KR101210156B1 - Biodegradable multi-layer sheet having an excellent heat and inpact resistance and preparing process thereof - Google Patents
Biodegradable multi-layer sheet having an excellent heat and inpact resistance and preparing process thereof Download PDFInfo
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Abstract
The present invention relates to a biodegradable multilayer sheet and a method of manufacturing the same, which can be excellently improved the impact resistance and heat resistance of the product without reducing the biodegradability of the polylactic acid, having the excellent impact resistance and heat resistance of the present invention The biodegradable sheet is a biodegradable sheet based on polylactic acid, wherein the sheet is 50.0 to 85.0 parts by weight of polylactic acid, at least one selected from aliphatic polymethyl methacrylate (PMMA) homopolymer or copolymer. Polymethyl methacrylate 10.0 to 30.0 parts by weight, rubber-modified vinyl-based graft copolymer resin is characterized in that consisting of 5.0 to 20.0 parts by weight.
The biodegradable multilayer sheet having excellent impact resistance and heat resistance of the present invention configured as described above adds specific components based on polylactic acid, and thus has excellent impact resistance and heat resistance without reducing the biodegradability which is an advantage of polylactic acid. As a result, the disposable packaging containers made of these sheets have excellent gloss and scratch resistance effects when used in the packaging and storage of products such as furniture, metal, plywood and electronics, and have similar properties and functionality to plastics. In addition, since it is biodegradable under general composting conditions after use, it is a useful invention with excellent practical value that enables the manufacture of environmentally friendly products that do not cause environmental problems due to disposal.
Description
The present invention relates to a biodegradable multilayer sheet having excellent impact resistance and heat resistance, and a method of manufacturing the same. More specifically, the biodegradability that can be excellently improved in impact resistance and heat resistance without reducing the biodegradability which is an advantage of polylactic acid. It relates to a multilayer sheet and a method of manufacturing the same.
In general, synthetic plastics are used for various purposes all over the world as packaging materials that are indispensable to modern life because of their excellent properties and cheap and light properties. However, synthetic plastics having the above-mentioned characteristics are environmental problems due to their advantages and disadvantages of poor decomposition, and thus, various countries have recently been interested in finding solutions to them. In other words, the conventional methods of landfilling, incineration and regeneration have been mainly used for treating synthetic plastics, but these methods could not completely solve the environmental pollution problem.
Therefore, attention is now focused on the development of so-called degradable plastics, which makes it possible to decompose the used plastic by itself. Currently, various kinds of degradable plastics have been developed from various technologies and raw materials. Among them, polylactic acid (hereinafter referred to as 'PLA') is produced in large quantities and inexpensively by the fermentation method of L-lactic acid. Under the conditions of composting, the decomposition rate is fast, and it has excellent characteristics such as resistance to mold and odor resistance to food. Several attempts are being made. For example, in order to commercialize such biodegradable sheets using polylactic acid, the heat and impact resistances mentioned in Japanese Patent Application Laid-Open No. 1998-120889 should be improved. A method of blending is disclosed. In particular, Japanese Laid-Open Patent Publication No. 1999-241008 discloses a composition composed of aliphatic polyester and other natural products having PLA and a melting point of 80 to 250 ° C and having a heat resistance of 60 to 120 ° C. It is starting.
However, the sheet using the conventional polylactic acid has a disadvantage in that it is still insufficient to realize sufficient heat resistance and mechanical strength.
Therefore, in order to solve the above-mentioned disadvantages of mechanical strength and heat resistance, International Patent Publication No. W02008 / 081617 attempts to solve the above-mentioned disadvantages by inducing a stereo complex crystal, but its effect is unclear and cost-effective. There is a limit. In another method, Korean Patent Publication No. 2009-0073933 discloses a method of improving heat resistance and impact resistance, including "(A) 10 to 80 parts by weight of polylactic acid resin; (B) rubber-modified vinyl graft copolymer resin 10 To 70 parts by weight, (C) 5 to 50 parts by weight of natural fibers, and (D) a polylactic acid comprising 0.01 to 5 parts by weight of a chain extender based on 100 parts by weight of the mixture of (A), (B) and (C). Resin composition ", but the method also has the disadvantage of reducing the biodegradability which is an advantage of the biodegradable resin due to the addition of a large amount of rubber-modified vinyl-based graft copolymer to improve the heat resistance and impact resistance. .
