is excellent, but it is difficult to form films and sheets and the toughness deteriorates. There are concerns. The average particle diameter of the inorganic material is not limited, but is preferably in the range of 0.01 to 20 μm, more preferably in the range of 0.1 to 5 μm.

In one embodiment, the polyethylene-based ionomer is a metal ion-neutralized carboxylic acid group-containing polyethylene-based copolymer, more specifically, 10 to 80% by weight of the carboxylic acid content of the carboxylic acid group-containing polyethylene-based copolymer is metal Neutralized with ions, if the degree of neutralization is less than 10% by weight, dispersibility to inorganic particles may decrease, and if the degree of neutralization exceeds 80% by weight, compatibility with polyolefin resin may decrease. The carboxylic acid group-containing polyethylene-based copolymer is a polyethylene-based copolymer having a carboxylic acid content of 3 to 50% by weight, and when the carboxylic acid content is less than 3% by weight, there is a concern that dispersibility to inorganic particles may be reduced, and 50% by weight If it exceeds, there is a risk that the rigidity of the resin itself is weakened, resulting in a decrease in the toughness of the polyolefin resin composition. The carboxylic acid group-containing polyethylene-based copolymer is specifically a methacrylic acid or acrylic acid-containing polyethylene-based copolymer, such as methacrylic acid-ethylene copolymer, acrylic acid-ethylene copolymer, methacrylic acid-methyl methacrylate-ethylene copolymer , Acrylic acid-methyl acrylate-ethylene copolymer, and the like, and more specific examples include Nucrel 0403 from DuPont, USA, an ethylene methacrylate copolymer, and Escor 6000 from ExxonMobil, USA, an acrylic acid-ethylene copolymer, and acrylic acid-methyl acrylate-ethylene. and Escor AT310 from ExxonMobil, USA, which is a copolymer. The metal of the metal ion is one or two or more selected from the group consisting of alkali metals such as lithium, sodium, potassium, and cesium, alkaline earth metals such as magnesium, calcium, and barium, and transition metals such as iron, copper, and zinc, among which lithium, sodium, and zinc this is more preferable As a more specific example of the polyethylene-based ionomer, DuPont's Surlyn, a polyethylene-based ionomer having a copolymer structure of methacrylic acid and ethylene neutralized with metal ions, and a copolymer structure of acrylic acid and ethylene neutralized with metal ions and ExxonMobil's Iotek, which is a polyethylene-based ionomer, but is not limited thereto. In the polyolefin resin composition of the present invention, the content of the polyethylene-based ionomer is 3 to 20% by weight, preferably 5 to 10% by weight. It is more preferred because it has excellent dispersibility and toughness in the above composition ratio, but is not limited thereto.

The nucleating agent may be an organic nucleating agent or an organometallic nucleating agent, and the organic nucleating agent is preferably a sorbitol-based nucleating agent or a nonitol-based nucleating agent. The sorbitol-based nucleating agent is preferably at least one selected from benzylidenesorbitol, methylbenzylidenesorbitol, ethylbenzylidenesorbitol, and 3,4-dimethylbenzylidenesorbitol, and the nonitol-based nucleating agent is 1,2,3-trideoxy -4,6:5,7-bis-0-[(4-propylphenyl)methylene]-nonitol is preferred. As the organometallic nucleating agent, a conventionally known organometallic nucleating agent for polypropylene may be used, and preferably at least one selected from aluminum para-tertiary butylbenzoic acid, sodium benzoic acid, and calcium benzoic acid. The nucleating agent may include any nucleating agent known in the art for modifying olefinic polymers. For example, non-limiting examples of nucleating agents may include carboxylates including sodium benzoate, talc, phosphates, metallic silicate hydrates, organic derivatives of dibenzylidene sorbitol, sorbitol acetals, organic phosphates, and combinations thereof. . Specific examples of the nucleating agent include Amfine Na-11 and Na-21 commercially available from Amfine Chemical, and Hyperform HPN-68L and Millad 3988 commercially available from Milliken Chemical. In the polyolefin resin composition of the present invention, the content of the nucleating agent is 0.01 to 2.0% by weight, preferably 0.05 to 0.5% by weight. When the content of the nucleating agent is less than 0.01% by weight, it is difficult to secure the desired toughness, and when the content of the nucleating agent exceeds 2.0% by weight, economic efficiency may be deteriorated because the nucleating agent is very expensive.

