KR101318474B1 - Compositions Comprising Crosslinked Biopolymer Having High Thermal Resistance And Elongation And Method of Producing the Same - Google Patents
Compositions Comprising Crosslinked Biopolymer Having High Thermal Resistance And Elongation And Method of Producing the Same Download PDFInfo
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- KR101318474B1 KR101318474B1 KR1020100028607A KR20100028607A KR101318474B1 KR 101318474 B1 KR101318474 B1 KR 101318474B1 KR 1020100028607 A KR1020100028607 A KR 1020100028607A KR 20100028607 A KR20100028607 A KR 20100028607A KR 101318474 B1 KR101318474 B1 KR 101318474B1
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Abstract
The biocrosslinked composition, which is crosslinked by incorporating a crosslinking monomer and a plasticizer into the biopolymer and irradiating electron beams, reduces the odor generated during the manufacturing process along with the reduction of harmful substances such as carbon dioxide, and is broken due to the hydrolysis of the existing bio resin. It has solved the problem, and is excellent in heat resistance, high elongation, light resistance and durability.
Description
The present invention relates to a bio-crosslinked body having heat resistance and high elongation characteristics and a method for manufacturing the same, and more particularly, to a heat-resistant, light-resistant, high elongation and The present invention relates to a bio-crosslinked composition and a method of manufacturing the same, which have durability characteristics, reduce odor generated during manufacture with reduction of harmful substances such as carbon dioxide, and solve problems of existing bio resins broken due to hydrolysis.
Plant-derived polymers have long been used as surgical threads because of their good adult suitability. Because it breaks down naturally, it is not necessary to remove the seams. Plant-derived polymer is a biodegradable resin, and is widely used as a substitute for vinyl chloride resin in disposable containers including disposable food containers or multi sticks for agriculture. In addition, since it does not contain allergens and toxic substances, the application of such as underwear is expanding.
Plant-derived carbon, on the other hand, is carbon neutral, also referred to as renewable. That is, since it is included in the temporal carbon purification, it does not increase carbon dioxide (CO 2 ). Conversely, fossil fuels such as petroleum, natural gas, and coal are carbon accumulated by the ancient earth through photosynthesis. The development of the petrochemical industry is currently used as fuel for internal combustion engines and various kinds of polymers. Since the ancient carbon is rapidly released in the present world, the concentration of carbon dioxide (CO 2 ) is increased significantly, causing a warming phenomenon. In many fields, research is being conducted on durable polymers that do not degrade well using carbon other than fossil fuels. Polymers using plant-derived carbon are called biopolymers or renewable polymers. At present, a test is being conducted to crosslink a biopolymer to provide strength and durability equivalent to that of a fossil polymer. In general, decomposition is promoted by electromagnetic waves having high penetrating power such as electron beams and gamma rays. Japanese Patent Application No. 2003-313214, filed by Yoshii Fumio's research team at the Japan Atomic Energy Research Institute, describes the addition of electron beam reactive monomers to biopolymers to inhibit crosslinking by inhibiting decomposition. However, there is a problem that the blend is hard and difficult to put to practical use.
The biopolymer is synthesized after producing lactic acid from sugars fermented with starch, such as corn, sweet potatoes, and potatoes, which are plant-derived bio raw materials currently used worldwide. Examples of biopolymers include polylactic acid, polybutylene succinate, polybutylene succinate-co-adipate, a copolymer of butylene succinate and adiphenadiate, PBSA) and polycarprolactone. Among them, polylactic acid has properties of materials closest to plastics derived from general petroleum. The polylactic acid is advantageous in that mass production is possible, the price is low, and the melting point (Tm) is 170 ° C. or more. However, since polylactic acid has a low crystallization rate and a glass transition temperature (Tg) of about 60 ° C., the polylactic acid is difficult to be molded, decomposed by moisture or bacteria, and has poor light and heat resistance. In addition, the characteristic smell derived from sugar remains. Since it is difficult to realize high elongation of polylactic acid, a plasticizer or the like is used. However, polylactic acid impregnated in plasticizer or polylactic acid impregnated in plasticizer has high glass transition temperature, so crystallization is performed in the process of cooling at room temperature after processing. As the plasticizer is discharged there is a problem.
In order to solve the problems of the prior art as described above, the present invention is a bio-crosslinking having the effect of reducing the harmful substances such as carbon dioxide derived from fossil resources and decomposing and reducing VOCs such as odorous substances and formaldehyde unique to biopolymers. It is an object to provide a body composition and a method for producing the same.
In addition, an object of the present invention is to provide a biocrosslinked composition having a durable property such as strength, heat resistance, light resistance, and the like, and a method for producing the same, as the fossil-derived polymer.
These and other objects of the present invention can be achieved by the present invention described below.
