KR102009819B1 - Method of biodegradable resin composition, biodegradable resin composition and biodegradable sheet - Google Patents
Method of biodegradable resin composition, biodegradable resin composition and biodegradable sheet Download PDFInfo
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- KR102009819B1 KR102009819B1 KR1020150077735A KR20150077735A KR102009819B1 KR 102009819 B1 KR102009819 B1 KR 102009819B1 KR 1020150077735 A KR1020150077735 A KR 1020150077735A KR 20150077735 A KR20150077735 A KR 20150077735A KR 102009819 B1 KR102009819 B1 KR 102009819B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/16—Biodegradable polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Abstract
Mixing a cellulose-based polymer and a plasticizer to form a plasticized cellulose-based polymer; And preparing a biodegradable resin composition by mixing the polylactic acid resin and the plasticized cellulose-based polymer.
Description
A method for producing a biodegradable resin composition, a biodegradable resin composition, and a biodegradable sheet.
Polymer synthetic resins produced from petroleum have excellent mechanical properties, chemical resistance, durability, and low cost, and are used in various industrial fields such as packaging materials, textiles, and automobiles.
However, such petroleum-based polymer synthetic resins are difficult to proceed in nature, and when incinerated, a large amount of harmful substances are released, causing environmental problems worldwide.
Thus, research on biodegradable resins that are easy to decompose in nature is being progressed, and recently, polylactic acid having excellent mechanical properties among environmentally friendly biodegradable resins is used for various purposes, but there are problems in that heat resistance and impact strength are weak.
On the other hand, cellulose is a natural polymer material, which has excellent heat resistance and biodegradability, and is used for various purposes such as fiber, paper, food processing, building materials, medicine, etc., but due to the hydroxyl group contained in the molecule, it forms hydrogen bonds between molecules. There is a problem that the solubility, the melting point and the like are low, and the melt processing is difficult.
In one embodiment of the present invention, there is provided a method for producing a biodegradable resin composition that simultaneously realizes excellent biodegradability, excellent mechanical properties, excellent heat resistance, and excellent processability.
In another embodiment of the present invention, a biodegradable resin composition prepared by the above method is provided.
In another embodiment of the present invention, a biodegradable sheet formed by molding the biodegradable resin composition is provided.
However, the technical problem to be achieved by the present invention is not limited to the above-mentioned problem, another task that is not mentioned will be clearly understood by those skilled in the art from the following description.
In one embodiment of the present invention, by introducing a method of plasticizing the cellulose-based polymer in advance, it is possible to impart flexibility to the overall uniformity, as described above, the cellulose-based polymer that is previously uniformly given flexibility is melt-processed with the polylactic acid resin In the process, a partially unmelted state does not occur, so that agglomeration can be effectively prevented.
As a result, the biodegradable compositions in which the polylactic acid resin and the plasticized cellulose polymer are mixed are suitably matched with their physical properties to achieve excellent biodegradability, excellent mechanical properties, and excellent heat resistance while increasing solubility and decreasing melting point. There is an advantage that can implement excellent workability. In addition, since the workability is improved, a process having a higher temperature than that of cellulose is not required, and thus the damage of the polylactic acid resin can be further prevented.
In another embodiment of the invention, polylactic acid resin; And a plasticized cellulose-based polymer, and provides a biodegradable resin composition having a glass transition temperature of about 60 ° C to about 150 ° C and a melt index of about 2g / 10 minutes to about 8g / 10 minutes. .
The plasticized cellulose-based polymer, that is, the pre-plasticized cellulose-based polymer is uniformly dispersed throughout when mixed with the polylactic acid resin, so that a partially unmelted state does not occur during processing, so that agglomeration can be effectively prevented. have.
As a result, the biodegradable composition has a good balance of physical properties of the polylactic acid resin and the plasticized cellulose polymer, so that the solubility is increased and the melting point is reduced while achieving excellent biodegradability, excellent mechanical properties, and excellent heat resistance. There is an advantage to implementing this. In addition, since the workability is improved, a process having a higher temperature than that of cellulose is not required, and thus the damage of the polylactic acid resin can be further prevented.