In one embodiment, the cyclic olefin copolymer is a copolymer containing a cyclic olefin as a main component. As a specific example, COC of TOPAS Advanced Polymers, an ethylene-norbornene copolymer, grade 9506F-04, 8007F-04, 8007F-400 , 6014F-04, etc., but is not limited thereto. In the polyolefin resin composition of the present invention, the content of the cyclic olefin copolymer is 1 to 10% by weight, preferably 3 to 7% by weight. When the content of the cyclic olefin copolymer is less than 1% by weight, it is difficult to secure the desired toughness, and when the content exceeds 10% by weight, the cyclic olefin copolymer is somewhat expensive, so there is a concern that economic efficiency may decrease.

The present invention may be an article obtained from the carbon-neutral environmentally friendly composition. Specifically, the article may be a film, sheet, or foam sheet such as a packaging film or an agricultural mulching film obtained by extrusion of a carbon-neutral eco-friendly composition.

In addition, the goods according to the present invention are shopping bags obtained from the film, delivery (courier) bags, air cap safety bags, ice pack bags, dry ice packaging bags, zipper bags, rollbacks, sanitary bags, wraps, clean bags, and tablecloths. can be

In addition, the sheet may be obtained by T-die extrusion molding of a conventional carbon-neutral eco-friendly composition, and the foam sheet may be obtained by extrusion molding by containing a foaming agent in the carbon-neutral eco-friendly composition. The foaming agent may be hydrocarbon-based volatile foaming agents such as propane, n-butane, iso-butane, and n-pentane, and inorganic gas foaming agents such as carbon dioxide, nitrogen, and air. In addition, the sheet or foam sheet may be an article such as a container, cup, plate, or the like obtained by a method selected from pressure molding, pressure vacuum molding, and vacuum molding.

In addition, the article according to the present invention may be an injection product such as a spoon, fork, knife, toothbrush handle, razor, chopsticks, toothpick obtained by injection molding of the carbon-neutral eco-friendly composition.

The carbon-neutral eco-friendly composition according to the present invention and the article obtained therefrom not only have excellent toughness, heat-sealability, and excellent recyclability upon disposal, but also eco-friendly that can respond to carbon neutrality because the amount of carbon dioxide generated is reduced as much as the inorganic material filled even if it is not recycled and is incinerated. It is expected to be useful as an inorganic material-filled polyolefin resin composition and articles obtained therefrom.

Hereinafter, an example will be described for detailed description of the present invention, but the present invention is not limited to the following examples.

The toughness, heat sealability, and carbon neutral eco-friendliness of the samples prepared according to the following Examples and Comparative Examples were evaluated as follows.

1. Toughness

The toughness of the sample was measured according to KS M3503: 2010, and the stiffness was measured by tensile strength (MPa) and the toughness was measured by elongation (%) and evaluated as 4 grades.

- Rigidity evaluation criteria division ◎(excellent) ○ (Good) △ (Normal) X (bad) tensile strength
(MPa) over 25 20+
less than 25 over 10
less than 20 less than 10

- Character evaluation criteria division ◎(excellent) ○ (good) △ (Normal) X (bad) elongation
(%) over 500 over 400
less than 500 over 200
less than 400 less than 200

2. Heat sealing synthesis

According to KS M 7137: 2016, the heat-sealing strength (N/15mm) was measured as a product sample and evaluated as 4 grades.

