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WO2018124743A2 - Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article - Google Patents

Polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article Download PDF

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Publication number
WO2018124743A2
WO2018124743A2 PCT/KR2017/015577 KR2017015577W WO2018124743A2 WO 2018124743 A2 WO2018124743 A2 WO 2018124743A2 KR 2017015577 W KR2017015577 W KR 2017015577W WO 2018124743 A2 WO2018124743 A2 WO 2018124743A2
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Prior art keywords
polyalkylene carbonate
resin composition
carbon atoms
carbonate
carbonate resin
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PCT/KR2017/015577
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French (fr)
Korean (ko)
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WO2018124743A3 (en
Inventor
박승영
김성경
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020170180257A external-priority patent/KR20180076350A/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780066381.5A priority Critical patent/CN110088196B/en
Priority to CA3044799A priority patent/CA3044799C/en
Priority to US16/465,976 priority patent/US10941291B2/en
Priority to JP2019519284A priority patent/JP6775681B2/en
Priority to EP17887519.1A priority patent/EP3533833B1/en
Publication of WO2018124743A2 publication Critical patent/WO2018124743A2/en
Publication of WO2018124743A3 publication Critical patent/WO2018124743A3/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a polyalkylene carbonate resin composition, and more specifically, to polyalkylene carbonate and polyketone, having excellent transparency and flexibility, oxygen barrier properties, mechanical and chemical properties, in particular excellent thermal stability It relates to a polyalkylene carbonate resin composition.
  • Polyalkylene carbonate is an amorphous transparent resin and has characteristics such as excellent transparency, excellent flexibility and high oxygen barrier property.
  • aromatic polycarbonate which is a similar series of engineering plastics, it has biodegradability and has no carbon residue since it is completely decomposed into carbon dioxide and water during combustion.
  • the present invention is to provide a resin composition capable of maintaining the inherent physical properties of polyalkylene carbonate and having excellent thermal stability and applicable to various fields.
  • the present invention provides a polyalkylene carbonaneart resin composition containing 1 to 100 parts by weight of polyketone, based on 100 parts by weight of polyalkylene carbonate.
  • the polyalkylene carbonate may include a repeating unit represented by the following formula (1).
  • R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms; Any two of R 1 to R 4 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms;
  • n is an integer of 10-1, 000.
  • Such polyalkylene carbonate is specifically, for example, polyethylene carbonate, polypropylene carbonate, polypentene carbonate, polynuxene It may be one or more selected from the group consisting of carbonates, polyoctene carbonates, polycyclonucleene carbonates and copolymers thereof.
  • the polyalkylene carbonate may have a weight average molecular weight of about 10, 000 to about l, 000, 00 () g / mol,
  • the polyketone may include a repeating unit represented by Formula 2 below.
  • the polyketone may be an aliphatic polyketone including ethylene, propylene, isopropylene, or butylene units.
  • the polyketone may be more preferably a binary copolymer or a ternary copolymer including two or more repeating units described above.
  • the polyketone has a weight average molecular weight of about 10, 000 to about l, 000, 000 g / n) l.
  • the polyalkylene carbonate resin composition may further include about 1 to about 30 parts by weight of polylactide based on 100 parts by weight of the polyalkylene carbonate.
  • the polyalkylene carbonate resin composition of the present invention may have a mass loss rate due to thermal decomposition at about 25 CTC when the mass loss rate according to the temperature change is about 1 (»or less).
  • this invention provides the polyalkylene carbonate resin molded article manufactured with the polyalkylene carbonate resin composition mentioned above. ⁇ Effects of the Invention ⁇
  • the polyalkylene carbonate resin composition according to the present invention has excellent thermal stability while maintaining the inherent physical properties of the polyalkylene carbonate, and is excellent in workability at high temperatures, and can be used in various fields.
  • 1 is illustrating a TGA analysis of the resin composition according to the embodiment, and comparative examples of the present invention graph.
  • the polyalkylene carbonate resin composition of this invention contains 1-100 weight part of polyketones with respect to 100 weight part of polyalkylene carbonates.
  • polyalkylene carbonate resin molded article of this invention is manufactured with the polyalkylene carbonate resin composition mentioned above.
  • terms such as first and second are used to describe various components, and the terms are used only to distinguish one component from another component.
  • polyalkylene carbonate resin composition according to an aspect of the present invention, 1 to 100 parts by weight of polyketone, based on 100 parts by weight of polyalkylene carbonate.
  • the polyalkylene carbonate may include a repeating unit represented by Formula 1 below.
  • R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms; Any two of R 1 to R 4 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms;
  • n is an integer of 10-1, 000.
  • the polyalkylene carbonate is, for example, one or more selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polypentene carbonate, polynuxene carbonate, polyoctene carbonate ⁇ polycyclonuxene carbonate, and copolymers thereof Can be.
  • the polyalkylene carbonate may have a weight average molecular weight of about 10,000 to about l, 000, 000 g / mol, preferably about 50, 000 to about 500, 000 g / mo 1.
  • Polyalkylene carbonate is an amorphous polymer containing a repeating unit represented by the formula (1).
  • the polyalkylene carbonate can be controlled within this range while having a relatively low glass transition temperature c of about 40 ° C., for example, about 10 to about 4 (rc about).
  • the manufacturing method of the polyalkylene carbonate used for this invention is not specifically limited, For example, it can obtain by copolymerizing an epoxide type compound and carbon dioxide. Or by ring-opening polymerization of cyclic carbonates. Copolymerization of the alkylene oxide and carbon dioxide can be carried out in the presence of a metal complex such as zinc or aluminum cobalt.
  • the epoxide compound is ethylene oxide, propylene oxide, 1-butene oxide 2—butene oxide, isobuty.
  • Such polyalkylene carbonate may be a homopolymer including a repeating unit represented by Formula 1; Or a copolymer including two or more repeating units belonging to the above Formula—1, or a copolymer including an alkylene oxide-based repeating unit together with the repeating unit represented by Formula 1.
  • the polyalkylene carbonate is represented by Chemical Formula 1 so that specific physical properties (eg elongation, flexibility, biodegradability or low glass transition temperature, etc.) due to the repeating unit represented by Chemical Formula 1 can be maintained. It may be a copolymer comprising at least about 40% by weight, preferably at least about 60% by weight, more preferably at least about 80% by weight, of at least one repeating unit.
  • the polyalkylene carbonate is, for example, polyethylene carbonate, polypropylene carbonate, polypentene carbonate, It may be polynucleene carbonate, polyoctene carbonate, polycyclonucenne carbonate, or a copolymer thereof, but is not limited thereto, and R1 to R4 may be used in consideration of physical properties of the resin to be finally obtained and a blend with polyketone. May be selected as appropriate functional groups.
  • the functional group when the functional group is hydrogen or a functional group having a relatively small carbon number, it may be more advantageous in terms of flexibility and compatibility with polyketone.
  • the functional group When the functional group has a relatively large carbon number, the mechanical properties such as the strength of the resin may be used. It may be advantageous from the side.
  • the polymerization degree m of the repeating unit represented by Formula 1 may be about 10 to 1,000.
  • polyalkylene carbonate is biodegradable with excellent transparency, flexibility, oxygen barrier properties, and mechanical properties, but due to low thermal stability, it easily decomposes when processed into pellets or films, and The disadvantage is that the temperature range is very narrow.
  • the inventors of the present invention have confirmed that the thermal stability of the polyalkylene carbonate resin can be significantly improved by using polyketone mixed with the polyalkylene carbonate, thereby completing the present invention.
  • the low thermal stability of polyalkylene carbonates is basically that when the hydrogen bonded to the hydroxy group at the end of the resin is released under high temperature conditions, the end of the resin becomes an anion, which attacks the carbonate group in the polymer chain close to the alkyl, This is due to the continuous reaction of the backbi ting, which shortens the length of the polymer chain while making a single molecule such as ethylene carbonate.
  • polymer resins are more advantageous than monomolecular substances having low melting points, because they can be put into the processing equipment in the form of pellets during processing, and do not require additional mixing equipment. This is because machining increases.
  • monomolecular substances after a certain time after processing The problem of migration to the surface of the product (migrat ion) may occur, which is advantageous in the case of a polymer resin because such a phenomenon rarely occurs.
  • polyketone its molecular structure is similar to that of polyalkylene carbonate, so that the compatibility between resins is very high. If there is a polyketone chain around the polyalkylene carbonate polymer chain, the negative oxygen at the end of the polyalkylene carbonate Since attacking hydrogen in the polyketone chain rather than the central carbon of the polyalkylene carbonate, it is possible to effectively suppress the above-mentioned back-biting reaction, and ultimately improve the thermal stability of the polyalkylene carbonate.
  • the polyketone may include a repeating unit represented by Formula 2 below.
  • the polyketone polymer having the above structure is prepared by reaction of a compound including carbon monoxide and an unsaturated double bond, and recently, an alternating copolymer in which repeating units composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon are alternately connected. Interest in the back is rising.
  • the polyketone resin can effectively prevent the phenomenon of polyalkylene carbonate decomposed by heat at a high temperature during processing of the polyalkylene carbonate resin composition, and can be processed at a high temperature. Workability can be exhibited.
  • Polyalkylene carbonate 100 may include at least 1 part by weight, more preferably about 5 parts by weight or about 10 parts by weight of polyketone, and does not impair the chemical and physical properties inherent to the polyalkylene carbonate resin. It may comprise up to 60 parts by weight, more preferably about 50 parts by weight, or up to about 30 parts by weight of polyketone, relative to parts by weight.
  • the polyketone is preferably an aliphatic polyketone containing ethylene, propylene, isopropylene, or butylene units.
  • the polyketone it may be preferable that the binary copolymer or ternary copolymer, specifically, for example, ethylene repeating unit, propylene repeating unit, isopropylene repeating unit, butyl Aliphatic polyketone forms of binary copolymers or ternary copolymers containing any one or more of lene repeat units can be used.
  • the binary copolymer or ternary copolymer specifically, for example, ethylene repeating unit, propylene repeating unit, isopropylene repeating unit, butyl Aliphatic polyketone forms of binary copolymers or ternary copolymers containing any one or more of lene repeat units can be used.