Therefore, the present invention has been made in view of the above technical problems in the prior art, the main object of the present invention can be improved excellent impact resistance and heat resistance of the product without reducing the biodegradability which is an advantage of polylactic acid. It is to provide a biodegradable multilayer sheet.
Another object of the present invention is to provide a method for more easily preparing a biodegradable multilayer sheet having improved impact resistance and heat resistance without reducing biodegradability.
The present invention may also be aimed at achieving, in addition to the above-mentioned specific objects, other objects which can be easily derived by those skilled in the art from this and the overall description of the present specification.
The object of the present invention described above is composed of a polylactic acid-based rubber modified vinyl graft copolymer resin added to the inner layer, the outer layer is selected from polymethyl methacrylate (PMMA) homopolymer or copolymer The present invention has been accomplished by finding that the impact resistance and heat resistance can be improved while maintaining biodegradability by forming a multilayer structure formed of a mixture of polymethyl methacrylate and polylactic acid.
Biodegradable sheet having excellent impact resistance and heat resistance of the present invention for achieving the above object;
In a biodegradable sheet based on polylactic acid, the sheet includes 50.0 to 85.0 parts by weight of polylactic acid, at least one polymethylmethacryl selected from aliphatic polymethylmethacrylate-based (PMMA) homopolymers or copolymers. Rate 10.0 to 30.0 parts by weight, the rubber-modified vinyl graft copolymer resin is characterized in that consisting of 5.0 to 20.0 parts by weight.
According to another configuration of the present invention, the polylactic acid is composed of L-lactic acid, D-lactic acid or L, D-lactic acid, the molecular weight is 10,000 or more, characterized in that they are used alone or in combination.
According to another configuration of the invention, the sheet is at least one selected from the (A) layer and the polymethyl methacrylate-based (PMMA) homopolymer or copolymer consisting of a rubber modified graft copolymer and a polylactic acid (B), which is an outer layer composed of a mixture of polymethyl methacrylate and polylactic acid, is characterized in that it is composed of a multilayer structure of B / A / B.
According to another configuration of the present invention, the biodegradable sheet of the B / A / B structure is characterized in that the thickness is formed from 0.15mm to 1.00mm.
According to another configuration of the present invention, the polymethyl methacrylate (PMMA) resin is a methyl methacrylate homopolymer or copolymer, the copolymer is methyl methacrylate, methyl acrylate, ethyl (meth) acrylic It is characterized by being a copolymer superposed | polymerized with one or more components chosen from the rate, butyl (meth) acrylate, and styrene.
According to another configuration of the present invention, the polymethyl methacrylate (PMMA) resin is characterized in that the weight average molecular weight of 60,000 ~ 15.
According to another configuration of the present invention, the rubber-modified vinyl-based graft copolymer resin constituting the inner layer is composed of 40 to 90 parts by weight of an aromatic vinyl compound and 1 to 30 parts by weight of a vinyl cyanide compound 30 to 60 parts by weight of the monomer mixture is characterized in that it is prepared by graft polymerization.
According to another configuration of the invention, the particle size of the rubber-modified vinyl-based graft copolymer resin is characterized in that the range of 0.05 to 4㎛.
According to another configuration of the present invention, the sheet is characterized in that 0.01 to 5 parts by weight of the chain extender is further added.
According to another configuration of the present invention, the chain extender is an epoxy functional group, the main chain is a copolymer prepared by selecting one or two or more selected from polyethylene, polypropylene, siloxane, aromatic vinyl monomer, vinyl cyanide monomer It is characterized by.
According to another configuration of the present invention, the sheet includes an additive selected from the group consisting of antioxidants, weathering agents, mold release agents, colorants, sunscreens, fillers, nucleating agents, plasticizers, adhesion aids, pressure sensitive adhesives, and mixtures thereof. It is characterized in that it further comprises.