In order to achieve the above object, the present invention provides 100 parts by weight of biopolymer, 0.1 to 10 parts by weight of crosslinking aid and 1 to 100 parts by weight of plasticizer, and other antioxidants, light absorbers, light stabilizers, pigments, flame retardants, After mixing the nucleating agent and other polymers to increase the filler glass transition temperature, processed into a sheet, irradiated with an electron beam of 5 ~ 200 kiloguraray (KGy), to form a three-dimensional network structure, Provided is a biocrosslinked composition having excellent light resistance.
By using a plant-derived polymer and a low-energy processing method such as an electron beam, emission of carbon dioxide (CO 2 ) can be suppressed and global warming can be prevented. It has heat resistance and high elongation characteristics and solves the problem of breakage due to hydrolysis of existing bio resins. In addition, the crosslinked biopolymers produced have the same strength and durability as the fossil resource-derived polymers, and have fewer problems such as odors. Biopolymers, such as vacuum forming, can be used, for example, in instrument panels and door trims of automobiles.
The present invention is to add a plasticizer having a functional group reacting with a crosslinkable monomer (crosslinking agent) and an electron beam to the biopolymer, and then crosslinking by irradiating an electron beam to create a three-dimensional network structure, such as flexible, heat resistance, light resistance, etc. A crosslinked biopolymer having durability and elongation at high temperatures in particular.
Hereinafter, the present invention will be described in detail.
The present invention is 100 parts by weight of biopolymer, 0.1 to 10 parts by weight of crosslinking aid and 1 to 100 parts by weight of plasticizer, and other antioxidants, light absorbers, light stabilizers, pigments, flame retardants, fillers, glass transition temperature according to the needs of use After mixing the nucleating agent and the other polymer to be processed into a sheet form, it is irradiated with an electron beam of 5 ~ 200 kiloguraray (KGy) to form a three-dimensional network structure, characterized in that the heat resistance or light resistance good biopolymer It provides a crosslinked product.
Detailed formulations for the biocrosslinker compositions are described below.
In main blending, (A) 100 parts by weight of the biopolymer (B) 0.1 to 10 parts by weight of the co-agent and (c) 1 to 100 parts by weight of the plasticizer are mixed and referred to as (D). In addition, pigments, antioxidants, light absorbers (UV-A), light stabilizers (HALS), flame retardants, nucleating agents, fillers, etc. can be used. If the biopolymer alone lacks physical properties when used in harsh applications, a polymer derived from fossil fuel may be added. Thus, if the sum total of mixtures other than (D) is (E), (D) + (E) = (F) is the composition whole quantity. Of course, there may be a case where (D) = (F). If there is a compound derived from a plant in a material other than (A), the sum of the compound is (G). It features.
The biopolymer used in the present invention may be various kinds including polylactic acid, but is not particularly limited. Specifically, polylactic acid, polybutylene succinate, polybutylene succinate-co-adipate and polycapro, which are copolymers of butylene succinate and adifen adipate It is preferable to use at least one selected from polycarprolactone and the like, more preferably polylactic acid or polybutylene succinate coadipate.
The reactive crosslinking aid used in the present invention is not particularly limited as long as it is a monomer capable of crosslinking by electron beam irradiation, but may include an allylic monomer, an acrylate monomer or a methacrylate monomer crosslinkable monomer. have. Allyl-type crosslinking adjuvant include triallyl isocyanate (TAIC), triallyl cyanurate (TAC), and diaryl phthalate (DAP). Acrylic and methacryl-type crosslinking adjuvant is a trimethylolpropane trimethacrylate (TMPTMA), a trimethylolpropane triacrylate TMPTA, etc. are mentioned. At least 1 type is selected and used from said crosslinking adjuvant. It is used within the range of 0.1 to 10 parts by weight based on 100 parts by weight of the biopolymer, in the above range, the crosslinking reaction with the biopolymer is good.
In the biopolymer, functional groups such as carboxyl group (-COOH) or hydroxyl group (-OH) are generally effective crosslinking starting points. Natural rubber may be used for crosslinking, or conventional chemical crosslinking with sulfur and peroxide may be used. However, there is a drawback that the reaction is complicated and the reproducibility is time-consuming. By using the electron beam according to the present invention, the three-dimensional network structure can be formed with high productivity in a stable state. Since less energy is required for crosslinking, less carbon dioxide is produced during manufacture.
The plasticizer with a crosslinking reaction group used in the present invention uses one or more selected from ester-based and glycol-based groups having a functional group such as carboxyl group (-COOH) or hydroxyl group (-OH), and 100 parts by weight of the biopolymer. It is used in the range of 1 to 200 parts by weight, and in that range, it is easy to change from the chain shape of the biopolymer and the crosslinking aid to the network complex crosslinked structure when irradiated with an electron beam of 5 to 200 kilogramray (KGy).