  • the polyketone may have a weight average molecular weight of about 10, 000 to about l, 000, 000 g / mol.
  • the polyalkylene carbonate resin composition may further include about 1 to about 30 parts by weight of polylactide based on 100 parts by weight of the polyalkylene carbonate.
  • the thermal stability of the polyalkylene carbonate can be primarily improved, whereby the kneading with the polyketone at a higher temperature can be more stably performed.
  • Lactide can be generally classified into L-lactide composed of L-lactic acid, D-lactide composed of D-lactic acid, and meso-lactide composed of one L-form and one D-form.
  • a mixture of L-lactide and D-lactide by 50:50 is referred to as D, L-lactide or racdecactide.
  • lactide polymerization using only L-lactide or D-lactide with high optical purity is known to yield L- or D-polylactide (PLLA or PDLA) having very high stereoregularity. Lactide is known to have higher crystallization rate and higher crystallization rate than polylactide having low optical purity.
  • lactide monomer herein is defined to include all types of lactide regardless of the difference in the properties of lactide according to each form and the difference in the properties of the polylactide formed therefrom.
  • the molecular structure of the polylactide may be polymerized from L-lactic acid, D-lactic acid or L, D-lactic acid.
  • the polylactide may be prepared by forming the following repeating unit by ring-opening polymerization of the lactide monomer, and the polymer after the process of forming the ring-opening polymerization and the repeating unit is completed may be referred to as the polylactide.
  • the lactide monomer may include all types of lactide as described above.
  • the polylactide may have a degree of polymerization of about 50 to 500, and may have a weight average molecular weight of about 100, 000 to about 1,000,000.
  • the polyalkylene carbonate resin composition can maintain the inherent physical properties of the polyalkylene carbonate and obtain a very excellent thermal stability effect even when processing at high temperatures. Can be.
  • polylactide includes polymers in all states after the ring-opening polymerization and the formation of the repeating unit are completed. For example, crude or purified after the ring-opening polymerization is completed. A polymer in a state, a polymer included in a liquid or solid resin composition before molding a product, or a polymer included in a plastic or a fabric finished molding a product, etc. may be all included. Or ring-opening polymerization of the lactide monomer under an organometallic catalyst. Polymer izat ion) is known.
  • the lactide monomer In the ring-opening polymerization method of lactide monomers, the lactide monomer must be prepared first from lactic acid, which makes the manufacturing process more complicated and requires higher cost than polycondensation polymerization.
  • the resin has a relatively large molecular weight through lactide ring-opening polymerization using an organometallic catalyst. Can be obtained relatively easily and control of the polymerization rate is advantageously applied commercially.
  • the resin composition of the present invention contains polyalkylene carbonate, polyketone, and polylactide in a specific ratio, and has excellent transparency, flexibility, oxygen barrier properties, mechanical properties, and biodegradability, and also between resins or products during processing. It has low inter-blocking phenomenon and excellent thermal stability. Therefore, it can be used not only for disposable products such as shopping bags and packaging films, but also for semi-permanent use of barrier multi-layer films, multilayer sheets, flooring materials, electronics packaging or automotive interior materials. .
  • the polyalkylene carbonate resin composition of the present invention may have a mass loss rate of about 10% or less due to thermal decomposition at about 25C C when the mass loss rate according to temperature change is measured.
  • the polyalkylene carbonate resin composition the mass loss rate due to pyrolysis at about 250 ° C when the mass loss rate according to the temperature change using a TGA analysis equipment is about 10% or less, preferably about 1 To 5%, more preferably no pyrolysis occurs at this temperature, and may have very low values with a mass loss of 0.5% or less.
  • the mass loss rate due to pyrolysis is about 20% or less, preferably about 1 to 1, and may have very good thermal stability, and therefore, workability at high temperature may also be very good.
  • Various additives can be added to the polyalkylene carbonate resin composition of this invention according to a use.
  • additives for modifying include, but are not limited to, additives for modifying, coloring agents (pigments, dyes, etc.), layering agents (carbon tablets, titanium oxide, talc, calcium carbonate, clay, and the like).
  • Modified additives include dispersants. Lubricants, plasticizers, flame retardants, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, crystallization accelerators and the like.
  • Various additives are used to pellet pellets from the polyalkylene carbonate resin composition. It may be added at the time of manufacture or when molding a pellet and manufacturing a molded object.
  • the manufacturing method of the polyalkylene carbonate resin composition of this invention various well-known methods can be used.
  • a method of obtaining a homogeneous mixture for example, the above-described polyalkylene carbonate, polyketone, polylactide and the like are added at a constant ratio, and a Hansel mixer, a ribbon blender, a blender, or the like. The mixing method is mentioned.
  • the melt kneading method a VAN Antonie Louis Barye mixer, a single or two-axis compressor, or the like can be used.
  • the shape of the resin composition of the present invention is not particularly limited, and for example, a fluid, a strand, a sheet, a film, or a pellet in which the mixture is melted It may be processed in such a way.
  • a polyalkylene carbonate resin molded article produced using the above-described polyalkylene carbonate resin composition.
  • Such molded articles may include, for example, films, film laminates, sheet filaments, nonwoven fabrics, injection molded articles, and the like.
  • the method for obtaining a molded article by molding the polyalkylene carbonate resin composition of the present invention is, for example, injection molding method, compression molding method, injection compression molding method, gas injection injection molding method, foam injection molding method, inflation method (inflation), T die method ( T die), calender (Calendar), blow molding (blow), vacuum molding, pressure forming, and the like, in addition to the processing method generally used in the technical field of the present invention can be used without particular limitation.
  • injection molding method compression molding method, injection compression molding method, gas injection injection molding method, foam injection molding method, inflation method (inflation), T die method ( T die), calender (Calendar), blow molding (blow), vacuum molding, pressure forming, and the like
  • injection molding method for example, injection molding method, compression molding method, injection compression molding method, gas injection injection molding method, foam injection molding method, inflation method (inflation), T die method ( T die), calender (Calendar), blow molding (blow), vacuum molding, pressure forming, and the like.
  • the resin composition thus prepared was prepared in the form of a film having a thickness of 100 using a twin screw extruder (BA-19, manufacturer: BAUTECH) to which T-die was fastened.
  • Example 2
  • the resin composition thus prepared was prepared in the form of a film having a thickness of 100 / im using a twin screw extruder (BA-19, manufacturer: BAUTECH) to which T-die was fastened.
  • Comparative Example 1 Comparative Example 1
  • the mass loss rate according to the temperature change was measured using a TGA analysis equipment.
  • TGA analysis measured under a nitrogen atmosphere at room temperature up to 550 ° C. at a rate of about 10 ° C./1 ⁇ 2 in. The results are shown in the graph of FIG. 1.
  • thermal decomposition starts from a temperature of about 180 ° C., and a half decomposition temperature (hal f loss). ) Is about 270 ° C, very weak at high conditions.
  • the polyalkylene carbonate resin composition according to the embodiment of the present invention it can be confirmed that has a high thermal stability, in particular excellent processability and heat even at high temperature processing conditions, such as forming a multilayer film or multilayer sheet by co-extrusion It can be assumed that it can have stability.

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Abstract

The present invention relates to a polyalkylene carbonate resin composition and, more specifically, to a polyalkylene carbonate resin composition containing a polyalkylene carbonate and a polyketone, having excellent transparency, flexibility, and mechanical and chemical properties, and exhibiting, especially, excellent thermal stability.

Description

【발명의 명칭】  [Name of invention]
폴리알킬렌 카보네이트 수지 조성물 및 폴리알킬렌 카보네이트 수지 성형품 【기술분야】  Polyalkylene Carbonate Resin Composition and Polyalkylene Carbonate Resin Molded Article
관련 출원 (들)과의 상호 인용  Cross Citation with Related Application (s)
본 출원은 2016년 12월 27일자 한국 특허 출원 제 10-2016-0180049호 및 2017년 12월 26일자 한국 특허 출원 제 10-2017-0180257호에 기초한 우선권의 이익을 주장하며， 해당 한국 특허 출원들의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다. 본 발명은 폴리알킬렌 카보네이트 수지 조성물에 대한 것으로， 더욱 구체적으로는， 폴리알킬렌 카보네이트 및 폴리케톤을 포함하며, 우수한 투명도와 유연성， 산소차단성， 기계적， 화학적 물성을 가지면서도， 특히 우수한 열적 안정성을 나타내는 폴리알킬렌 카보네이트 수지 조성물에 관한 것이다.  This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0180049 dated December 27, 2016 and Korean Patent Application No. 10-2017-0180257 dated December 26, 2017. All content disclosed in the literature is included as part of this specification. The present invention relates to a polyalkylene carbonate resin composition, and more specifically, to polyalkylene carbonate and polyketone, having excellent transparency and flexibility, oxygen barrier properties, mechanical and chemical properties, in particular excellent thermal stability It relates to a polyalkylene carbonate resin composition.
【배경기술】 Background Art
폴리알킬렌 카보네이트는 비결정성의 투명 수지로서， 우수한 투명도， 뛰어난 유연성， 높은 산소차단성 등의 특징을 가지고 있다. 또， 유사 계열의 엔지니어링 플라스틱인 방향족 폴리카보네이트와 달리， 생분해성을 나타내며 연소 시 이산화탄소와 물로 완전히 분해되어 탄소 잔류물이 없다는 장점을 가지고 있다.  Polyalkylene carbonate is an amorphous transparent resin and has characteristics such as excellent transparency, excellent flexibility and high oxygen barrier property. In addition, unlike the aromatic polycarbonate, which is a similar series of engineering plastics, it has biodegradability and has no carbon residue since it is completely decomposed into carbon dioxide and water during combustion.
그런데， 폴리알킬렌 카보네이트는 펠렛이나 필름 또는 시트 형태로 가공할 경우 자가점착성에 의해 수지 또는 제품 간 블로킹 (b locking) 현상이 나타나 취급이 용이하지 않고, 열 안정성이 낮아 가공조건이 매우 까다로운 단점이 있다.  However, when polyalkylene carbonate is processed into pellets, films, or sheets, blocking occurs between resins or products due to self-adhesiveness, so handling is not easy, and thermal stability is low, and processing conditions are very difficult. have.