The biodegradable resin composition includes a pre-plasticized cellulose-based polymer so that the glass transition temperature is about 60 ° C to about 150 ° C and the melt index is about 2g / 10min to 8g / 10min. It can be formed, thereby having a sufficient level of heat resistance and does not require high temperature processing conditions, it is possible to prevent the change in the physical properties of the polylactic acid resin, and also to improve the workability can implement excellent stability and excellent economical efficiency.
The method for preparing the biodegradable resin composition, the biodegradable resin composition and the biodegradable sheet may simultaneously realize excellent biodegradability, excellent mechanical properties, excellent heat resistance, and excellent processability.
1 is a schematic process flow diagram of a method for producing a biodegradable resin composition according to an embodiment of the present invention.
Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present invention. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
In order to clearly describe the present invention, parts irrelevant to the description are omitted, and like reference numerals designate like elements throughout the specification.
In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. In the drawings, the thicknesses of layers and regions are exaggerated for clarity.
In the following, any configuration is formed on the top (or bottom) of the substrate or on the top (or bottom) of the substrate, not only means that the arbitrary configuration is formed in contact with the top (or bottom) of the substrate, but also the substrate It is not limited to not including other configurations between and any configuration formed on (or under) the substrate.
In one embodiment of the present invention, the step of mixing the cellulose-based polymer and the plasticizer to form a plasticized cellulose-based polymer; And preparing a biodegradable resin composition by mixing the polylactic acid resin and the plasticized cellulose-based polymer.
Generally, polylactic acid having excellent mechanical properties among various eco-friendly biodegradable resins is used for various purposes, but heat resistance and impact strength are weak, and cellulose is a natural polymer material having excellent heat resistance and biodegradability. It is used in various applications such as building materials, medicine, etc., but due to the hydroxyl group contained in the polymer can form hydrogen bonds between the polymer, low solubility and high melting point, there is a problem that melt processing is difficult.
In order to solve this problem, polylactic acid resin and cellulose may be mixed and used, but conditions for high temperature are required to melt-process cellulose, thereby degrading polylactic acid resin having poor heat resistance and degrading performance.
In addition, in order to lower the processing temperature, when polylactic acid resin, cellulose, and a plasticizer are added at a time and mixed composition is used, it is difficult to uniformly give flexibility to the cellulose, so that the cellulose is partially unmelted during processing. As a result, agglomeration occurs, whereby mechanical properties and heat resistance are reduced, and it is difficult to realize uniform physical properties.
Thus, in one embodiment of the present invention, by introducing a method of plasticizing the cellulose-based polymer in advance, the overall flexibility can be given uniformly, as described above, the cellulose-based polymer, which is previously uniformly given flexibility, is melted with the polylactic acid resin. In the process of processing, a partially unmelted state does not occur, so that agglomeration can be effectively prevented.
As a result, the biodegradable compositions in which the polylactic acid resin and the plasticized cellulose polymer are mixed are suitably matched with their physical properties to achieve excellent biodegradability, excellent mechanical properties, and excellent heat resistance while increasing solubility and decreasing melting point. There is an advantage that can implement excellent workability. In addition, since the workability is improved, a process having a higher temperature than that of cellulose is not required, and thus the damage of the polylactic acid resin can be further prevented.
Figure 1 schematically shows a process flow diagram of the manufacturing method. The manufacturing method comprises the steps of forming a plasticized cellulose-based polymer by mixing a cellulose-based polymer and a plasticizer (S1); And mixing the polylactic acid resin and the plasticized cellulose-based polymer to prepare a biodegradable resin composition (S2).
Overall, the cellulose-based polymer and the plasticizer may be mixed to form a plasticized cellulose-based polymer. In the present specification, the plasticized cellulose-based polymer is thus present, wherein the plasticizer is present between the cellulose-based polymers. It means a cellulose-based polymer in a state in which a force acting between the polymers is reduced and overall flexibility is given.
The cellulose-based polymer and the plasticizer may be mixed at a temperature of, for example, about 140 ° C. to about 180 ° C., so that the plasticizer may be more uniformly dispersed between the cellulose-based polymers and not change their physical properties. have.