The biodegradable multilayer sheet having excellent impact resistance and heat resistance of the present invention configured as described above adds specific components based on polylactic acid, and thus has excellent impact resistance and heat resistance without reducing the biodegradability which is an advantage of polylactic acid. As a result, the disposable packaging containers made of these sheets have excellent gloss and scratch resistance effects when used in the packaging and storage of products such as furniture, metal, plywood and electronics, and have similar properties and functionality to plastics. In addition, since it is biodegradable under general composting conditions after use, it is a useful invention with excellent practical value that enables the manufacture of environmentally friendly products that do not cause environmental problems due to disposal.
EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in more detail by preferable embodiment.
The polymethyl methacrylate (PMMA) resin used according to a preferred embodiment of the present invention is a methyl methacrylate homopolymer or copolymer, and the copolymer is methyl methacrylate, methyl acrylate and ethyl (meth) acrylic. It consists of resin which is a copolymer superposed | polymerized with one or more components chosen from the rate, butyl (meth) acrylate, and styrene. The composition ratio of the comonomers described above is not particularly limited as long as methyl methacrylate (MMA) is used as the main component, but is preferably polymerized in a ratio of 50 to 99 parts by weight of methyl methacrylate and 1 to 50 parts by weight of comonomer. It is good to use. More preferably, the use of 65 to 97 parts by weight of MMA and 35 to 3 parts by weight of comonomer does not lose wear resistance and transparency.
Preferably the weight average molecular weight of the said PMMA system resin used for this invention is 60,000-150,000, More preferably, it is 70,000-130,000. When the molecular weight of the resin exceeds 150,000, the impact strength and the dispersing effect of the composition are improved, but the flowability of the composition is reduced, and post-processing property is lowered. On the contrary, when the molecular weight is less than 60,000, the fluidity of the composition is good, but the impact strength is good. It is not preferable because it lacks dispersibility.
The rubber-modified vinyl-based graft copolymer resin is styrene, α-methylstyrene, halogen or alkyl substituted styrene, C 1 -C 8 methacrylic acid alkyl esters, C 1 -C 8 acrylic acid alkyl esters, or mixtures thereof 5 to 95 parts by weight of a monomer mixture consisting of 50 to 95 parts by weight and 5 to 50 parts by weight of acrylonitrile, methacrylonitrile, maleic anhydride or a mixture thereof, butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, One or a mixture thereof selected from the group consisting of acrylonitrile / butadiene rubber, isoprene rubber, terpolymer of ethylene-propylene-diene (EPDM), polyorganosiloxane / polyalkyl (meth) acrylate rubber composite 5 to 95 It is prepared by graft polymerization with parts by weight.
The C 1 -C 8 methacrylic acid alkyl esters or C 1 -C 8 acrylic acid alkyl esters are esters obtained from monohydryl alcohols containing 1 to 8 carbon atoms, respectively, as alkyl esters of methacrylic acid or acrylic acid. Ryu. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid propyl ester, acrylic acid ethyl ester or acrylic acid methyl ester. According to a preferred embodiment of the present invention, preferred examples of the rubber-modified vinyl-based graft copolymers are styrene and acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in butadiene rubber, acrylic rubber, or styrene / butadiene rubber. And graft copolymerized in the form of a mixture.
Examples of other preferred rubber-modified vinyl-based graft copolymers include those obtained by graft copolymerization of a monomer of (meth) acrylic acid methyl ester to butadiene rubber, acrylic rubber, or styrene / butadiene rubber. In one embodiment of the present invention is prepared by graft polymerization of 60 to 30 parts by weight of a monomer mixture consisting of 50 to 95 parts by weight of an aromatic vinyl compound and 5 to 50 parts by weight of a vinyl cyanide compound to 40 to 70 parts by weight of a rubbery polymer.
An example of the most preferred rubber modified graft copolymer in the present invention is an ABS graft copolymer. In the manufacture of the graft copolymer, the particle diameter of the rubber particles is preferably in the range of 0.05 to 4 μm in order to improve impact resistance and surface properties of the molded product.
The method for preparing the graft copolymer is well known to those skilled in the art, and any one of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization may be used. Under the above-mentioned aromatic vinyl monomer, it is preferable to carry out emulsion polymerization or block polymerization using a polymerization initiator.