그에 따라， 폴리알킬렌 카보네이트의 물성을 개선할 수 있는 다른 종류의 수지， 예를 들면， 폴리락타이드 등을 흔합하여 사용하려는 시도가 이루어지고 있다. 그런데， 이전에 알려진 폴리알킬렌 카보네이트와 폴리락타이드를 포함하는 수지 조성물은 폴리락타이드의 함량이 늘어날수록 폴리알킬렌 카보네이트가 갖는 고유의 물성이 급격하게 저하되는 등 물성 상쇄 정도가 크게 나타나고， 고온에서의 열 안정성 등의 물성 개선의 효과도 층분하지 않은 한계가 있다. Accordingly, attempts have been made to mix and use other types of resins, such as polylactide, which can improve the physical properties of polyalkylene carbonates. By the way, the resin composition containing the polyalkylene carbonate and polylactide known in the prior art exhibits a large degree of physical offset such that the inherent physical properties of the polyalkylene carbonate rapidly decrease as the content of the polylactide increases. The effects of improving physical properties such as thermal stability at Eq.
【발명의 상세한설명】 Detailed Description of the Invention
【기술적 과제】  [Technical problem]
본 발명은 폴리알킬렌 카보네이트가 가지는 고유의 물성을 유지할 수 있으면서도, 우수한 열 안정성을 가지고 있어， 다양한 분야에 응용이 가능한， 수지 조성물을 제공하기 위한 것이다.  The present invention is to provide a resin composition capable of maintaining the inherent physical properties of polyalkylene carbonate and having excellent thermal stability and applicable to various fields.
【기술적 해결방법】 Technical Solution
본 발명은， 폴리알킬렌 카보네이트 100중량부에 대하여， 폴리케톤 1 내지 100중량부를 포함하는， 폴리알킬렌 카보네아트 수지 조성물을 제공한다. 상기 폴리알킬렌 카보네이트는, 하기 화학식 1로 표시되는 반복 단위를 포함하는 것일 수 있다.  The present invention provides a polyalkylene carbonaneart resin composition containing 1 to 100 parts by weight of polyketone, based on 100 parts by weight of polyalkylene carbonate. The polyalkylene carbonate may include a repeating unit represented by the following formula (1).
[화학식 1]  [Formula 1]
Figure imgf000004_0001
Figure imgf000004_0001
상기 화학식 1에서，  In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소， 탄소수 1 내지 20의 선형 또는 분지형의 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 1 내지 20의 알케닐기 또는 탄소수 3 내지 20의 시클로알킬기이고; R1 내지 R4 중 적도 어느 두 개는 서로 연결되어 탄소수 3 내지 10의 사이클로알킬기를 형성할 수 있고; R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms; Any two of R 1 to R 4 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms;
m은 10 내지 1 , 000의 정수이다.  m is an integer of 10-1, 000.
이러한 폴리알킬렌 카보네이트는， 구체적으로 예를 들어， 폴리에틸렌 카보네이트， 폴리프로필렌 카보네이트, 폴리펜텐 카보네이트, 폴리핵센 카보네이트， 폴리옥텐 카보네이트， 폴리시클로핵센 카보네이트 및 이들의 공중합체로 이루어지는 군에서 선택된 1종 이상인 것일 수 있다. Such polyalkylene carbonate is specifically, for example, polyethylene carbonate, polypropylene carbonate, polypentene carbonate, polynuxene It may be one or more selected from the group consisting of carbonates, polyoctene carbonates, polycyclonucleene carbonates and copolymers thereof.
그리고， 상기 폴리알킬렌 카보네이트는, 중량 평균 분자량이 약 10 , 000 내지 약 l , 000 , 00()g/mol일 수 있다, In addition, the polyalkylene carbonate may have a weight average molecular weight of about 10, 000 to about l, 000, 00 () g / mol,
그리고， 상기 폴리케톤은， 하기 화학식 2로 표시되는 반복 단위를 포함하는 것일 수 있다.  The polyketone may include a repeating unit represented by Formula 2 below.
[화학식 2]
Figure imgf000005_0001
[Formula 2]
Figure imgf000005_0001
상기 화학식 2에서，  In Chemical Formula 2,
R은,  R is
탄소수 1 내지 10의， 선형 또는 분지형 알킬렌; 탄소수 1 내지 10의, 아릴렌; 탄소수 1 내지 10의, 알킬에테르; 탄소수 1 내지 10의， 아릴에테르; 탄소수 1 내지 10의 알킬에스터; 또는 탄소수 1 내지 10의， 아릴에스터이고 n은 10 내지 1000의 정수이다.  Linear or branched alkylene having 1 to 10 carbon atoms; Arylene having 1 to 10 carbon atoms; Alkyl ethers having 1 to 10 carbon atoms; Aryl ethers having 1 to 10 carbon atoms; Alkyl esters having 1 to 10 carbon atoms; Or an aryl ester having 1 to 10 carbon atoms and n is an integer of 10 to 1000.
더욱 구체적으로, 상기 폴리케톤은， 에틸렌， 프로필렌， 이소프로필렌， 또는 부틸렌 단위를 포함하는 지방족 폴리케톤일 수 있다.  More specifically, the polyketone may be an aliphatic polyketone including ethylene, propylene, isopropylene, or butylene units.
그리고, 상기 폴리케톤은， 상술한 반복단위를 둘 이상 포함하는， 2원 공중합체 또는 3원 공중합체인 것이 더욱 바람직할 수 있다.  The polyketone may be more preferably a binary copolymer or a ternary copolymer including two or more repeating units described above.
발명의 일 예에 따르면， 상기 폴리케톤은， 중량 평균 분자량이 약 10, 000 내지 약 l , 000, 000g/n )l인 것이 바람직할수 있다.  According to one embodiment of the invention, it is preferable that the polyketone has a weight average molecular weight of about 10, 000 to about l, 000, 000 g / n) l.
그리고， 본 발명의 다른 일 예에 따르면， 폴리알킬렌 카보네이트 수지 조성물은， 상기 폴리알킬렌 카보네이트 100중량부에 대하여， 폴리락타이드 약 1 내지 약 30중량부를 더 포함할 수도 있다.  In addition, according to another embodiment of the present invention, the polyalkylene carbonate resin composition may further include about 1 to about 30 parts by weight of polylactide based on 100 parts by weight of the polyalkylene carbonate.
이러한 조성으로 인하여， 본 발명의 폴리알킬렌 카보네이트 수지 조성물은， 온도 변화에 따른 질량 손실율을 측정하였을 때， 약 25CTC에서 열분해에 의한 질량 손실율이 약 1(» 이하일 수 있다.  Due to this composition, the polyalkylene carbonate resin composition of the present invention may have a mass loss rate due to thermal decomposition at about 25 CTC when the mass loss rate according to the temperature change is about 1 (»or less).
또한， 본 발명은, 상술한 폴리알킬렌 카보네이트 수지 조성물에 의해 제조되는， 폴리알킬렌 카보네이트 수지 성형품을 제공한다. 【발명의 효과】 Moreover, this invention provides the polyalkylene carbonate resin molded article manufactured with the polyalkylene carbonate resin composition mentioned above. 【Effects of the Invention】
본 발명에 따른 폴리알킬렌 카보네이트 수지 조성물은， 폴리알킬렌 카보네이트가 가지는 고유의 물성을 유지할 수 있으면서도, 우수한 열 안정성을 가지고 있어, 고온에서의 가공성이 우수하며， 다양한 분야에 웅용이 가능하다.  The polyalkylene carbonate resin composition according to the present invention has excellent thermal stability while maintaining the inherent physical properties of the polyalkylene carbonate, and is excellent in workability at high temperatures, and can be used in various fields.
[도면의 간단한 설명】 [Brief Description of Drawings]
도 1은 본 발명의 실시예 · 및 비교예에 따른 수지 조성물에 대한 TGA 분석 결과를 도시한그래프이다. 1 is illustrating a TGA analysis of the resin composition according to the embodiment, and comparative examples of the present invention graph.
【발명의 실시를 위한 형태】 [Form for implementation of invention]
본 발명의 폴리알킬렌 카보네이트 수지 조성물은， 폴리알킬렌 카보네이트 100중량부에 대하여， 폴리케톤 1 내지 100중량부를 포함한다.  The polyalkylene carbonate resin composition of this invention contains 1-100 weight part of polyketones with respect to 100 weight part of polyalkylene carbonates.
그리고， 본 발명의 폴리알킬렌 카보네이트 수지 성형품은, 상술한 폴리알킬렌 카보네이트 수지 조성물에 의해 제조된다. 본 명세서에서， 제 1， 제 2 등의 용어는 다양한 구성요소들을 설명하는데 사용되며， 상기 용어들은 하나의 구성 요소를 다른 구성 요소로부터 구별하는 목적으로만사용된다.  And the polyalkylene carbonate resin molded article of this invention is manufactured with the polyalkylene carbonate resin composition mentioned above. In this specification, terms such as first and second are used to describe various components, and the terms are used only to distinguish one component from another component.
또한， 본 명세서에서 사용되는 용어는 단지 예시적인 실시예들을 설명하기 위해 사용된 것으로， 본 발명을 한정하려는 의도는 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한， 복수의 표현을 포함한다. 본 명세서에서， "포함하다"， "구비하다" 또는 "가지다" 등의 용어는 실시된 특징， 숫자， 단계 , 구성 요소 또는 이들을 조합한 것이 존재함을 지정하려는 것이지 , 하나 또는 그 이상의 다른 특징들이나 숫자， 단계， 구성 요소， 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.  In addition, the terminology used herein is for the purpose of describing example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, and one or more other features, It is to be understood that the present invention does not exclude the possibility of adding or presenting numbers, steps, components, or a combination thereof.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 형태를 가질 수 있는 바ᅳ 특정 실시예들을 예시하고 하기에서 상세하게 설명하고자 한다. 그러나， 이는 본 발명을 특정한 개시 형태에 대해 한정하려는 것이 아니며， 본 발명의 사상 및 기술 범위에 포함되는 모든 변경， 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 이하， 본 발명의 폴리알킬렌 카보네이트 수지 조성물 및 폴리알킬렌 카보네이트 수지 성형품을 상세하게 설명한다 . 본 발명의 일 측면에 따른 폴리알킬렌 카보네이트 수지 조성물은， 폴리알킬렌 카^네이트 100중량부에 대하여， 폴리케톤 1 내지 100중량부를 포함한다. The present invention is intended to illustrate specific embodiments that can be modified in various ways and to have a variety of forms and will be described in detail below. But, It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and it is to be understood that the invention includes all modifications, equivalents, and substitutes included in the spirit and scope of the invention. Hereinafter, the polyalkylene carbonate resin composition and polyalkylene carbonate resin molded article of this invention are demonstrated in detail. Polyalkylene carbonate resin composition according to an aspect of the present invention, 1 to 100 parts by weight of polyketone, based on 100 parts by weight of polyalkylene carbonate.
