JP7615646B2 - Method for recycling polyester resin and method for manufacturing synthetic resin container - Google Patents
Method for recycling polyester resin and method for manufacturing synthetic resin container Download PDFInfo
- Publication number
- JP7615646B2 JP7615646B2 JP2020203010A JP2020203010A JP7615646B2 JP 7615646 B2 JP7615646 B2 JP 7615646B2 JP 2020203010 A JP2020203010 A JP 2020203010A JP 2020203010 A JP2020203010 A JP 2020203010A JP 7615646 B2 JP7615646 B2 JP 7615646B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- solid
- state polymerization
- flakes
- polyester resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 35
- 239000004645 polyester resin Substances 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 229920003002 synthetic resin Polymers 0.000 title claims description 6
- 239000000057 synthetic resin Substances 0.000 title claims description 6
- 238000004064 recycling Methods 0.000 title description 11
- 229920005989 resin Polymers 0.000 claims description 75
- 239000011347 resin Substances 0.000 claims description 75
- 238000006116 polymerization reaction Methods 0.000 claims description 70
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 50
- 239000008188 pellet Substances 0.000 claims description 46
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 claims description 16
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 claims description 16
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 238000000071 blow moulding Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 239000013638 trimer Substances 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 1
- 238000011069 regeneration method Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229940087305 limonene Drugs 0.000 description 2
- 235000001510 limonene Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYSWHUOYGUCXQB-UHFFFAOYSA-N (2,4-dinitrophenyl)hydrazine;phosphoric acid Chemical compound OP(O)(O)=O.NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RYSWHUOYGUCXQB-UHFFFAOYSA-N 0.000 description 1
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010924 used plastic bottle Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、ポリエステル系樹脂の再生方法、及び合成樹脂製容器の製造方法に関する。 The present invention relates to a method for recycling polyester resins and a method for manufacturing synthetic resin containers.
従来、ポリエチレンテレフタレートなどのポリエステル系樹脂を用いて有底筒状のプリフォームを作製し、次いで、このプリフォームを二軸延伸ブロー成形などによってボトル状に成形してなる合成樹脂製の容器が、各種飲料品、各種調味料等を内容物とする容器として広い分野で利用されている。この種の容器は、一般に、ＰＥＴボトルとして認知されており、近年にあっては、社会的な要請により、使用済みのＰＥＴボトルを回収し、これをリサイクル材料として再利用してＰＥＴボトルを製造する「ボトルｔｏボトル」と称されるリサイクル技術が検討されている。 Conventionally, a polyester resin such as polyethylene terephthalate is used to make a cylindrical preform with a bottom, which is then molded into a bottle shape by biaxial stretch blow molding or the like to produce synthetic resin containers, which are used in a wide range of fields as containers for various beverages, seasonings, and the like. This type of container is generally known as a PET bottle, and in recent years, due to social demand, a recycling technology called "bottle-to-bottle" has been considered, in which used PET bottles are collected and reused as recycled material to manufacture PET bottles.
例えば、特許文献１には、使用済みプラスチックボトルを粉砕して洗浄することによって樹脂フレークを生成し、樹脂フレークに含まれる汚染物質を真空下で加熱することによって揮発させて除染した後に、溶融状態でフィルターを介して射出成形機に供給して、プリフォームを射出成形するメカニカルリサイクルに関する技術が開示されている。 For example, Patent Document 1 discloses a technology for mechanical recycling in which used plastic bottles are crushed and washed to produce resin flakes, contaminants contained in the resin flakes are decontaminated by volatilizing them through heating under vacuum, and the flakes are then fed in a molten state through a filter to an injection molding machine to injection mold preforms.
ところで、使用済みのＰＥＴボトルなどのポリエステル系樹脂成形品を回収し、メカニカルリサイクルによるリサイクル材料として再利用して、回収品からリサイクル品を製造するに際しては、当該回収品の製造時に受けた熱履歴などに起因する樹脂の品質劣化による固有粘度などの低下が、リサイクル品の製造工程での不具合の原因となるという問題がある。さらに、ポリエステル系樹脂の熱分解によって生じるアセトアルデヒド（ＡＡ）、ポリエステル系樹脂の解重合によって生じるビスヒドロキシエチルテレフタレート（ＢＨＥＴ），モノヒドロキシエチルテレフタレート（ＭＨＥＴ），サイクリックトリマー（ＣＴ）等のオリゴマー、内容物由来のリモネンなどが、リサイクル材料に多く残存していると、製造されるリサイクル品の品質に影響を及ぼすだけでなく、製造装置を汚損してしまうなどして生産性を低下させる原因になるという問題もある。 However, when polyester resin molded products such as used PET bottles are collected and reused as recycled materials by mechanical recycling to manufacture recycled products from the collected products, there is a problem that a decrease in intrinsic viscosity and other properties due to deterioration in the quality of the resin caused by the heat history received during the manufacture of the collected products can cause problems in the manufacturing process of the recycled products. Furthermore, if a large amount of acetaldehyde (AA) produced by thermal decomposition of polyester resin, oligomers such as bishydroxyethyl terephthalate (BHET), monohydroxyethyl terephthalate (MHET), and cyclic trimer (CT) produced by depolymerization of polyester resin, and limonene derived from the contents remain in the recycled materials, they not only affect the quality of the recycled products produced, but also cause problems such as soiling the manufacturing equipment, thereby reducing productivity.