For example, the cellulose-based polymer and the plasticizer may be mixed by stirring to more uniformly disperse the plasticizer in the cellulose-based polymer, thereby realizing more uniform physical properties while preventing aggregation.
The agitation can be performed, for example, at a stirring speed of about 60 rpm to about 250 rpm. By performing at a stirring speed within the above range it is possible to sufficiently plasticize the cellulose-based polymer at a suitable time and cost.
In one embodiment, about 10 parts by weight to about 80 parts by weight of the plasticizer may be mixed with respect to about 100 parts by weight of the cellulose-based polymer. By mixing the content within the above range, it is possible to plasticize the cellulose-based polymer sufficiently to give the overall flexibility and to prevent the dissolution of the plasticizer, to realize a long-term uniform physical properties and excellent surface appearance. Specifically, when the plasticizer is mixed in excess of about 80 parts by weight, the plasticizer may be eluted from the cellulose-based polymer after product production, thereby deteriorating physical properties and surface appearance.
For example, the cellulose-based polymer may include a cellulose derivative, and specifically, cellulose nitrate (CN), cellulose acetate (CA), cellulose diacetate (CDA), It may include at least one selected from the group consisting of cellulose acetate propionate (CAP), methyl cellulose (MC), ethyl cellulose (AC), and combinations thereof.
For example, the cellulose derivative may be formed by modifying a hydroxy group in a cellulose molecule by performing an acetylation reaction or an etherification reaction, and thus converting a part or all of the hydroxy group in the cellulose molecule to another functional group to form a hydroxyl group. The content can be reduced.
As such, the cellulose-based polymer may include the cellulose-based derivative so that the hydrogen bonding force between the cellulose-based polymers is reduced, so that the solubility is relatively increased and the melting point is lowered.
Accordingly, since high temperature process conditions are not required, the cost is reduced and the stability is improved, so that excellent processability can be realized, and there is no fear that the physical properties of the polylactic acid resin will be changed. Can be.
The weight average molecular weight of the plasticized cellulose-based polymer resin may be about 100,000 g / mol to about 300,000 g / mol. By having a weight average molecular weight within the above range it can be implemented excellent mechanical properties and excellent workability. Specifically, the mechanical strength is lowered when less than about 100,000 g / mol, there is a problem that melt processing is difficult when more than about 300,000 g / mol.
The plasticizer may include, for example, at least one selected from the group consisting of acetate plasticizers, phthalate plasticizers, citrate plasticizers, glycerin ester plasticizers, phosphate plasticizers, benzoate plasticizers, and combinations thereof. It is not limited to this. Specifically, including the benzoate-based plasticizer, it is excellent compatibility with both the cellulose-based polymer and the polylactic acid resin to have a single glass transition temperature, so that the heat resistance further improves the hydroxyl group present in the cellulose-based polymer Through the electrostatic interaction of the eluting phenomenon of the plasticizer can be more effectively prevented to achieve a long-term uniform physical properties and excellent surface appearance.
In one embodiment, a biodegradable resin composition may be prepared by mixing a polylactic acid resin and the plasticized cellulose-based polymer.
The polylactic acid resin and the plasticized cellulose-based polymer are mixed at a temperature of, for example, about 140 ° C. to about 180 ° C., so that they are mixed more uniformly and do not change their physical properties. All can be implemented at an excellent level.
For example, the polylactic acid resin and the plasticized cellulose-based polymer are mixed by stirring, so that they are more uniformly mixed in the biodegradable resin composition, thereby achieving excellent mechanical properties and excellent heat resistance at a more uniform level. Can be.
The agitation can be performed, for example, at a stirring speed of about 60 rpm to about 250 rpm. By performing at a stirring speed within the above range it can be mixed sufficiently uniformly at an appropriate time and cost.
The polylactic acid resin may be formed by polycondensation of monomers including lactic acid, for example, but may be formed by polycondensation of L-lactic acid and D-lactic acid, but is not limited thereto.