상기 폴리알킬렌 카보네이트는， 하기 화학식 1로 표시되는 반복 단위를 포함하는 것일 수 있다.  The polyalkylene carbonate may include a repeating unit represented by Formula 1 below.
1]  One]
Figure imgf000007_0001
Figure imgf000007_0001
상기 화학식 1에서，  In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소， 탄소수 1 내지 20의 선형 또는 분지형의 알킬기， 탄소수 6 내지 20의 아릴기， 탄소수 1 내지 20의 알케닐기 또는 탄소수 3 내지 20의 시클로알킬기이고; R1 내지 R4 중 적도 어느 두 개는 서로 연결되어 탄소수 3 내지 10의 사이클로알킬기를 형성할 수 있고; R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms; Any two of R 1 to R 4 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms;
m은 10 내지 1 , 000의 정수이다.  m is an integer of 10-1, 000.
이러한 폴리알킬렌 카보네이트는, 구체적으로 예를 들어， 폴리에틸렌 카보네이트， 폴리프로필렌 카보네이트， 폴리펜텐 카보네이트， 폴리핵센 카보네이트， 폴리옥텐 카보네이트ᅳ 폴리시클로핵센 카보네이트 및 이들의 공중합체로 이루어지는 군에서 선택된 1종 이상인 것일 수 있다.  Specifically, the polyalkylene carbonate is, for example, one or more selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polypentene carbonate, polynuxene carbonate, polyoctene carbonate ᅳ polycyclonuxene carbonate, and copolymers thereof Can be.
그리고， 상기 폴리알킬렌 카보네이트는， 중량 평균 분자량이 약 10，000 내지 약 l , 000 , 000g/mol , 바람직하게는 약 50 , 000 내지 약 500， 000g/mo 1일 수 있다. 폴리알킬렌 카보네이트는 상기 화학식 1로 표시되는 반복 단위를 포함하는 비결정성의 고분자이다. The polyalkylene carbonate may have a weight average molecular weight of about 10,000 to about l, 000, 000 g / mol, preferably about 50, 000 to about 500, 000 g / mo 1. Polyalkylene carbonate is an amorphous polymer containing a repeating unit represented by the formula (1).
또한， 상기 폴리알킬렌 카보네이트는 약 40°C 이하, 예를 들어， 약 10 내지 약 4(rc 정도의 비교적 낮은 유리전이온도 c )를 가지면서 이 범위 내에서의 조절이 가능하다. In addition, the polyalkylene carbonate can be controlled within this range while having a relatively low glass transition temperature c of about 40 ° C., for example, about 10 to about 4 (rc about).
본 발명에 사용되는 폴리알킬렌 카보네이트의 제조 방법은 특별히 한정되지는 않지만， 예를 들면， 에폭사이드계 화합물과 이산화탄소를 공중합하여 얻어질 수 있다. 또는 환상 카보네이트의 개환중합에 의해서도 얻어질 수 있다. 상기 알킬렌 옥사이드와 이산화탄소의 공중합은 아연， 알루미늄 코발트 등의 금속 착화합물의 존재 하에서 행할 수 있다.  Although the manufacturing method of the polyalkylene carbonate used for this invention is not specifically limited, For example, it can obtain by copolymerizing an epoxide type compound and carbon dioxide. Or by ring-opening polymerization of cyclic carbonates. Copolymerization of the alkylene oxide and carbon dioxide can be carried out in the presence of a metal complex such as zinc or aluminum cobalt.
유기금속 촉매의 존재 하에 에폭사이드계 화합물과 이산화탄소를 사용하여 공중합을 통해 폴리알킬렌 카보네이트를 제조하는 경우， 상기 에폭사이드계 화합물은 에틸렌 옥사이드， 프로필렌 옥사이드， 1-부텐 옥사이드 2—부텐 옥사이드， 이소부티렌 옥사이드， 1-펜텐 옥사이드， 2-펜텐 옥사이드， 1-핵센 옥사이드， 1-옥텐 옥사이드， 시클로펜텐 옥사이드， 시클로핵센 옥사이드, 스티렌 옥사이드 또는 부타디엔 모노옥사이드 등이나， 이들 중에 선택된 2종 이상의 다양한 에폭사이드계 화합물일 수 있으나， 이에 한정되는 것은 아니다.  When the polyalkylene carbonate is prepared by copolymerization using an epoxide compound and carbon dioxide in the presence of an organometallic catalyst, the epoxide compound is ethylene oxide, propylene oxide, 1-butene oxide 2—butene oxide, isobuty. Ethylene oxide, 1-pentene oxide, 2-pentene oxide, 1-nuxene oxide, 1-octene oxide, cyclopentene oxide, cyclonuxene oxide, styrene oxide or butadiene monooxide, etc. It may be a compound, but is not limited thereto.
이러한 폴리알킬렌 카보네이트는 상기 화학식 1로 표시되는 반복 단위를 포함하는 단일 중합체일 수 있으며; 또는 상기 화학식— 1의 범주에 속하는 2 종 이상의 반복 단위를 포함하는 공중합체이거나, 상기 화학식 1로 표시되는 반복 단위와 함께 알킬렌 옥사이드계 반복 단위 등을 포함하는 공중합체일 수 있다.  Such polyalkylene carbonate may be a homopolymer including a repeating unit represented by Formula 1; Or a copolymer including two or more repeating units belonging to the above Formula—1, or a copolymer including an alkylene oxide-based repeating unit together with the repeating unit represented by Formula 1.
다만, 상기 화학식 1로 표시되는 반복 단위로 인한 특유의 물성 (예를 들어 신율， 유연성， 생분해성 또는 낮은 유리 전이 온도 등)이 유지될 수 있도록， 상기 폴리알킬렌 카보네이트는 상기 화학식 1로 표시되는 반복 단위의 1 종 이상을 약 40 중량 % 이상， 바람직하게는 약 60 중량 % 이상, 보다 바람직하게는 약 80 중량 % 이상으로 포함하는 공중합체로 될 수 있다.  However, the polyalkylene carbonate is represented by Chemical Formula 1 so that specific physical properties (eg elongation, flexibility, biodegradability or low glass transition temperature, etc.) due to the repeating unit represented by Chemical Formula 1 can be maintained. It may be a copolymer comprising at least about 40% by weight, preferably at least about 60% by weight, more preferably at least about 80% by weight, of at least one repeating unit.
본 발명의 일 실시예에 따르면， 상기 폴리알킬렌 카보네이트는， 예를 들면， 폴리에틸렌 카보네이트， 폴리프로필렌 카보네이트， 폴리펜텐 카보네이트, 폴리핵센 카보네이트， 폴리옥텐 카보네이트， 폴리시클로핵센 카보네이트, 또는 이들의 공중합체일 수 있으나， 이에 한정되는 것은 아니며， 상기 R1 내지 R4는 최종적으로 얻고자 하는 수지의 물성 및 폴리케톤과의 블렌드를 고려하여 적절한 작용기로 선택될 수 있다. According to one embodiment of the invention, the polyalkylene carbonate is, for example, polyethylene carbonate, polypropylene carbonate, polypentene carbonate, It may be polynucleene carbonate, polyoctene carbonate, polycyclonucenne carbonate, or a copolymer thereof, but is not limited thereto, and R1 to R4 may be used in consideration of physical properties of the resin to be finally obtained and a blend with polyketone. May be selected as appropriate functional groups.
예를 들어， 상기 작용기가 수소이거나 상대적으로 작은 탄소수를 갖는 작용기일 경우에는 유연성 및 폴리케톤과의 상용성 측면에서 보다 유리할 수 있고， 상대적으로 많은 탄소수를 갖는 작용기일 경우 수지의 강도 등 기계적 물성의 측면에서 유리할 수 있다.  For example, when the functional group is hydrogen or a functional group having a relatively small carbon number, it may be more advantageous in terms of flexibility and compatibility with polyketone. When the functional group has a relatively large carbon number, the mechanical properties such as the strength of the resin may be used. It may be advantageous from the side.
그리고， 상기 폴리알킬렌 카보네이트에서， 상기 화학식 1로 표시되는 반복 단위의 중합도 m은 약 10 내지 1 , 000으로 될 수 있다.  In addition, in the polyalkylene carbonate, the polymerization degree m of the repeating unit represented by Formula 1 may be about 10 to 1,000.
폴리알킬렌 카보네이트는， 상술한 바와 같이, 우수한 투명성, 유연성， 산소차단성， 기계적 물성과 함께 생분해성을 가지지만， 낮은 열 안정성으로 인해， 펠렛이나 필름 형태로 가공할 경우 쉽게 분해가 일어나고, 가공 온도 영역이 매우 좁은 단점이 있다.  As described above, polyalkylene carbonate is biodegradable with excellent transparency, flexibility, oxygen barrier properties, and mechanical properties, but due to low thermal stability, it easily decomposes when processed into pellets or films, and The disadvantage is that the temperature range is very narrow.
본 발명의 발명자들은, 폴리알킬렌 카보네이트에 폴리케톤을 혼합 사용하여, 폴리알킬렌 카보네이트 수지의 열 안정성을 획기적으로 향상시킬 수 있음을 확인하여 본 발명을 완성하게 되었다.  The inventors of the present invention have confirmed that the thermal stability of the polyalkylene carbonate resin can be significantly improved by using polyketone mixed with the polyalkylene carbonate, thereby completing the present invention.