The polylactic acid and polymethyl methacrylate, rubber modified graft copolymer constituting the present invention may further include a chain extender. It is preferable to use a chain extender having a functional group capable of reacting with a hydroxy or carboxyl end group of polylactic acid, which can improve compatibility of natural fibers. It is preferable to use what contains an epoxy functional group as said functional group. The chain extender is a copolymer having an epoxy functional group bonded to the main chain, wherein the content of the epoxy functional group in the copolymer is 0.1 to 40 mol%, more preferably 10 to 20 mol% with respect to the copolymer. . The main chain is preferably a copolymer selected from the group consisting of polyethylene, polypropylene, siloxane, aromatic vinyl monomers, vinyl cyanide monomers, and combinations thereof. As the aromatic vinyl monomer, styrene substituted with an alkyl group having 1 to 4 carbon atoms such as α-methylstyrene, styrene substituted with halogen, and the like can be preferably used. As said vinyl cyanide monomer, acrylonitrile, methacrylonitrile, etc. can be used preferably. Moreover, it is more preferable to use styrene as said aromatic vinyl monomer, and it is more preferable to use acrylonitrile as a vinyl cyanide monomer.
The content of the chain extender is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the composition. When the content of the chain extender is 0.01 to 5 parts by weight, mechanical strength and heat resistance may be improved, and viscosity may be increased during melt extrusion to a level at which mixing is performed.
In the preparation of the biodegradable multilayer sheet according to the present invention, an additive may be further included in the polylactic acid resin composition. Such additives include antioxidants, weathering agents, mold release agents, colorants, sunscreen agents, fillers, nucleators, and plasticizers. , Flame retardants, and mixtures thereof.
Specifically, as the antioxidant, phenol type, phosphite type, thioether type, or amine type antioxidant can be preferably used. As the weathering agent, a benzophenone type or an amine weathering agent can be preferably used, and as the release agent, a fluorine-containing polymer, a silicone oil, a metal salt of stearyl acid, a metal salt of montanic acid, a montanic acid ester wax, or a polyethylene wax Can be preferably used. In addition, a dye or a pigment may be preferably used as the colorant, and titanium oxide or carbon black may be preferably used as the sunscreen. Silica, clay, calcium carbonate, calcium sulfate, or glass beads may be preferably used as the filler, and talc or clay may be preferably used as the nucleating agent. As the plasticizer, a polyester plasticizer, a glycerin plasticizer, a phosphate ester plasticizer, a polyalkylene glycol plasticizer, an epoxy plasticizer, and the like are preferably used. Can be. The flame retardant may be preferably a bromine flame retardant, a phosphorus flame retardant, an antimony compound, a melamine compound, or the like.
In addition, according to a preferred embodiment of the present invention, such additives may be included as part of a composition based on polylactic acid resin constituting the biodegradable multilayer sheet of the present invention. For example, the chain extender is to mix and process the polylactic acid to prepare a master batch, and then further mix the vinyl copolymer resin and the polylactic acid resin. The master batch may be prepared using a batch type mixer or an extruder type or the like.
In the present invention, the chain expander and the polylactic acid resin are prepared in a master batch, so that feeding is easy during extrusion, and the viscosity of the composition is increased while improving the compatibility of the polylactic acid, the chain extender and the rubber-modified vinyl graft copolymer. It has the advantage of being able to.
According to another preferred embodiment of the present invention, the pellet can be prepared by a known method using the polylactic acid resin composition for producing a biodegradable multilayer sheet according to the present invention. For example, after mixing the above-described composition and additives of the present invention, it may be melt extruded in an extruder to produce and use pellets.
According to another preferred embodiment of the present invention, a molded article prepared by molding the polylactic acid resin composition for producing a biodegradable multilayer sheet according to the present invention can be provided. The molded article using the polylactic acid resin composition may be used in molded articles in fields requiring durability, heat resistance and transparency, for example, office equipment such as automobiles, mechanical parts, electrical and electronic parts, computers, and miscellaneous goods. . In particular, it may be preferably applied to housings of electrical and electronic products such as televisions, computers, printers, washing machines, cassette players, audio, mobile phones, and the like.
Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited thereto.
First, the measurement and evaluation methods necessary for the explanation of the present invention were performed under the following conditions.
(1) impact resistance;
Izod impact strength of the sheet prepared under the same conditions was measured according to ASTM D256. If the impact strength is less than 3kg ~ cm / cm there is a risk of problems such as cracking during assembly.