- Criteria for evaluation of heat sealability division ◎(excellent) ○ (good) △ (Normal) X (bad) heat sealing strength
(N/15mm) 12 or more over 10
less than 12 5 or more
less than 10 less than 5

3. Carbon Neutral Environmentally Friendly

In accordance with ISO-3451-1: 2008, the amount of inorganic matter (wt%) contained in the sample was measured from the amount of ash when the sample was placed in a crucible and completely incinerated at a temperature of 600 ° C. rated by grade.

division ◎(excellent) ○ (Good) △ (Normal) X (bad) Inorganic content (% by weight) over 50 over 30
less than 50 over 10
less than 30 less than 10

[Example 1]

Calcium carbonate (CaCO ₃ (A)) with an average particle diameter of 1.5 μm coated with stearic acid as an inorganic material, and a high density of polyolefin resin with a density of 0.956 (g/cm ³ ) and a melt index of 0.044 (g/10 min, 190℃, 2.16Kg) Polyethylene (Hanwha Total Petrochemical, grade F120A, PE(A)), polyolefin resin containing hydrophilic group, melt viscosity 0.9 (g/10 min, 190℃, 2.16Kg), neutralized with sodium ion (neutralization degree 60%) methacrylic acid ( 15% by weight) and ethylene (85% by weight) polyethylene ionomer (DuPont, Surlyn 8920, PEI (A)), bicyclo[2.2.1]heptane-2,3-dicarboxylic acid as a nucleating agent Disodium salt (Mliken Chemical, Hyperform HPN-68L, NA(A)) was prepared. A mixture obtained by mixing these with the composition shown in Table 5 was put into a Banbury mixer and compounded to obtain a polyolefin resin composition. A film having a thickness of 30 μm was prepared from the polyolefin resin composition in a blown film molding machine, and toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness thereof were evaluated, and the results are shown in Table 5.

[Example 2]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Example 3]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Example 4]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Example 5]

Cyclic olefin copolymer (TOPAS Advanced Polymers, grade 8007F-04), which is an ethylene-norbornene copolymer with a density of 1.020 (g/cm ³ ) and a melt index of 1.9 (g/10 min, 190℃, 2.16Kg). , COC (A)) was prepared, and a 30 μm thick film was prepared in the same manner as in Example 1, except that the mixture was mixed with the composition shown in Table 5, and the toughness (stiffness, toughness) and heat sealability thereof were prepared. And carbon neutral eco-friendliness was evaluated, and the results are shown in Table 5.

[Example 6]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Example 7]

As a cyclic olefin copolymer, a cyclic ^olefin copolymer (TOPAS Advanced Polymers, grade 9506F-04, COC (B)), a polyolefin resin containing a hydrophilic group, with a melt index of 5.0 (g/10 min, 190℃, 2.16Kg), neutralized with zinc ions (degree of neutralization 37%), methacrylic acid (35% by weight) and ethylene (65 A polyethylene-based ionomer (DuPont, Surlyn 9950, PEI (B)), which is a copolymer with weight %), was prepared. It was carried out in the same manner as in Example 1 except that the mixture was mixed in the composition shown in Table 5 to obtain a thickness of 30 μm. A film of was prepared, and its toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated, and the results are shown in Table 5.

[Example 8]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Comparative Example 1]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Comparative Example 2]

Polyolefin resin containing hydrophilic group, density 0.938 (g/cm ³ ), melt viscosity 0.4 (g/10 min, 190℃, 2.16Kg), ethylene-vinyl acetate copolymer (vinyl acetate content 14% by weight) (Hanwha Solution, grade 1214 , EVA (A)) was prepared, and a 30 μm thick film was prepared in the same manner as in Example 1, except for using the compound mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability thereof And carbon neutral eco-friendliness was evaluated, and the results are shown in Table 5.