폴리알킬렌 카보네이트의 낮은 열 안정성은， 기본적으로, 수지 말단의 히드록시 그룹에 결합되어 있는 수소가 고온 조건에서 이탈되면서， 수지 말단이 음이온으로 되고， 이것이 가까운 고분자 체인 내의 카보네이트 그룹을 공격하여， 알킬렌 카보네이트와 같은 단분자를 만들면서 고분자 체인의 길이가 짧아지는 백바이팅 (backbi t ing) 반응이 연속적으로 일어나는 현상에 기인하는 것이다.  The low thermal stability of polyalkylene carbonates is basically that when the hydrogen bonded to the hydroxy group at the end of the resin is released under high temperature conditions, the end of the resin becomes an anion, which attacks the carbonate group in the polymer chain close to the alkyl, This is due to the continuous reaction of the backbi ting, which shortens the length of the polymer chain while making a single molecule such as ethylene carbonate.
따라서, 이를 억제하여， 열 안정성을 향상시키기 위해서는， 폴리알킬렌 카보네이트와 상용성이 우수하면서도 백바이팅 반응을 효과적으로 억제할 수 있는 물질이 요구된다.  Therefore, in order to suppress this and to improve thermal stability, a material having excellent compatibility with polyalkylene carbonate and capable of effectively suppressing the backbiting reaction is required.
이 경우， 특히 녹는점이 낮은 단분자 형태의 물질보다는, 고분자 수지가 유리한데， 그 이유는, 가공 시， 펠렛 형태로 가공 설비에 투입이 가능하여， 추가적인 흔련 (mixing) 설비를 필요로 하지 않고， 가공 증 흔련이 가능하기 때문이다. 또한， 단분자 물질의 경우， 가공 후 일정 시간이 지나면 제품의 .표면으로 유출 (migrat ion)되는 문제가 발생하기도 하는데， 고분자 수지의 경우, 이러한 현상이 거의 발생하지 않기 때문에 유리하다. In this case, in particular, polymer resins are more advantageous than monomolecular substances having low melting points, because they can be put into the processing equipment in the form of pellets during processing, and do not require additional mixing equipment. This is because machining increases. In addition, in the case of monomolecular substances, after a certain time after processing The problem of migration to the surface of the product (migrat ion) may occur, which is advantageous in the case of a polymer resin because such a phenomenon rarely occurs.
폴리케톤의 경우， 그 분자 구조가 폴리알킬렌 카보네이트와 유사하여 수지 간 상용성이 매우 높으며 , 폴리알킬렌 카보네이트 고분자 체인 주변에 폴리케톤 체인이 있으면， 폴리알킬렌 카보네이트 말단의 음이은 상태의 산소가， 폴리알킬렌 카보네이트의 중심 탄소보다 폴리케톤 체인 내의 수소를 공격하기 때문에， 상술한 백바이팅 반응을 효과적으로 억제하여， 궁극적으로 폴리알킬렌 카보네이트의 열 안정성을 향상시킬 수 있게 된다.  In the case of polyketone, its molecular structure is similar to that of polyalkylene carbonate, so that the compatibility between resins is very high. If there is a polyketone chain around the polyalkylene carbonate polymer chain, the negative oxygen at the end of the polyalkylene carbonate Since attacking hydrogen in the polyketone chain rather than the central carbon of the polyalkylene carbonate, it is possible to effectively suppress the above-mentioned back-biting reaction, and ultimately improve the thermal stability of the polyalkylene carbonate.
상기 폴리케톤은， 하기 화학식 2로 표시되는 반복 단위를 포함하는 것일 수 있다.  The polyketone may include a repeating unit represented by Formula 2 below.
[화학식 2]
Figure imgf000010_0001
[Formula 2]
Figure imgf000010_0001
상기 화학식 2에서，  In Chemical Formula 2,
R은，  R is
탄소수 1 내지 10의, 선형 또는 분지형 알킬렌; 탄소수 1 내지 10와， 아릴렌; 탄소수 1 내지 10의， 알킬에테르; 탄소수 1 내지 10의， 아릴에테르; 탄소수 1 내지 10의 알킬에스터; 또는 탄소수 1 내지 10의， 아릴에스터이고， n은 10 내지 1000의 정수이다.  Linear or branched alkylene having 1 to 10 carbon atoms; C1-C10, arylene; Alkyl ether of 1 to 10 carbon atoms; Aryl ethers having 1 to 10 carbon atoms; Alkyl esters having 1 to 10 carbon atoms; Or an aryl ester having 1 to 10 carbon atoms, and n is an integer of 10 to 1000.
상기와 같은 구조의 폴리케톤 고분자는 일산화탄소 및 불포화 이중결합을 포함하는 화합물의 반웅에 의해 제조되며， 최근에는， 일산화탄소 및 적어도 1종 이상의 에틸렌성 불포화 탄화수소로 구성되는 반복 단위가 교대로 이어지는 교호 공중합체 등에 대한 관심이 높아지고 있다.  The polyketone polymer having the above structure is prepared by reaction of a compound including carbon monoxide and an unsaturated double bond, and recently, an alternating copolymer in which repeating units composed of carbon monoxide and at least one ethylenically unsaturated hydrocarbon are alternately connected. Interest in the back is rising.
폴리케톤 수지는， 상술한 원리에 따라 폴리알킬렌 카보네이트 수지 조성물의 가공 시， 높은 온도에서 열에 의해 폴리알킬렌 카보네이트가 분해되는 현상을 효과적으로 방지할 수 있으며， 높은 온도에서의 가공을 가능케 하여， 뛰어난 가공성을 나타낼 수 있게 된다.  The polyketone resin, according to the above-described principle, can effectively prevent the phenomenon of polyalkylene carbonate decomposed by heat at a high temperature during processing of the polyalkylene carbonate resin composition, and can be processed at a high temperature. Workability can be exhibited.
구체적으로， 본 발명의 일 예에 따른 폴리알킬렌 카보네이트 수지 조성물은， 상술한 효과를 위하여, 폴리알킬렌 카보네이트 100중량부에 대하여， 1중량부 이상， 더욱 바람직하게는 약 5중량부 또는 약 10중량부 이상의 폴리케톤을 포함할 수 있으며， 폴리알킬렌 카보네이트 수지 고유의 화학적 물리적 물성을 저해하지 아니하는 범위에서， 폴리알킬렌 카보네이트 100중량부에 대하여， 60중량부 이하， 더욱 바람직하게는 약 50 중량부, 또는 약 30중량부 이하의 폴리케톤을 포함할 수 있다. Specifically, the polyalkylene carbonate resin composition according to an embodiment of the present invention, for the above-described effect, based on 100 parts by weight of polyalkylene carbonate, Polyalkylene carbonate 100 may include at least 1 part by weight, more preferably about 5 parts by weight or about 10 parts by weight of polyketone, and does not impair the chemical and physical properties inherent to the polyalkylene carbonate resin. It may comprise up to 60 parts by weight, more preferably about 50 parts by weight, or up to about 30 parts by weight of polyketone, relative to parts by weight.
폴리케톤이 상기 범위보다 적은 양으로 사용되는 경우， 폴리알킬렌 카보네이트의 고온 안정성을 높일 수 있는 상술한 본 발명의 효과가 기대에 미치지 못하는 문제점이 발생할 수 있으며， 폴리케톤이 지나치게 많이 사용되는 경우 폴리알킬렌 카보네이트의 고유한 물리적， 화학적 성질이 발현되기 어려운 문제점이 발생할 수 있다.  When the polyketone is used in an amount less than the above range, the above-described effects of the present invention, which can increase the high temperature stability of the polyalkylene carbonate, may occur. The inherent physical and chemical properties of alkylene carbonate may be difficult to express.
발명의 일 실시예에 따르면， 상기 폴리케톤은， 에틸렌， 프로필렌， 이소프로필렌， 또는 부틸렌 단위를 포함하는 지방족 폴리케톤인 것아바람직할 수 있다.  According to one embodiment of the invention, the polyketone is preferably an aliphatic polyketone containing ethylene, propylene, isopropylene, or butylene units.
그리고， 발명의 일 실시예에 따르면， 상기 폴리케톤은， 2원 공중합체 또는 3원 공중합체인 것이 바람직할 수 있으며， 구체적으로 예를 들면， 에틸렌 반복 단위， 프로필렌 반복 단위, 이소프로필렌 반복 단위, 부틸렌 반복 단위 중 어느 하나 이상을 포함하는， 2원 공중합체， 또는 3원 공중합체의 지방족 폴리 케톤 형태를 사용할 수 있다.  And, according to one embodiment of the invention, the polyketone, it may be preferable that the binary copolymer or ternary copolymer, specifically, for example, ethylene repeating unit, propylene repeating unit, isopropylene repeating unit, butyl Aliphatic polyketone forms of binary copolymers or ternary copolymers containing any one or more of lene repeat units can be used.
그리고， 상기 폴리케톤은， 중량 평균 분자량이 약 10 , 000 내지 약 l , 000 , 000g/mol일 수 있다. The polyketone may have a weight average molecular weight of about 10, 000 to about l, 000, 000 g / mol.