In the present invention, it is possible to add a general polymer 1 to 300 parts by weight based on 100 parts by weight of the biopolymer. Thermoplastic elastomers are suitable for not increasing the hardness. In the case of thermoplastic elastomers, urethane-based thermoplastic elastomers (TPU), styrene-based thermoplastic elastomers (TPS), olefin-based thermoplastic elastomers (TPO), random ethylene-octene copolymers (EOC), ethyl acrylate resins, and ethyl methyl Acrylate resins, ethylmethyl methacrylate resins and the like can be used. In addition, conventional additives used in the art may be used.
The following is an example of a method for producing a biocrosslinked composition having heat resistance and high elongation characteristics of the present invention. 100 parts by weight of biopolymer, 0.1 to 10 parts by weight of crosslinking aid and 1 to 100 parts by weight of plasticizer and other additives to increase antioxidant, light absorbing agent, light stabilizer, pigment, flame retardant, filler, glass transition temperature according to the needs of use Nucleating agents and other polymers are blended and processed into sheets and irradiated with an electron beam of 5 to 200 kilograms (KGy).
In the manufacturing method of the biocrosslinked composition of this invention, it manufactures in the following procedure.
a) 100 parts by weight of the biopolymer, 0.1 to 10 parts by weight of the crosslinking aid, and 1 to 100 parts by weight of the plasticizer by melt kneading at a temperature of 150 ° C to 200 ° C for 5 to 30 minutes; And
b) irradiating an electron beam of 5 to 250 kilograms (KGY) once to 5 times with an acceleration voltage of 150 to 1,200 KV.
First, the biopolymer resin, the plasticizer, the crosslinking crosslinking aid, and other blends were put into a Brabender Plastograph, melt kneaded at 180 ° C. for 10 minutes, and then kneaded and sheeted at a temperature of 180 ° C. for 5 minutes with two tester rolls, followed by 0.5 Get the material in mm.
The step of irradiating an electron beam is to irradiate an electron beam having a range of 5 to 250 kilograms (KGy) once to five times with an acceleration voltage of 150 to 1,200 kV. The ionizing radiation is not limited to an electron beam here, but the electron beam is suitable for the present biopolymer crosslinked material for the following reasons. Types of ionizing radiation include electron beams, including alpha rays, beta rays, gamma rays, and the like.The electron beams emit electrons at high speed through the device, and the other ionizing radiations are caused by the decay of radioactive materials such as cobalt blue. Difficulties in radioactive leakage management, etc. In addition, alpha rays cannot be used because they have a weak penetrating power of 4He. Gamma rays are neutral and unsuitable for crosslinking reactions, but their use is increasing for sterilization applications such as meat because of their strong permeability. However, the kilogram Laray (KGy) refers to the electron dose. The crosslinkability of a biopolymer, a crosslinking aid, and a crosslinkable plasticizer is good within the electron beam dose, acceleration voltage, and electron beam irradiation recovery range.
In the present invention, a surface treatment step and an embossing step may be included after the above step, but the surface treatment method is in accordance with conventional methods used in the art.
Bio-crosslinked composition according to the present invention is usefully used for automotive interior materials or packaging films.
Hereinafter, the present invention will be described in more detail with reference to Examples, but it does not mean that the present invention is limited to the following Examples.
Example One
The biopolymer is 100 parts by weight of 4030D of Nature Work, the crosslinking monomer is 1 part by weight of triallyl isocyanate (TAIC) from Nippon Kasei, and the plasticizer is 10 parts by weight of PL-012 from Riken Viatamin. The part was previously put into a brabender plasuttograph and kneaded at 180 ° C. for 10 minutes. The kneaded mixture was sheeted in two tester rolls with 200 parts by weight of a conventional polymer, Mitsui Co., Ltd. (Milastomer 6560N) to prepare a 0.5 mm material. The prepared material was irradiated with 20 kilograms (KGy) by the electron accelerator (acceleration voltage 2.54MeV).
Example 2
Example 1 was carried out in the same manner as in Example 1 except that the electron beam irradiation dose was carried out in 40 kilograms (KGy).
Example 3
Example 1 was carried out in the same manner as in Example 1 except that the irradiation dose of electron beam at 60 kilogramray (KGy).
Comparative Example
Except that the crosslinking in the electron accelerator in Example 1 was carried out in the same manner as in Example 1.