[Comparative Example 3]

Hydrophilic group-containing polyolefin resin, density 0.92 (g/cm ³ ), melt viscosity 1.1 (g/10 min, 190°C, 2.16Kg), maleic anhydride grafted polyethylene (Mitsui Chemical, trade name ADMER, grade GT6E, MAH-g-PE (A)) was prepared, and a 30 μm thick film was prepared in the same manner as in Example 1, except that the mixture was mixed with the composition shown in Table 5, and its toughness (stiffness, toughness), heat sealability and carbon Neutral eco-friendliness was evaluated and the results are shown in Table 5.

[Comparative Example 4]

Polyolefin resin containing hydrophilic group, melt viscosity 25 (g/10 min, 190℃, 2.16Kg), glycidyl methacrylate grafted polyethylene (Ferro Plast, trade name GRAFTABOND, grade HD-GMA02530C, GMA-g-PE(A) ) was prepared, and a film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the compound mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealing synthesis, and carbon neutral eco-friendliness were prepared. was evaluated and the results are shown in Table 5.

[Comparative Example 5]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Comparative Example 6]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Comparative Example 7]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Comparative Example 8]

A film having a thickness of 30 μm was prepared in the same manner as in Example 1 except for using the mixture mixed with the composition shown in Table 5, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness were evaluated. is shown in Table 5.

[Examples 9 to 12, Comparative Examples 9 to 14]

The mixtures of Examples and Comparative Examples in Table 6 were put into a Banbury mixer and compounded to obtain a polyolefin resin composition. A sheet having a thickness of 0.9 mm was prepared from the polyolefin resin composition in a T-die extrusion sheet molding machine, and the toughness (stiffness, toughness), heat sealability, and carbon neutral eco-friendliness thereof were evaluated, and the results are shown in Table 6.

CaCO ₃ (A): calcium carbonate with an average particle diameter of 1.5 μm coated with stearic acid

PP(A): Polypropylene (Lotte Chemical, grade TI-640) with a density of 0.9 (g/cm ³ ) and a melt index of 5.0 (g/10 min, 230℃, 2.16Kg)

PEI (A): Copolymerization of methacrylic acid (15% by weight) and ethylene (85% by weight) neutralized with sodium ions (60% by weight), melt viscosity 0.9 (g / 10 minutes, 190 ° C, 2.16Kg) Chain polyethylene-based ionomer (DuPont, Surlyn 8920)

PEI (B): Polyethylene-based ionomer (DuPont, Surlyn 9950), which is a copolymer of methacrylic acid (35% by weight) and ethylene (65% by weight) neutralized with zinc ions (neutralization degree 37%)

EVA (A): density 0.938 (g / cm ³ ), melt viscosity 0.4 (g / 10 minutes, 190 ℃, 2.16Kg), ethylene-vinyl acetate copolymer (vinyl acetate content 14% by weight) (Hanwha Solution, grade 1214 )

MAH-g-PP(A): maleic anhydride grafted polypropylene (Mitsui Chemical, trade name: ADMER, grade QB520E) with a density of 0.90 (g/cm ³ ) and a melt viscosity of 1.8 (g/10 min, 230°C, 2.16Kg)

NA(A): Bicyclo[2.2.1]heptane-2,3-dicarboxylic acid disodium salt (Mliken Chemical, Hyperform HPN-68L)

NA(B): 1,3:2,4-bis(3,4-dimethyrobenzylideno) sorbitol ((Mliken Chemical, Millad 3988)

COC(A): cyclic olefin copolymer (TOPAS Advanced Polymers, grade 8007F-04), an ethylene-norbornene copolymer with a density of 1.020 (g/cm ³ ) and a melt index of 1.9 (g/10 min, 190℃, 2.16Kg) )

COC(B): Density 1.020 (g/cm ³ ), melt index 0.9 (g/10 min, 190℃, 2.16Kg) ethylene-norbornene cyclic olefin copolymer (TOPAS Advanced Polymers, grade 9506F-04)

First, in the case of a film formed from a polyolefin resin composition containing polyethylene, a polyethylene-based ionomer, and a nucleating agent in an excess (30% to 85% by weight) of an inorganic material according to the present invention (Examples 1 to 4), toughness, heat sealability and carbon It can be seen that the neutral eco-friendliness is excellent, and in the case of a film formed from a polyolefin resin composition additionally containing polyethylene, a polyethylene-based ionomer, and a cyclic olefin copolymer in addition to a nucleus in an excess of inorganic materials (Examples 5 to 8) toughness , it can be seen that heat sealability and carbon neutral eco-friendliness are more excellent.