The weight average molecular weight of the polylactic acid resin may be about 100,000g / mol to about 200,000g / mol. By having a weight average molecular weight within the above range can be implemented excellent workability, specifically, less than about 100,000g / mol lacks mechanical and thermal properties can not be used in the process of melting, foaming, etc. for the production of products In the case of more than about 200,000 g / mol, the melt viscosity and the processing temperature may be increased, and the processing conditions may be disadvantageous.
For example, the weight ratio of the polylactic acid resin to the plasticized cellulose polymer may be mixed, for example, from about 1: 9 to about 9: 1, specifically about 7: 3 to about 8: It can be mixed so as to be 2. By mixing at a weight ratio within the above range, the polylactic acid resin and the plasticized cellulose-based polymer may be suitably matched to each other, thereby achieving excellent biodegradability, mechanical properties, and heat resistance.
The plasticized cellulose-based polymer may be mixed, for example, from about 9% to about 81% by weight, and may also be mixed, for example, from about 18% to about 27% by weight. By mixing in an amount within the above range it is possible to achieve a good level of mechanical properties while achieving sufficient heat resistance.
Thus, the polylactic acid resin may be mixed, for example, in about 9% by weight to about 81% by weight, and may also be mixed in, for example, about 63% by weight to about 72% by weight. By mixing in an amount within the above range it can be realized to excellent levels of heat resistance while implementing sufficient mechanical properties.
In one embodiment, further comprising mixing at least one selected from the group consisting of a compatibilizer, a chain extender, a peroxide, and a combination thereof in the biodegradable resin composition, and thus may further include the object and The physical properties of the biodegradable resin composition can be appropriately adjusted according to the use.
Such compatibilizers include, for example, ethylene-vinyl acetate copolymers, polyethylene-grafted maleic anhydrides, polypropylene-grafted maleic anhydrides, and combinations thereof. It may include at least one selected from the group consisting of.
Specifically, the compatibilizer may comprise an ethylene vinyl acetate copolymer, the ethylene vinyl acetate copolymer contains a vinyl acetate group as a functional group common to both the polylactic acid resin and the cellulose-based polymer, further compatibility It is excellent, and thus the biodegradable composition can have a single glass transition temperature, it is possible to implement more excellent heat resistance. In addition, the vinyl acetate group may be included to improve tensile strength and elongation due to the nature of the functional group.
When the compatibilizer is mixed, it may be mixed in an amount of about 4 parts by weight to about 20 parts by weight based on about 100 parts by weight of the polylactic acid resin. By mixing in an amount within the above range it is possible to realize a sufficient compatibility and at the same time excellent processability. If the compatibilizer is mixed in excess of about 20 parts by weight, processing may be difficult due to the increase in molecular weight.
The chain extender may use a kind known in the art, and examples thereof include, but are not limited to, diisocyanate, epoxy copolymer, hydroxycarboxylic acid compound, and the like.
When the chain extender is mixed, about 0.5 parts by weight to about 5 parts by weight based on about 100 parts by weight of the polylactic acid resin may be mixed. By mixing in an amount within the above range it is possible to implement excellent processability while achieving excellent mechanical and thermal properties. Specifically, when the mixture is less than about 0.5 parts by weight, the molecular weight of each of the plasticized cellulose-based polymer and the polylactic acid resin does not increase sufficiently, so that the effect of improving mechanical and thermal properties is insignificant, and their compatibility is improved. In addition, the effect is also reduced, when mixing more than about 5 parts by weight there is a problem that melt processing is difficult because the molecular weight is too increased.
The peroxide is, for example, dicumyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, t-butyl peroxy isopropyl carbonate, t-butyl peroxy laurate, t-butyl peroxy acetate, t-dibutyl Peroxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, 1,3-bis (t-butylperoxyisopropyl) benzene, methylethylketone peroxide, 2,5-dimethyl-2,5- Di (benzoyloxy) hexane, 2,5-dimethyl-2,5-di (t-buperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5- (t-butylperoxy ) -3-hexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 1, It may include, but is not limited to, at least one selected from the group consisting of 3-bis (t-butylperoxyisopropyl) benzene and combinations thereof.