그리고， 본 발명의 다른 일 예에 따르면， 폴리알킬렌 카보네이트 수지 조성물은， 상기 폴리알킬렌 카보네이트 100중량부에 대하여， 폴리락타이드 약 1 내지 약 30증량부를 더 포함할 수도 있다. 폴리락타아드를 흔합 사용하는 경우， 폴리알킬렌 카보네이트의 열 안정성을 일차적으로 향상시킬 수 있으며, 이로 인해， 보다 고온에서의 폴리케톤과의 혼련을 보다 안정적으로 수행할 수 있다. 폴리락타이드가 상기 범위보다 지나치게 적게 포함하는 경우, 고은에서 폴리케톤과 폴리알킬렌 카보네이트의 흔련 시， 폴뫼알킬렌 카보네이트의 분해가 일어날 수 있으며， 폴리락타이드가 상기 범위보다 지나치게 많이 포함되는 경우， 폴리알킬렌 카보네이트의 고유한 물성을 잃게되는 문제점이 발생할 수 있다. 통상 락타이드는 L-락트산으로 이루어진 L-락타이드， D-락트산으로 이루어진 D-락타이드， L-형태와 D-형태가 각각 하나씩으로 이루어진 meso- 락타이드로 구분될 수 있다. 또한， L-락타이드와 D-락타이드가 50 : 50으로 섞여 있는 것을 D ,L-락타이드 혹은 racᅳ락타이드라고 한다. 이들 락타이드 중 광학적 순도가 높은 L-락타이드 혹은 D-락타이드만을 이용해 중합을 진행하면 입체 규칙성이 매우 높은 L- 혹은 D-폴리락타이드 (PLLA혹은 PDLA)가 얻어지는 것으로 알려져 있고， 이러한 폴리락타이드는 광학적 순도가 낮은 폴리락타이드 대비 결정화 속도가 빠르고 결정화도 또한 높은 것으로 알려져 있다. 다만， 본 명세서에서 "락타이드 모노머 "라 함은 각 형태에 따른 락타이드의 특성 차이 및 이로부터 형성된 폴리락타이드의 특성 차이에 관계없이 모든 형태의 락타이드를 포함하는 것으로 정의된다. In addition, according to another embodiment of the present invention, the polyalkylene carbonate resin composition may further include about 1 to about 30 parts by weight of polylactide based on 100 parts by weight of the polyalkylene carbonate. When the polylactide is used in combination, the thermal stability of the polyalkylene carbonate can be primarily improved, whereby the kneading with the polyketone at a higher temperature can be more stably performed. When the polylactide contains too less than the above range, when the polyketone and the polyalkylene carbonate are stirred in the silver, the decomposition of the polmoalkylene carbonate may occur, and when the polylactide is included more than the above range, The problem of losing the inherent physical properties of polyalkylene carbonate can occur. Lactide can be generally classified into L-lactide composed of L-lactic acid, D-lactide composed of D-lactic acid, and meso-lactide composed of one L-form and one D-form. In addition, a mixture of L-lactide and D-lactide by 50:50 is referred to as D, L-lactide or racdecactide. Among these lactides, polymerization using only L-lactide or D-lactide with high optical purity is known to yield L- or D-polylactide (PLLA or PDLA) having very high stereoregularity. Lactide is known to have higher crystallization rate and higher crystallization rate than polylactide having low optical purity. However, the term "lactide monomer" herein is defined to include all types of lactide regardless of the difference in the properties of lactide according to each form and the difference in the properties of the polylactide formed therefrom.
폴리락타이드의 분자구조로서는 L-락트산， D-락트산 또는 L ,D- 락트산으로부터 중합되는 것일 수 있다. 폴리락타이드는 락타이드 모노머의 개환 중합에 의해 하기 반복 단위를 형성하는 단계를 포함하여 제조될 수 있으며， 이러한 개환 중합 및 반복 단위의 형성 공정이 완료된 후의 폴리머를 상기 폴리락타이드로 지칭할 수 있다. 이때， 락타이드 모노머의 범주에는 상술한 바와 같이 모든 형태의 락타이드가 포함될 수 있다.  The molecular structure of the polylactide may be polymerized from L-lactic acid, D-lactic acid or L, D-lactic acid. The polylactide may be prepared by forming the following repeating unit by ring-opening polymerization of the lactide monomer, and the polymer after the process of forming the ring-opening polymerization and the repeating unit is completed may be referred to as the polylactide. . In this case, the lactide monomer may include all types of lactide as described above.
본 발명의 일 실시예에 따르면, 상기 폴리락타이드는， 중합도가 약 바람직하게는 50 내지 500으로 될 수 있고， 약 100, 000 내지 약 1，000，000의 중량 평균 분자량을 가질 수 있다. 상기 폴리락타이드가 상기 중합도 및 중량 평균 분자량을 가짐에 따라， 이로부터 폴리알킬렌 카보네이트 수지 조성물이 폴리알킬렌 카보네이트의 고유한 물성을 유지할 수 있으며, 고온에서 가공 시에도 매우 우수한 열 안정성 효과를 얻을 수 있다.  According to an embodiment of the present invention, the polylactide may have a degree of polymerization of about 50 to 500, and may have a weight average molecular weight of about 100, 000 to about 1,000,000. As the polylactide has the polymerization degree and the weight average molecular weight, from this, the polyalkylene carbonate resin composition can maintain the inherent physical properties of the polyalkylene carbonate and obtain a very excellent thermal stability effect even when processing at high temperatures. Can be.
상기 "폴리락타이드' '로 지칭될 수 있는 폴리머의 범주에는， 상기 개환 중합 및 반복 단위의 형성 공정이 완료된 후의 모든 상태의 폴리머.， 예를 들어， 상기 개환 중합이 완료된 후의 미정제 또는 정제된 상태의 폴리머， 제품 성형 전의 액상 또는 고상의 수지 조성물에 포함된 폴리머, 또는 제품 성형이 완료된 플라스틱 또는 직물 등에 포함된 폴리머 등이 모두 포함될 수 있다. 폴리락타이드의 제조 방법으로는 락트산을 직접 축중합하거나， 상기 락타이드 모노머를 유기 금속 촉매 하에 개환 중합 (r ing opening polymer izat ion)하는 방법이 알려져 있다. 락타이드 모노머의 개환 중합 방법은 락트산에서 락타이드 모노머를 먼저 제조하여야 하므로 축중합에 비해 제조공정이 복잡하고 높은 단가가 소요되지만， 유기금속 촉매를 이용한 락타이드 개환중합을 통해서 상대적으로 큰 분자량의 수지를 비교적 용이하게 얻을 수 있고 중합속도의 조절이 유리해서 상업적으로 적용되고 있다. The category of the polymer which may be referred to as “polylactide” includes polymers in all states after the ring-opening polymerization and the formation of the repeating unit are completed. For example, crude or purified after the ring-opening polymerization is completed. A polymer in a state, a polymer included in a liquid or solid resin composition before molding a product, or a polymer included in a plastic or a fabric finished molding a product, etc. may be all included. Or ring-opening polymerization of the lactide monomer under an organometallic catalyst. Polymer izat ion) is known. In the ring-opening polymerization method of lactide monomers, the lactide monomer must be prepared first from lactic acid, which makes the manufacturing process more complicated and requires higher cost than polycondensation polymerization. However, the resin has a relatively large molecular weight through lactide ring-opening polymerization using an organometallic catalyst. Can be obtained relatively easily and control of the polymerization rate is advantageously applied commercially.
본 발명의 수지 조성물은 폴리알킬렌 카보네이트， 폴리케톤， 및 폴리락타이드를 특정 비율로 포함하여， 우수한 투명성， 유연성， 산소차단성， 기계적 물성， 생분해성을 갖고 있으면서도， 가공과정에서 수지간 또는 제품간 블로킹현상이 적고， 열적 안정성 또한 뛰어나며， 이에 따라， 쇼핑백， 포장 필름 등 일회용품 뿐만 아니라, 차단성 다층필름이나 다층시트， 바닥재， 전자제품 패키징 혹은 자동차 내장재 등의 반영구적 용도로도 바람직하게 사용될 수 있다.  The resin composition of the present invention contains polyalkylene carbonate, polyketone, and polylactide in a specific ratio, and has excellent transparency, flexibility, oxygen barrier properties, mechanical properties, and biodegradability, and also between resins or products during processing. It has low inter-blocking phenomenon and excellent thermal stability. Therefore, it can be used not only for disposable products such as shopping bags and packaging films, but also for semi-permanent use of barrier multi-layer films, multilayer sheets, flooring materials, electronics packaging or automotive interior materials. .
이러한 조성으로 인하여, 본 발명의 폴리알킬렌 카보네이트 수지 조성물은， 온도 변화에 따른 질량 손실율을 측정하였을 때, 약 25C C에서 열분해에 의한 질량 손실율이 약 10% 이하일 수 있다.  Due to this composition, the polyalkylene carbonate resin composition of the present invention may have a mass loss rate of about 10% or less due to thermal decomposition at about 25C C when the mass loss rate according to temperature change is measured.
더욱 구체적으로， 상기 폴리알킬렌 카보네이트 수지 조성물은， TGA분석 장비를 이용하여 온도 변화에 따른 질량 손실율을 측정하였을 때 약 250°C에서 열분해에 의한 질량 손실율이 약 10% 이하， 바람직하게는 약 1 내지 5% , 더욱 바람직하게는 상기 온도에서 열 분해가 발생하지 않아， 질량 손실이 0.5% 이하인 매우 낮은 수치를 가질 수 있다. 또한, 약 30CTC의 온도에서도， 열분해에 의한 질량 손실율이 약 20% 이하， 바람직하게는 약 1 내지 로， 매우 우수한 열 안정성을 가질 수 있으며， 이에 따라, 고온에서의 가공성 역시 매우 우수할 수 있다. 본 발명의 폴리알킬렌 카보네이트 수지 조성물에는 용도에 따라 각종의 첨가제를 첨가할 수 있다. 예를 들면, 개질용 첨가제， 착색제 (안료， 염료 등) , 층진제 (카본블택, 산화티탄， 활석， 탄산칼슘， 클레이 등) 등을 들 수 있으며 이에 한정되지 않는다. 개질용 첨가제로는 분산제. 윤활제， 가소제， 난연제， 산화방지제， 대전 방지제， 광안정제， 자외선 흡수제， 결정화 촉진제 등을 들 수 있다. 각종 첨가제는 폴리알킬렌 카보네이트 수지 조성물로부터 펠렛을 제조할 때 또는 펠렛을 성형하여 성형체를 제조할 때 첨가할 수도 있다. More specifically, the polyalkylene carbonate resin composition, the mass loss rate due to pyrolysis at about 250 ° C when the mass loss rate according to the temperature change using a TGA analysis equipment is about 10% or less, preferably about 1 To 5%, more preferably no pyrolysis occurs at this temperature, and may have very low values with a mass loss of 0.5% or less. In addition, even at a temperature of about 30CTC, the mass loss rate due to pyrolysis is about 20% or less, preferably about 1 to 1, and may have very good thermal stability, and therefore, workability at high temperature may also be very good. Various additives can be added to the polyalkylene carbonate resin composition of this invention according to a use. Examples include, but are not limited to, additives for modifying, coloring agents (pigments, dyes, etc.), layering agents (carbon tablets, titanium oxide, talc, calcium carbonate, clay, and the like). Modified additives include dispersants. Lubricants, plasticizers, flame retardants, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, crystallization accelerators and the like. Various additives are used to pellet pellets from the polyalkylene carbonate resin composition. It may be added at the time of manufacture or when molding a pellet and manufacturing a molded object.