[Gel fraction evaluation]
The biopolymer electron beam crosslinked product prepared in Examples 1 to 3 and Comparative Example was dried before the test to measure the mass first, and then wrapped in a wire mesh of 325 mesh size and placed in a flask containing xylene solution, at a temperature of 180 ° C. After boiling for 6 hours in oil, the sol component dissolved in xylene was removed to obtain the remaining gel component. It dried at 120 degreeC for 4 hours, the xylene in a gel was removed, and the dry mass of the gel component was measured. Based on the measured mass value, the gel fraction was calculated by the following formula.
Gel fraction (%) = (dry gel component mass / dry mass of biopolymer crosslinked product) X100 (%)
Warm and room temperature Elongation evaluation
The prepared crosslinked product was cut into dumbbell No. 1 specimen, and mechanical properties were evaluated as follows at a tensile speed of 200 m / min at a temperature of 140 ° C.
As shown in Table 2, the bio-crosslinked composition according to Examples 1 to 3 of the present invention was confirmed that the elongation is superior to the biopolymer according to the comparative example without undergoing the cross-linking process by the electron beam irradiation.
Claims (12)
The crosslinking aid is a biocrosslinked composition, characterized in that at least one reactive monomer capable of crosslinking by electron beam irradiation.
The thermoplastic elastomers include urethane-based thermoplastic elastomers (TPU), styrene-based thermoplastic elastomers (TPS), olefin-based thermoplastic elastomers (TPO), random ethylene octene copolymers, ethyl acrylate resins, ethyl methyl acrylate resins and ethyl methyl methacrylate resins. Bio-crosslinked composition, characterized in that at least one selected from the group consisting of.
The bio-crosslinked composition further comprises one or more additives selected from the group consisting of antioxidants, light absorbers, light stabilizers, pigments, flame retardants, fillers, nucleating agents.
The biocrosslinked composition is a biocrosslinked composition, characterized in that the three-dimensional network structure.
b) irradiating an electron beam of 5 to 250 kilogram larays (KGY) once to five times with an acceleration voltage of 150 to 1,200 KV, wherein the biopolymer is polybutylene succinate resin and polybutylene silica. At least one member selected from the group consisting of nitrate adipate resins, the crosslinking aid is at least one member selected from the group consisting of trimetholpropane trimethacrylate and trimetholpropane triacrylate, and the plasticizer is carboxyl It is an ester type or glycol type compound which has a group or a hydroxyl group, The manufacturing method of the biocrosslinked composition characterized by the above-mentioned.
Surface treatment after step b); And
Method for producing a bio-crosslinked composition, characterized in that it further comprises the step of embossing.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020100028607A KR101318474B1 (en) | 2010-03-30 | 2010-03-30 | Compositions Comprising Crosslinked Biopolymer Having High Thermal Resistance And Elongation And Method of Producing the Same |
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| KR101523813B1 (en) * | 2012-04-06 | 2015-05-28 | (주)엘지하우시스 | Sheet having styrene co-polymer and olefin co-polymer, multilayer sheet and method of manufacturing the multilayer sheet using the same |
| KR101523814B1 (en) * | 2012-04-06 | 2015-05-28 | (주)엘지하우시스 | Polymer sheet with excellent strength, wear resistance, flame resistance and embossing maintenance, and method of manufacturing the polymer sheet |
| EP2842988A4 (en) * | 2012-09-21 | 2016-02-17 | Lg Hausys Ltd | Bioresin-added interior sheet for vehicles and method for manufacturing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680806A (en) * | 1992-09-02 | 1994-03-22 | Tonen Chem Corp | Production of water absorbable crosslinked resin |
| JPH06192375A (en) * | 1992-12-25 | 1994-07-12 | Nippon Unicar Co Ltd | Crosslinked material of polymer composition and its production |
| KR20070119632A (en) * | 2005-03-14 | 2007-12-20 | 스미토모덴코파인폴리머 가부시키가이샤 | Process for producing crosslinked material of polylactic acid and crosslinked material of polylactic acid |
| JP2008291095A (en) | 2007-05-23 | 2008-12-04 | Sumitomo Electric Fine Polymer Inc | Method for producing resin crosslinked product and resin crosslinked product produced by the production method |
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- 2010-03-30 KR KR1020100028607A patent/KR101318474B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0680806A (en) * | 1992-09-02 | 1994-03-22 | Tonen Chem Corp | Production of water absorbable crosslinked resin |
| JPH06192375A (en) * | 1992-12-25 | 1994-07-12 | Nippon Unicar Co Ltd | Crosslinked material of polymer composition and its production |
| KR20070119632A (en) * | 2005-03-14 | 2007-12-20 | 스미토모덴코파인폴리머 가부시키가이샤 | Process for producing crosslinked material of polylactic acid and crosslinked material of polylactic acid |
| JP2008291095A (en) | 2007-05-23 | 2008-12-04 | Sumitomo Electric Fine Polymer Inc | Method for producing resin crosslinked product and resin crosslinked product produced by the production method |
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