When the peroxide is mixed, it may be mixed in an amount of about 0.1 parts by weight to about 0.5 parts by weight based on about 100 parts by weight of the polylactic acid resin. By mixing at a low content within the above range it can be achieved excellent compatibility and excellent mechanical and thermal properties. Specifically, when less than about 0.1 part by weight, crosslinking is insufficiently formed, and the effect of increasing compatibility and physical properties is insignificant. When the amount is greater than about 0.5 part by weight, the decomposition reaction of the polymers is greatly caused by radicals generated during decomposition of the peroxide. Therefore, there is a problem of lowering mechanical and thermal properties.
In another embodiment of the invention, polylactic acid resin; And a plasticized cellulose-based polymer, and provides a biodegradable resin composition having a glass transition temperature of about 60 ° C to about 150 ° C and a melt index of about 2g / 10 minutes to about 8g / 10 minutes. . The biodegradable resin composition may be prepared by the above-described manufacturing method in one embodiment.
The plasticized cellulose-based polymer, that is, the pre-plasticized cellulose-based polymer is uniformly dispersed throughout when mixed with the polylactic acid resin, so that a partially unmelted state does not occur during processing, so that agglomeration can be effectively prevented. have.
As a result, the biodegradable composition has a good balance of physical properties of the polylactic acid resin and the plasticized cellulose polymer, so that the solubility is increased and the melting point is reduced while achieving excellent biodegradability, excellent mechanical properties, and excellent heat resistance. There is an advantage to implementing this. In addition, since the workability is improved, a process having a higher temperature than that of cellulose is not required, and thus the damage of the polylactic acid resin can be further prevented.
As described above, the biodegradable resin composition includes a pre-plasticized cellulose-based polymer, and thus has a glass transition temperature of about 60 ° C. to about 150 ° C. and a melt index of about 2 g / 10 min to 8 g /. It can be formed at an appropriate level of 10 minutes, thereby having a sufficient level of heat resistance and no need for high temperature processing conditions, thereby preventing the change of physical properties of the polylactic acid resin, and also improving the processability, thereby providing excellent stability and excellent economy. Can be implemented.
The polylactic acid resin and the plasticized cellulose polymer are as described above in one embodiment.
The plasticized cellulose-based polymer may be plasticized in advance by mixing about 10 parts by weight to about 80 parts by weight of a plasticizer to about 100 parts by weight of the cellulose-based polymer.
By mixing the content within the above range, it is possible to plasticize the cellulose-based polymer sufficiently to give the overall flexibility and to prevent the dissolution of the plasticizer, to realize a long-term uniform physical properties and excellent surface appearance. Specifically, when the plasticizer is mixed in excess of about 80 parts by weight, the plasticizer may be eluted from the cellulose-based polymer after product production, thereby deteriorating physical properties and surface appearance.
The plasticizer may include, for example, at least one selected from the group consisting of acetate plasticizers, phthalate plasticizers, citrate plasticizers, glycerin ester plasticizers, phosphate plasticizers, benzoate plasticizers, and combinations thereof. It is not limited to this. Specifically, including the benzoate-based plasticizer, it is excellent compatibility with both the cellulose-based polymer and the polylactic acid resin to have a single glass transition temperature, so that the heat resistance further improves the hydroxyl group present in the cellulose-based polymer Through the electrostatic interaction of the eluting phenomenon of the plasticizer can be more effectively prevented to achieve a long-term uniform physical properties and excellent surface appearance.
The weight ratio of the polylactic acid resin to the plasticized cellulose polymer may be, for example, about 1: 9 to about 9: 1, specifically about 7: 3 to about 8: 2.
By including in the weight ratio within the above range, the polylactic acid resin and the plasticized cellulose-based polymers can be properly balanced to achieve high levels of biodegradability, mechanical properties, and heat resistance.
For example, the plasticized cellulose-based polymer may include, for example, about 9 wt% to about 81 wt%, and for example, about 18 wt% to about 27 wt%. . By including a content within the above range it can be realized to a good level while maintaining sufficient heat resistance mechanical properties.