(2) transparency;
A sample of 10 cm x 10 cm sample was placed vertically in an HAITMATIC DIGITAL HAZEMETER (manufactured by Nippon Densoku Co., Ltd.) in a vertical position, and light was transmitted through light having a wavelength of 400 to 700 nm in a direction perpendicular to the vertically placed sample. The value was measured.
In this case, the haze value was calculated from Equation 1 below.
&Quot; (1) "
Haze (%) = (1-amount of scattered light / total transmission of light) × 100
(3) Heat resistance (heat deformation temperature):
The measurement was carried out according to ASTM D648, the sheet was prepared according to the contents shown in Table 1 under the same conditions, and the measurement was performed.
Examples 1 to 3
These components were mixed with the resin and the additive components shown in Table 1 below, and their composition ratio contents, and the composition was introduced from the hopper while the resin composition was stirred using a twin screw extruder. The screw front end (1 ~ 2 zones) was maintained at about 155 ℃ and the back end (3-7 zones) was kept at about 185 ℃ for melt kneading. The extrusion die temperature was kept at 225 ℃ and extruded at 600kg / hr. And cooled to prepare sheets having a thickness of 0.3 mm, respectively. The sheet thus prepared was measured for impact resistance, transparency and heat deflection temperature according to the above method, and the results are shown in Table 2 below.
Comparative Examples 1 and 2
The resin and the additive components and their composition ratio content were the same as in the above Examples except as shown in Table 1 below.
(kJ / ㎡)
(%)
(℃)
As shown in Table 2, the sheets of Examples 1 to 3 according to the present invention to which rubber-modified vinyl graft copolymer resin and PMMA were added were found to have significantly increased impact resistance compared to Comparative Example 1. . In addition, even in the heat deflection temperature, Examples 2 to 3 according to the present invention to which the chain growth agent was added had a higher heat deflection temperature, thereby the heat resistance of the polylactic acid can be effectively improved by the chain growth agent. have.
In conclusion, it can be seen that the impact resistance is remarkably improved by constructing the PMMA / PLA / PMMA multilayer structure according to the present invention and by constructing the rubber-modified vinyl-based graft copolymer in the inner layer. By adding the chain growth agent, it can be seen that the heat resistance can be increased significantly.
The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (11)
The sheet includes (A) an inner layer consisting of the rubber-modified graft copolymer resin and a polylactic acid, and at least one polymethyl methacrylate selected from the polymethyl methacrylate (PMMA) homopolymer or copolymer. A biodegradable sheet having excellent impact resistance and heat resistance, wherein the (B) layer, which is an outer layer composed of a mixture of polylactic acid, is composed of a multilayer structure of B / A / B.
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| KR1020100110880A KR101210156B1 (en) | 2010-11-09 | 2010-11-09 | Biodegradable multi-layer sheet having an excellent heat and inpact resistance and preparing process thereof |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US9987820B2 (en) | 2009-11-17 | 2018-06-05 | Arkema France | Multilayer structures containing biopolymers |
| US10518508B2 (en) | 2012-07-27 | 2019-12-31 | Arkema France | Multilayer structures containing biopolymers |
| KR102044168B1 (en) * | 2012-12-17 | 2019-11-14 | 도레이첨단소재 주식회사 | The method for preparing multi-layer sheet having an improved heat resistance and impact resistance |
| KR102044172B1 (en) * | 2012-12-17 | 2019-11-14 | 도레이첨단소재 주식회사 | The method for preparing multi-layer sheet having a reinforced heat resistance and impact resistance |
| KR102164256B1 (en) * | 2018-10-19 | 2020-10-12 | 서울대학교산학협력단 | Biodegradable polymer composites having improved mechanical properties |
| CN114634769B (en) * | 2022-03-18 | 2023-07-14 | 揭阳市国为新技术有限公司 | Degradable in-mold label, preparation method thereof and treatment method of degradable plastic bottle |
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| JP2010053316A (en) * | 2008-08-29 | 2010-03-11 | Nippon A&L Inc | Thermoplastic resin composition |
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| JP2010053316A (en) * | 2008-08-29 | 2010-03-11 | Nippon A&L Inc | Thermoplastic resin composition |
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