본 발명의 폴리알킬렌 카보네이트 수지 조성물의 제조 방법으로는 공지의 각종 방법을 사용할 수 있다. 균일한 혼합물을 얻는 방법으로는 예를 들면， 상술한 폴리알킬렌 카보네이트， 폴리케톤， 및 폴리락타이드 등을 일정한 비율로 첨가하고， 헨젤믹서， 리본 흔합기 (ribbon blender), 혼합기 (blender) 등에 의하여 혼합하는 방법을 들 수 있다.  As the manufacturing method of the polyalkylene carbonate resin composition of this invention, various well-known methods can be used. As a method of obtaining a homogeneous mixture, for example, the above-described polyalkylene carbonate, polyketone, polylactide and the like are added at a constant ratio, and a Hansel mixer, a ribbon blender, a blender, or the like. The mixing method is mentioned.
용융 흔련 방법으로는 밴 배리 믹서 (VAN Antonie Louis Barye mixer), 1축 또는 2축 압축기 등을 이용할 수 있다. 본 발명의 수지 조성물의 형상은 특별한 제한이 없으며， 예를 들면, 흔합물이 용융된 유체상 (compound), 스트랜드 (strand), 시트상 (sheet), 평판상 (film), 펠렛상 (pellet) 등으로 가공한 것일 수도 있다.  As the melt kneading method, a VAN Antonie Louis Barye mixer, a single or two-axis compressor, or the like can be used. The shape of the resin composition of the present invention is not particularly limited, and for example, a fluid, a strand, a sheet, a film, or a pellet in which the mixture is melted It may be processed in such a way.
본 발명의 또 다른 일 측면에 따르면， 상술한 폴리알킬렌 카보네이트 수지 조성물을 이용하여 제조되는， 폴리알킬렌 카보네이트 수지 성형품이 제공된다.  According to another aspect of the present invention, there is provided a polyalkylene carbonate resin molded article produced using the above-described polyalkylene carbonate resin composition.
이러한 성형품은， 예를 들면, 필름， 필름 적층체， 시트 필라멘트， 부직포, 사출 성형품 등을 포함할 수 있다.  Such molded articles may include, for example, films, film laminates, sheet filaments, nonwoven fabrics, injection molded articles, and the like.
본 발명의 폴리알킬렌 카보네이트 수지 조성물을 성형하여 성형품을 얻는 방법은， 예를 들면 사출성형법， 압축성형법， 사출압축 성형법， 가스주입 사출 성형법， 발포 사출 성형법， 인플레이션법 (inflation), T 다이법 (T die), 캘린더법 (Calendar), 블로우 성형법 (blow), 진공 성형， 압공 성형 등을 들 수 있으며， 그 외에도 본 발명이 속한 기술 분야에서 일반적으로 사용되는 가공 방법을 특별한 제한 없이 사용할 수 있다. 이하， 발명의 구체적인 실시예를 통해， 발명의 작용 및 효과를 보다 상술하기로 한다. 다만 이러한 실시예는 발명의 예시로 제시된 것에 불과하며, 이에 의해 발명의 권리범위가 정해지는 것은 아니다  The method for obtaining a molded article by molding the polyalkylene carbonate resin composition of the present invention is, for example, injection molding method, compression molding method, injection compression molding method, gas injection injection molding method, foam injection molding method, inflation method (inflation), T die method ( T die), calender (Calendar), blow molding (blow), vacuum molding, pressure forming, and the like, in addition to the processing method generally used in the technical field of the present invention can be used without particular limitation. Hereinafter, the operation and effects of the invention will be described in more detail with reference to specific embodiments of the invention. However, these embodiments are only presented as an example of the invention, whereby the scope of the invention is not determined.
<실시예 > <Example>
폴리에틸렌 카보네이트수지 제조  Polyethylene carbonate resin manufacturing
디에틸—아연 촉매를 사용해 에틸렌 옥시드와 이산화탄소를 공중합하여 폴리에틸렌 카보네이트 수지를 다음의 방밥으로 제조하였다 (Journal of Polymer Science B 1969， 7， 287； Journal of Control led release 1997 , 49 , 263) . Co-polymerization of ethylene oxide and carbon dioxide using diethyl-zinc catalyst Polyethylene carbonate resin was prepared by the following method (Journal of Polymer Science B 1969, 7, 287; Journal of Control led release 1997, 49, 263).
교반기가 달린 오토클레이브 반응기에 건조한 디에틸 -아연 촉메 ( lg) 와 디옥산 용매 10mL를 넣고 천천히 교반하면서 5mL 디옥산 용매에 묽힌 정제수 O . lg을 넣었다. 이산화탄소를 10기압 정도 층진한 후， 120°C에서 1시간 동안 교반하였다. 이후 정제된 에틸렌 옥시드 (10g)를 넣고， 이산화탄소를 다시 50기압 정도 층진한 후 온도를 60°C로 조절하여 48시간 정도 반응시켰다. 반응 후 미반응 에틸렌옥시드를 저압 하에 제거하고 디클로로메탄 용매에 녹였다. 염산 수용액 (0. 1M)으로 세척하고 메탄올 용매에 침전시켜 폴리에틸렌 카보네이트 수지를 얻었다. 회수한 수지는 15g 정도였고， 그 생성을 핵자기 공명 스펙트럼으로 확인하였으며， GPC를 통해 분석한 중량 평균 분자량은 약 174 , 000g/mol 임을 확인하였다. 폴리락타이드블렌딩 펠렛 제조 Into an autoclave reactor equipped with a stirrer, dry diethyl-zinc catalyst (lg) and 10 mL of dioxane solvent were added and purified water diluted with 5 mL dioxane solvent with slow stirring. I put in lg. After layering about 10 atm of carbon dioxide, the mixture was stirred at 120 ° C for 1 hour. Thereafter, purified ethylene oxide (10 g) was added, and carbon dioxide was further layered at about 50 atmospheres, and then the temperature was adjusted to 60 ° C. for 48 hours. After the reaction, unreacted ethylene oxide was removed under low pressure and dissolved in dichloromethane solvent. Washed with aqueous hydrochloric acid solution (0.1M) and precipitated in methanol solvent to obtain polyethylene carbonate resin. The recovered resin was about 15g, the production was confirmed by nuclear magnetic resonance spectrum, and the weight average molecular weight analyzed by GPC was confirmed to be about 174, 000g / mol. Manufacture of Polylactide Blended Pellets
상기 제조한 폴리에틸렌 카보네이트에， 폴리락타이드 (NatureWorks PLA 3001D)를 혼합하여， 폴리락타이드의 함량이 5 %가 되도록， 펠렛을 제조하였,다. 실시예 1  To the polyethylene carbonate prepared above, polylactide (NatureWorks PLA 3001D) was mixed and pellets were prepared so that the content of polylactide was 5%. Example 1
450g의 폴리에틸렌 카보네이트 (중량 평균 분자량 174 , 000g/mol , 450 g polyethylene carbonate (weight average molecular weight 174, 000 g / mol,
NatureWorks PLA 3001D 5wt%함유) 펠렛과， 50g의 폴리케톤 (효성, M620A) 펠렛을 상온에서 드라이 블렌딩하였다. NatureWorks PLA 3001D 5wt%) pellets and 50 g polyketone (Hyosung, M620A) pellets were dry blended at room temperature.
이렇게 제조한 수지 조성물은， T-die가 체결된 트원 스크류 압출기 (twin screw extruder , BA—19 , 제조사: BAUTECH)를 사용하여， 두께 100 의 필름 형태로 제조하였다. 실시예 2  The resin composition thus prepared was prepared in the form of a film having a thickness of 100 using a twin screw extruder (BA-19, manufacturer: BAUTECH) to which T-die was fastened. Example 2
350g의 폴리에틸렌 카보네이트 (중량 평균 분자량 174 , 000g/mol , NatureWorks PLA 300 ID 5wt%함유) 펠렛과， 150g와 폴리케톤 (효성， M620A) 펠렛을 상온에서 드라이 블렌딩하였다. 이렇게 제조한 수지 조성물은， T-die가 체결된 트원 스크류 압출기 (twin screw extruder , BA-19 , 제조사: BAUTECH)를 사용하여， 두께 100 의 필름 형태로 제조하였다. 실시예 3 350 g polyethylene carbonate (weight average molecular weight 174, 000 g / mol, NatureWorks PLA 300 ID 5 wt%) pellets and 150 g polyketone (Hyosung, M620A) pellets were dry blended at room temperature. The resin composition thus prepared was prepared in the form of a film having a thickness of 100 using a twin screw extruder (BA-19, manufacturer: BAUTECH) to which T-die was fastened. Example 3
250g의 폴리에틸렌 카보네이트 (중량 평균 분자량 174, 000g/mol , 250 g polyethylene carbonate (weight average molecular weight 174, 000 g / mol,
NatureWorks PLA 3001D 5wt%함유) 펠렛과， 250g의 폴리케톤 (효성， M620A) 펠렛을상온에서 드라이 블렌딩하였다. NatureWorks PLA 3001D 5wt%) pellets and 250 g polyketone (Hyosung, M620A) pellets were dry blended at room temperature.