Accordingly, the polylactic acid resin may include, for example, about 9 wt% to about 81 wt%, and may also include, for example, about 63 wt% to about 72 wt%. By including a content within the above range it can be realized to a good level of heat resistance while implementing sufficient mechanical properties.
In another embodiment, the biodegradable resin composition may further include at least one selected from the group consisting of a compatibilizer, a chain extender, a peroxide, and a combination thereof.
Such compatibilizers include, for example, ethylene-vinyl acetate copolymers, polyethylene-grafted maleic anhydrides, polypropylene-grafted maleic anhydrides, and combinations thereof. It may include at least one selected from the group consisting of.
Specifically, the compatibilizer may comprise an ethylene vinyl acetate copolymer, the ethylene vinyl acetate copolymer contains a vinyl acetate group as a functional group common to both the polylactic acid resin and the cellulose-based polymer, further compatibility It is excellent, and thus the biodegradable composition can have a single glass transition temperature, it is possible to implement more excellent heat resistance. In addition, the vinyl acetate group may be included to improve tensile strength and elongation due to the nature of the functional group.
When including the compatibilizer may be included in about 4 parts by weight to about 20 parts by weight based on about 100 parts by weight of the polylactic acid resin. By including a content within the above range can realize a good compatibility and at the same time excellent workability. If it contains more than about 20 parts by weight of the compatibilizer may be difficult to process due to the increase in molecular weight.
The chain extender may use a kind known in the art, and examples thereof include, but are not limited to, diisocyanate, epoxy copolymer, hydroxycarboxylic acid compound, and the like.
In the case of including the chain extender, it may include about 0.5 parts by weight to about 5 parts by weight based on about 100 parts by weight of the polylactic acid resin. By including the content within the above range it is possible to implement excellent processability while implementing excellent mechanical and thermal properties. Specifically, when included in less than about 0.5 parts by weight, the molecular weight of each of the plasticized cellulose-based polymer and the polylactic acid resin does not increase sufficiently, so that the effect of improving mechanical and thermal properties is insignificant, and their compatibility is improved. In addition, the effect is also reduced, when included in more than about 5 parts by weight there is a problem that melt processing is difficult because the molecular weight is too increased.
The peroxide is, for example, dicumyl peroxide, dibenzoyl peroxide, cyclohexanone peroxide, t-butyl peroxy isopropyl carbonate, t-butyl peroxy laurate, t-butyl peroxy acetate, t-dibutyl Peroxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, 1,3-bis (t-butylperoxyisopropyl) benzene, methylethylketone peroxide, 2,5-dimethyl-2,5- Di (benzoyloxy) hexane, 2,5-dimethyl-2,5-di (t-buperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5- (t-butylperoxy ) -3-hexane, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 1, It may include, but is not limited to, at least one selected from the group consisting of 3-bis (t-butylperoxyisopropyl) benzene and combinations thereof.
In the case of including the peroxide, about 0.1 part by weight to about 0.5 part by weight based on about 100 parts by weight of the polylactic acid resin. By including a low content within the above range it can be achieved excellent compatibility and excellent mechanical and thermal properties. Specifically, when less than about 0.1 part by weight, crosslinking is insufficiently formed, and the effect of increasing compatibility and physical properties is insignificant. When the amount is greater than about 0.5 part by weight, the decomposition reaction of the polymers is greatly caused by radicals generated during decomposition of the peroxide. Therefore, there is a problem of lowering mechanical and thermal properties.
In another embodiment of the present invention, a biodegradable sheet formed by molding the biodegradable resin composition is provided. The biodegradable resin composition is as described above in another embodiment.
The biodegradable sheet can be implemented at the same time excellent biodegradability, excellent mechanical properties, excellent heat resistance and excellent workability.
The biodegradable resin composition may be molded by at least one method selected from the group including, for example, extrusion molding, calendaring molding, blow molding, and the like. The extrusion, calendering molding and blow molding may be performed by methods known in the art, and are not particularly limited.
The biodegradable sheet may be a sheet for making a packaging container, for example, the sheet may be made into a food or food packaging container.