On the other hand, in the case of a film formed from a polyolefin resin composition composed of only polyethylene and an excess of inorganic materials according to the prior art (Comparative Example 1), the toughness is very poor, and polyethylene and ethylene-vinyl acetate copolymer, maleic anhydride grafted polyethylene, In the case of a film molded from a polyolefin resin composition containing a polyolefin containing a hydrophilic group such as glycidyl methacrylate grafted polyethylene or polyethylene ionomer (Comparative Examples 2 to 6), the toughness is slightly improved, but the improvement in stiffness is very insignificant. In the case of a film molded from a polyolefin resin composition containing polyethylene and a nucleating agent in an excess of inorganic materials (Comparative Example 7) and a film molded from a polyolefin resin composition containing polyethylene and a cyclic olefin copolymer in an excess of inorganic materials In this case (Comparative Example 8), the stiffness is slightly improved, but the improvement in toughness is very insignificant, so it cannot be used as a product.

In addition, in the case of a sheet molded from a polyolefin resin composition containing polypropylene, a polyethylene-based ionomer, and a nucleating agent in excess of inorganic materials according to the present invention, or further containing a cyclic olefin copolymer therein (Examples 9 to 12), toughness, It can be seen that heat sealing synthesis and carbon neutral eco-friendliness are very excellent.

On the other hand, in the case of a sheet molded from a polyolefin resin composition composed of an excess of inorganic materials and polypropylene according to the prior art (Comparative Example 9), the toughness is very poor, and polypropylene, ethylene-vinylacetate copolymer, and maleic anhydride graft In the case of sheets molded from polyolefin resin compositions containing hydrophilic group-containing polyolefins such as polyethylene and polyethylene ionomer (Comparative Examples 10 to 12), toughness is somewhat improved, but the improvement in stiffness is very insignificant, so it cannot be used as a product, and excessive In the case of a sheet molded from a polyolefin resin composition containing polypropylene and a nucleating agent in inorganic materials (Comparative Example 13) and in the case of a sheet molded from a polyolefin resin composition containing polypropylene and a cyclic olefin copolymer in an excess of inorganic materials (Comparative Example 14) The stiffness is slightly improved, but the improvement in toughness is very insignificant, so it cannot be used as a product.

The eco-friendly inorganic material-filled polyolefin resin composition and the article obtained therefrom according to the present invention not only have excellent toughness, heat-sealability, and excellent recyclability upon disposal, but also respond to carbon neutrality because the amount of carbon dioxide generated is reduced as much as the inorganic material filled even if it is not recycled and incinerated. know that it is possible.

As described above, the present invention has been described by specific details and limited embodiments and drawings, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, and the present invention Those skilled in the art can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and it will be said that not only the claims to be described later, but also all modifications equivalent or equivalent to these claims belong to the scope of the present invention. .

Claims (25)