이렇게 제조한 수지 조성물은， T-die가 체결된 트원 스크류 압출기 (twin screw extruder , BA-19 , 제조사: BAUTECH)를 사용하여， 두께 100/im의 필름 형태로 제조하였다. 비교예 1  The resin composition thus prepared was prepared in the form of a film having a thickness of 100 / im using a twin screw extruder (BA-19, manufacturer: BAUTECH) to which T-die was fastened. Comparative Example 1
500g의 폴리에틸렌 카보네이트 (중량 평균 분자량 약 174, 000g/mol , NatureWorks PLA 300 ID 5wt%함유) 펠렛 단독으로， T— die가 체결된 트윈 스크류 압출기 (twin screw extruder , BA-19 , 제조사: BAUTECH)를 사용하여， 두께 100/皿의 필름 형태로 제조하였다.  500g polyethylene carbonate (weight average molecular weight about 174, 000g / mol with NatureWorks PLA 300 ID 5wt%) pellets alone, twin screw extruder (BA-19, manufactured by BAUTECH) In the form of a film having a thickness of 100 / mm 3 was used.
<실험예 > Experimental Example
상기 실시예 및 비교예에서 제조된 필름 형태의 수지에 대해， TGA분석 장비를 이용하여 온도 변화에 따른 질량 손실율를 측정하였다. TGA 분석 시， 질소 분위기 하에서， 상온에서 550°C까지， 약 10°C/½in의 속도로 승온시키면서 측정하였으며 그 결과를 도 1의 그래프로 도시하였다. For the resin in the form of a film prepared in the above Examples and Comparative Examples, the mass loss rate according to the temperature change was measured using a TGA analysis equipment. In the TGA analysis, measured under a nitrogen atmosphere at room temperature up to 550 ° C. at a rate of about 10 ° C./½ in. The results are shown in the graph of FIG. 1.
도 1을 참조하면， 폴리에틸렌 카보네이트 (폴리락타이드 5%함유)만을 단독으로 사용한 비교예 1의 경우, 약 180°C의 온도에서부터 열 분해가 시작되는 것을 확인할 수 있으며， 반 분해 온도 (hal f loss)가 약 270°C로， 고은 조건에서 매우 취약한 것을 확인할 수 있다. Referring to FIG. 1, in Comparative Example 1 using only polyethylene carbonate (containing 5% polylactide) alone, thermal decomposition starts from a temperature of about 180 ° C., and a half decomposition temperature (hal f loss). ) Is about 270 ° C, very weak at high conditions.
그러나， 폴리케톤을 포함하는 본 발명의 실시예의 경우， 약 250°C의 온도에서도， 열 분해가 전혀 일어나지 않은 것을 명확히 확인할 수 있으며, 약 270 °C 이상으로 온도가 높아지면서부터 열 분해가 일부 발생하지만， 약 300°C 이상의 온도에서도 질량 손실이 약 20% 미만이고 (폴리케톤이 없는 경우 약 300°C에서의 질량손실은 90¾이상)， 반 분해 온도가 약 320°C 이상으로， 상기 비교예에 비해 약 50 °C 더 높아， 열에 대한 안정성이 매우 높은 것을 명확히 확인할 수 있다. However, in the embodiment of the present invention including polyketone, even at a temperature of about 250 ° C, it can be clearly seen that no thermal decomposition at all, and some of the thermal decomposition occurs as the temperature increases above about 270 ° C. However, about 300 ° C Or more less than in the 20% mass loss temperature, and (if there are no polyketone about 300 ° mass loss in C is at least 90¾), the anti-degradation temperature above about 320 ° C, about 50 ° C compared to the Comparative Examples It is clear that it is higher and the heat stability is very high.
이에 따라， 본 발명의 실시예에 따른 폴리알킬렌 카보네이트 수지 조성물은， 높은 열 안정성을 가지는 것을 확인할 수 있으며， 특히 공압출 등에 의한 다층필름이나 다층시트 성형 등 높은 온도의 가공 조건에서도 우수한 가공성과 열 안정성을 가질 수 있음을 미루어 짐작할 수 있다.  Accordingly, the polyalkylene carbonate resin composition according to the embodiment of the present invention, it can be confirmed that has a high thermal stability, in particular excellent processability and heat even at high temperature processing conditions, such as forming a multilayer film or multilayer sheet by co-extrusion It can be assumed that it can have stability.

Claims

【청구의 범위】 [Range of request]
[청구항 1】  [Claim 1]
폴리알킬렌 카보네이트 100중량부에 대하여，  Per 100 parts by weight of polyalkylene carbonate,
폴리케톤 1 내지 100중량부를 포함하는， 폴리알킬렌 카보네이트 조성물.  Polyalkylene carbonate composition comprising 1 to 100 parts by weight of polyketone.
【청구항 2] [Claim 2]
제 1항에 있어서，  The method of claim 1,
상기 폴리알킬렌 카보네이트는， 하기 화학식 1로 표시되는 반복 단위를 포함하는， 폴리알킬렌 카보네이트 수지 조성물:  The polyalkylene carbonate, polyalkylene carbonate resin composition comprising a repeating unit represented by the following formula (1):
[화학식 1]  [Formula 1]
Figure imgf000018_0001
Figure imgf000018_0001
상기 화학식 1에서，  In Chemical Formula 1,
R1 내지 R4는 각각 독립적으로 수소， 탄소수 1 내지 20의 선형 또는 분지형의 알킬기， 탄소수 6 내지 20의 아릴기, 탄소수 1 내지 20의 알케닐기 또는 탄소수 3 내지 20의 시클로알킬기이고; R1 내지 R4 중 적도 어느 두 개는 서로 연결되어 탄소수 3 내지 10의 사이클로알킬기를 형성할수 있고; R 1 to R 4 are each independently hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms; Any two of R 1 to R 4 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms;
m은 10 내지 1,000의 정수이다.  m is an integer from 10 to 1,000.
[청구항 3】 [Claim 3]
제 1 항에 있어서，  The method of claim 1,
상기 폴리알킬렌 카보네이트는 폴리에틸렌 카보네이트， 폴리프로필렌 카보네이트， 폴리펜텐 카보네이트， 폴리핵센 카보네이트， 폴리옥텐 카보네이트 폴리시클로핵센 카보네이트 및 이들의 공중합체로 이루어지는 군에서 선택된 1종 이상인， 폴리알킬렌 카보네이트 수지 조성물.  The polyalkylene carbonate is at least one member selected from the group consisting of polyethylene carbonate, polypropylene carbonate, polypentene carbonate, polynuxene carbonate, polyoctene carbonate polycyclonucleene carbonate, and copolymers thereof, polyalkylene carbonate resin composition.
【청구항 4] 제 1항에 있어서， [Claim 4] The method of claim 1,
상기 폴리알킬렌 카보네이트는， 중량 평균 분자량이 ' 10 The polyalkylene carbonate, the weight average molecular weight "10
l,000 ,000g/m 인， 폴리알킬렌 카보네이트 수지 조성물. 1,000,000 g / m, polyalkylene carbonate resin composition.
【청구항 5】 [Claim 5]
제 1항에 있어서，  The method of claim 1,
상기 폴리케톤은， 하기 화학식 2로 표시되는 반복 단위를  The polyketone is a repeating unit represented by the following formula (2)
폴리알킬렌 카보네이트 수지 조성물: Polyalkylene Carbonate Resin Compositions:
[ 학식 2]
Figure imgf000019_0001
[Learning 2]
Figure imgf000019_0001
상기 화학식 2에서，  In Chemical Formula 2,
R은，  R is
탄소수 1 내지 10의， 선형 또는 분지형 알킬렌; 탄소수 1 내지 10의, 아릴렌; 탄소수 1 내지 10의， 알킬에테르; 탄소수 1 내지 10의， 아릴에테르; 탄소수 1 내지 10의 알킬에스터; 또는 탄소수 1 내지 10의， 아릴에스터이고， n은 10 내지 1000의 정수이다.  Linear or branched alkylene having 1 to 10 carbon atoms; Arylene having 1 to 10 carbon atoms; Alkyl ether of 1 to 10 carbon atoms; Aryl ethers having 1 to 10 carbon atoms; Alkyl esters having 1 to 10 carbon atoms; Or an aryl ester having 1 to 10 carbon atoms, and n is an integer of 10 to 1000.
【청구항 6] [Claim 6]
제 1항에 있어서，  The method of claim 1,
상기 폴리케톤은， 에틸렌， 프로필렌， 이소프로필렌， 또는 부틸렌 단위를 포함하는 지방족 폴리케톤인, 폴리알킬렌 카보네이트 수지 조성물.  The polyketone is an aliphatic polyketone comprising ethylene, propylene, isopropylene, or butylene units, polyalkylene carbonate resin composition.
【청구항 7] [Claim 7]
제 1항에 있어서，  The method of claim 1,
상기 폴리케톤은， 2원 공중합체 또는 3원 공중합체인, 폴리알킬렌 카보네이트 수지 조성물.  The polyketone is a polyalkylene carbonate resin composition, which is a binary copolymer or ternary copolymer.
【청구항 8] ' 제 1항에 있어서，. [Claim 8] In accordance with claim 1.
상기 폴리케톤은， 중량 평균 분자량이 10 , 000 내지 l ,000 , 000g/nx)l인， 폴리알킬렌 카보네이트 수지 조성물. [청구항 9】  The polyketone has a weight average molecular weight of 10, 000 to l, 000, 000 g / nx) l, polyalkylene carbonate resin composition. [Claim 9]
제 1항에 있어서，  The method of claim 1,
상기 폴리알킬렌 카보네이트 100중량부에 대하여， 폴리락타이드 1 내지 30중량부를 더 포함하는， 폴리알킬렌 카보네이트 수지 조성물. 【청구항 10】  The polyalkylene carbonate resin composition further comprising 1 to 30 parts by weight of polylactide, based on 100 parts by weight of the polyalkylene carbonate. [Claim 10]
제 1항에 있어서， .  The method of claim 1, wherein.
온도 변화에 따른 질량 손실율을 측정하였을 때, 250°C에서 열분해에 의한 질량 손실율이 10% 이하인， 폴리알킬렌 카보네이트 수지 조성물. [청구항 11] When the mass loss rate according to the temperature change, the mass loss rate by thermal decomposition at 250 ° C. is 10% or less, polyalkylene carbonate resin composition. [Claim 11]
제 1항의 폴리알킬렌 카보네이트 수지 조성물에 의해 제조되는， 폴리알킬렌 카보네이트 수지 성형품.  The polyalkylene carbonate resin molded article manufactured by the polyalkylene carbonate resin composition of Claim 1.
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