Tensile strength according to ASTM D638 of the biodegradable sheet may be about 60MPa to about 120MPa. By having an appropriate level of tensile strength in the above range it can be achieved excellent impact strength after being produced into the product by, for example, thermoforming, foaming, and the like.
The elongation according to the conditions of ASTM D4018 of the biodegradable sheet may be, for example, about 15% to about 50%. By having an appropriate level of elongation within the above range, for example, excellent workability in thermoforming and foaming can be realized.
The biodegradable sheet may have a thickness of about 1 mm to about 20 mm, but is not limited thereto, and may be appropriately formed according to the purpose and use of the invention.
The following presents specific embodiments of the present invention. However, the embodiments described below are merely for illustrating or explaining the present invention in detail, and the present invention is not limited thereto.
Example
Example One
100 parts by weight of the cellulose polymer and 20 parts by weight of triacetin as an acetate plasticizer were mixed and stirred under the conditions of a temperature of 180 ° C. and a stirring speed of 60 rpm to prepare a plasticized cellulose polymer.
Then, 45% by weight of polylactic acid resin, 45% by weight of the plasticized cellulose-based polymer, 4 parts by weight of ethylene vinyl acetate copolymer, and 1 part by weight of chain extender based on 100 parts by weight of the polylactic acid resin at a temperature of 180 ° C and The biodegradable resin composition was prepared by mixing and stirring under the condition of a stirring rate of 60 pm, and the weight ratio of the polylactic acid resin to the plasticized cellulose polymer in the biodegradable resin composition was 1: 1.
The weight average molecular weight of the polylactic acid resin was 160,000 g / mol, and the weight average molecular weight of the plasticized cellulose polymer was 100,000 g / mol.
Comparative Example 1 (When polylactic acid resin, cellulose polymer and plasticizer were mixed and stirred at once without plasticizing in advance)
Without plasticizing the cellulose polymer in advance, 45% by weight of polylactic acid resin, 45% by weight of cellulose polymer, and 20 parts by weight of triacetin as a plasticizer to 100 parts by weight of the cellulose polymer are mixed and stirred at a time, and the polylactic acid The biodegradable resin composition was prepared by further mixing and stirring 4 parts by weight of ethylene vinyl acetate copolymer and 1 part by weight of chain extender based on 100 parts by weight of the resin, and specifically, under conditions of a temperature of 180 ° C. and a stirring speed of 60 rpm. Mix and stir. The content of the polylactic acid resin and the cellulose polymer is a value based on the resin composition excluding the plasticizer.
Comparative Example 3 (when the weight ratio is less)
4.5% by weight of polylactic acid resin and 85.5% by weight of plasticized cellulose polymer were mixed and stirred, except that the weight ratio of the polylactic acid resin to the plasticized cellulose polymer in the biodegradable resin composition was 1:19. Prepared a biodegradable resin composition under the same conditions and methods as in Example 1.
Comparative Example 3 (When the Weight Ratio is Excess)
85.5 wt% of polylactic acid resin and 4.5 wt% of plasticized cellulose polymer were mixed and stirred, except that the weight ratio of the polylactic acid resin to the plasticized cellulose polymer in the biodegradable resin composition was 19: 1. Prepared a biodegradable resin composition under the same conditions and methods as in Example 1.
Experimental Example
The biodegradable sheet was produced by the hydraulic press method using the biodegradable resin composition according to Example 1 and Comparative Examples 1 and 2.
The physical properties of each of the biodegradable resin compositions and the respective biodegradable sheets were evaluated, and are shown in Table 1 below.
Assessment Methods
(Glass transition temperature)
Measurement method: The biodegradable resin compositions according to Example 1 and Comparative Examples 1 and 2 were measured at a heating rate of 32 ° C./minute using a dynamic mechanical analysis.
(Melt index)
Measuring method: For each of the biodegradable resin compositions according to Example 1 and Comparative Examples 1 and 2, the weight was measured using a weight of 2.16 kg at a temperature of 190 ° C. according to the conditions of ASTM D1238. The values averaged over these were evaluated as the melt index.
(The tensile strength)
Measuring method: The biodegradable sheets prepared using the biodegradable resin compositions according to Example 1 and Comparative Examples 1 and 2 were measured using a universal testing machine (UTM (INSTRON)) according to ASTM D638.