30% to 85% by weight of inorganic materials, polyolefin resin, polyethylene ionomer and nucleating agent, tensile strength of 20 MPa or more according to KS M3503: 2010, elongation of 400% or more, and according to KS M 7137: 2016 A carbon-neutral eco-friendly polyolefin resin composition having a heat-sealing strength of 10 N/15 mm or more. According to claim 1,
The carbon-neutral eco-friendly polyolefin resin composition further comprises a cyclic olefin copolymer, a carbon-neutral eco-friendly polyolefin resin composition According to claim 1,
The polyolefin resin is at least one selected from the group consisting of low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene homopolymer, polypropylene random copolymer, polypropylene block copolymer, and polybutene, a carbon-neutral eco-friendly polyolefin resin. composition According to claim 1,
The inorganic material is calcium carbonate, talc, clay, kaolin, silica, diatomaceous earth, magnesium carbonate, calcium chloride, calcium sulfate, barium sulfate, aluminum hydroxide, zinc oxide, magnesium hydroxide, titanium oxide, alumina, mica, asbestos powder, zeolite, silicic acid At least one selected from white clay and mixtures thereof, carbon neutral eco-friendly polyolefin resin composition According to claim 1,
The polyethylene-based ionomer is a carbon-neutral eco-friendly polyolefin resin composition, which is a polyethylene-based copolymer containing a carboxylic acid group neutralized with metal ions According to claim 1,
The polyethylene-based ionomer is a carbon-neutral eco-friendly polyolefin resin composition in which 10 to 80% by weight of the carboxylic acid content of the polyethylene-based copolymer containing a carboxylic acid group is neutralized with metal ions. According to claim 5,
The metal is at least one selected from the group consisting of alkali metals, alkaline earth metals and transition metals, carbon neutral eco-friendly polyolefin resin composition According to claim 5,
The carboxylic acid group-containing polyethylene-based copolymer is a polyethylene-based copolymer containing methacrylic acid or acrylic acid, a carbon-neutral eco-friendly polyolefin resin composition According to claim 5,
The carboxylic acid group-containing polyethylene-based copolymer is a carbon neutral eco-friendly polyolefin resin composition having a carboxylic acid content of 3 to 50% by weight According to claim 1 or 2,
A carbon-neutral eco-friendly polyolefin resin composition having the polyethylene-based ionomer content of 3 to 20% by weight According to claim 1 or 2,
The nucleating agent is an organic nucleating agent or an organometallic nucleating agent, a carbon neutral eco-friendly polyolefin resin composition According to claim 11,
The organic nucleating agent is at least one selected from the group consisting of a sorbitol-based nucleating agent, a nonitol-based nucleating agent, and a benzotrisamide-based nucleating agent, a carbon-neutral eco-friendly polyolefin resin composition According to claim 11,
The organometallic nucleating agent is at least one selected from the group consisting of aluminum para-tertiary butyl benzoic acid, sodium benzoic acid and calcium benzoic acid, carbon neutral eco-friendly polyolefin resin composition According to claim 1 or 2,
Carbon-neutral eco-friendly polyolefin resin composition having 0.01 to 2.0% by weight of the nucleating agent According to claim 2,
The cyclic olefin copolymer is an ethylene-norbornene copolymer, a carbon neutral eco-friendly polyolefin resin composition According to claim 2,
A carbon-neutral eco-friendly polyolefin resin composition in which the content of the cyclic olefin copolymer is 1 to 10% by weight An article obtained from the carbon-neutral eco-friendly polyolefin resin composition of claim 1 or 2. According to claim 17.
An article in which the article is a film, sheet or foam sheet obtained by extrusion molding of a carbon-neutral eco-friendly polyolefin resin composition. According to claim 18.
An article in which the film is a packaging film or an agricultural mulching film. A shopping bag, a delivery (courier) bag, an air cap safety bag, an ice pack bag, a dry ice packaging bag, a zipper bag, a rollback bag, a sanitary bag, a wrap, a clean bag or a tablecloth, and an article obtained from the film of claim 18. According to claim 18.
The article is a foam sheet formed by extrusion foaming by containing a foaming agent in the carbon-neutral eco-friendly polyolefin resin composition. An article obtained from the sheet or foam sheet according to claim 18 by a method selected from pressure molding, pressure vacuum molding and vacuum molding. The method of claim 22,
An article, wherein the article is a container, cup or plate. According to claim 17.
The article is an injection product obtained by injection molding of the carbon-neutral eco-friendly polyolefin resin composition. According to claim 24,
An article in which the extruded article is a spoon, fork, knife, toothbrush holder, razor, chopsticks or toothpick.