Specifically, the measurement was performed under a condition of 100 mm / min stretching speed and 100 mm distance between grips, and the average value of a total of five tests was evaluated as tensile strength.
(Elongation)
Measuring method: The elongation at which the biodegradable sheet was broken while the respective biodegradable sheets were stretched under the same conditions and methods as the tensile strength was measured to evaluate the average value of a total of five tests as the elongation.
As shown in Table 1, the biodegradable sheet by the biodegradable resin composition according to Example 1 was clearly confirmed that the glass transition temperature, the melt index, the tensile strength and elongation were all implemented at an excellent level.
On the other hand, the biodegradable sheet according to the biodegradable composition according to Comparative Example 1 is too low in glass transition temperature and melt index, the heat resistance is inferior, but the tensile strength is too low, the impact strength is significantly reduced after the product is produced, the elongation is too low workability We can clearly expect this to fall significantly.
In addition, the biodegradable sheet according to the biodegradable composition according to Comparative Example 2 is inferior in heat resistance due to the low melt index, tensile strength is too high after being produced as a product, the impact strength is significantly high, can be easily broken, elongation is low workability You can clearly expect this to fall. In addition, the biodegradable resin composition according to Comparative Example 3 is also inferior in heat resistance due to the low glass transition temperature, the tensile strength is too low after the product is produced as a product, the impact strength is significantly reduced, elongation is low can be clearly predicted workability. .
Claims (18)
Preparing a biodegradable resin composition by mixing a polylactic acid resin and the plasticized cellulose polymer;
To include, mixing so that the weight ratio of the polylactic acid resin to the plasticized cellulose polymer is 1: 9 to 9: 1
Method for producing a biodegradable resin composition.
10 parts by weight to 80 parts by weight of the plasticizer is mixed with respect to 100 parts by weight of the cellulose polymer.
Method for producing a biodegradable resin composition.
Mixing the plasticized cellulose-based polymer in 9% by weight to 81% by weight
Method for producing a biodegradable resin composition.
The weight ratio of the polylactic acid resin to the plasticized cellulose polymer is 1: 9 to 9: 1,
Glass transition temperature is 60 ℃ to 150 ℃,
A melt index of 2 g / 10 min to 8 g / 10 min
Biodegradable resin composition.
The plasticized cellulose-based polymer is pre-plasticized by mixing 10 parts by weight to 80 parts by weight of a plasticizer in 100 parts by weight of cellulose-based polymer.
Biodegradable resin composition.
The cellulose polymer is cellulose nitrate (CN), cellulose acetate (CA), cellulose diacetate (CDA), cellulose acetate propionate (cellulose acetate propinonate, CAP), methyl cellulose ( methyl cellulose (MC), ethyl cellulose (ethyl cellulose, AC) and a combination of at least one selected from the group consisting of
Biodegradable resin composition.
The plasticized cellulose-based polymer is contained in 9% by weight to 81% by weight
Biodegradable resin composition.
The weight average molecular weight of the polylactic acid resin is 100,000g / mol to 200,000g / mol
Biodegradable resin composition.
The weight average molecular weight of the plasticized cellulose-based polymer resin is 100,000g / mol to 300,000g / mol
Biodegradable resin composition.
Further comprising at least one selected from the group consisting of compatibilizers, chain extenders, peroxides and combinations thereof
Biodegradable resin composition.
The compatibilizer in the group consisting of ethylene vinyl acetate copolymer (ethylene-vinyl acetate copolymer), polyethylene-grafted maleic anhydride, polypropylene-grafted maleic anhydride and combinations thereof Containing at least one selected
Biodegradable resin composition.
In the case of including the peroxide, 0.1 parts by weight to 0.5 parts by weight based on 100 parts by weight of the polylactic acid resin.
Biodegradable resin composition.
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| KR102656673B1 (en) * | 2021-09-15 | 2024-04-12 | 에스케이마이크로웍스 주식회사 | Biodegradable film, preperation method thereof, and environment-friendly packing material comprising the same |
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