そこで、本発明者らは、メカニカルリサイクルによるリサイクル材料として、回収されたポリエステル系樹脂成形品を再利用する際の上記の如き問題を解消するべく鋭意検討を重ねた結果、本発明を完成するに至った。 The inventors therefore conducted extensive research to resolve the above-mentioned problems that arise when reusing recovered polyester resin molded products as recycled materials through mechanical recycling, and as a result, they have completed the present invention.
本発明に係るポリエステル系樹脂の再生方法は、回収されたポリエステル系樹脂成形品をフレーク状に粉砕してなる樹脂フレークを、５０ｍｂａｒ以下の減圧条件下で、ガラス転移点以上、溶融温度未満の範囲内の固相重合反応が進行する温度で加熱して、前記樹脂フレークを溶融させることなく、フレーク状の形態のまま固相重合反応を進行させる一次固相重合工程と、前記一次固相重合工程を経た前記樹脂フレークを可塑化し、溶融混錬してペレット状に造粒する造粒工程と、前記造粒工程で作製された樹脂ペレットを、２０ｍｂａｒ以下の減圧条件下で、１８０～２３０℃の範囲内の固相重合反応が進行する温度で加熱して、再度、固相重合反応を進行させる二次固相重合工程とを含む方法としてある。 The method for recycling polyester resin according to the present invention includes a primary solid-state polymerization step in which resin flakes obtained by crushing recovered polyester resin molded products into flakes are heated under reduced pressure conditions of 50 mbar or less at a temperature at which a solid-state polymerization reaction proceeds within a range from the glass transition point to below the melting temperature , thereby allowing the solid-state polymerization reaction to proceed while the resin flakes remain in the flake-like form without melting them ; a granulation step in which the resin flakes that have undergone the primary solid-state polymerization step are plasticized, melt-kneaded, and granulated into pellets; and a secondary solid-state polymerization step in which the resin pellets produced in the granulation step are heated under reduced pressure conditions of 20 mbar or less at a temperature at which a solid-state polymerization reaction proceeds within a range of 180 to 230° C. , thereby allowing the solid-state polymerization reaction to proceed again .
本発明に係る合成樹脂製容器の製造方法は、上記方法により再生された、ペレット状の再生ポリエステル系樹脂を可塑化し、溶融混錬して、射出成形又は圧縮成形により有底筒状のプリフォームを作製し、次いで、前記プリフォームをブロー成形する方法としてある。 The method for manufacturing synthetic resin containers according to the present invention involves plasticizing the pellet-shaped recycled polyester resin recycled by the above-mentioned method, melt-kneading it, and producing a bottomed cylindrical preform by injection molding or compression molding, and then blow molding the preform.
本発明によれば、回収されたポリエステル系樹脂成形品をメカニカルリサイクルによるリサイクル材料として再利用するに際し、ポリエステル系樹脂が良好に再生されることにより、リサイクル材料として好適に再利用することができる。 According to the present invention, when the recovered polyester resin molded products are reused as recycled materials by mechanical recycling, the polyester resin is well regenerated, so that it can be suitably reused as a recycled material.
以下、本発明の好ましい実施形態について説明する。 A preferred embodiment of the present invention is described below.
本実施形態にあっては、回収されたポリエステル系樹脂成形品をメカニカルリサイクルによるリサイクル材料として好適に再利用できるように、当該回収品を形成する品質が劣化したポリエステル系樹脂を再生するが、「回収されたポリエステル系樹脂成形品」には、資源ごみとして分別収集された使用済みのＰＥＴボトルなどのポリエステル系樹脂成形品の外、ポリエステル系樹脂成形品を製造する過程で生じたスクラップ材を含めることができる。 In this embodiment, the degraded polyester resin that forms the collected polyester resin molded products is regenerated so that the collected polyester resin molded products can be suitably reused as recycled materials by mechanical recycling. The "collected polyester resin molded products" can include polyester resin molded products such as used PET bottles that have been collected separately as resource waste, as well as scrap materials generated during the manufacturing process of polyester resin molded products.
また、再生の対象とされるポリエステル系樹脂としては、例えば、ポリエチレンテレフタレート，ポリブチレンテレフタレート，ポリエチレンナフタレート，ポリエチレンフラノエート又はこれらの共重合体などが挙げられる。 Examples of polyester resins that can be recycled include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene furanoate, and copolymers of these.
本実施形態では、先ず、回収されたポリエステル系樹脂成形品をフレーク状に粉砕するとともに、アルカリ洗浄、温水洗浄などの任意の洗浄手段によって洗浄し、粉砕された樹脂フレークの表面に残る内容物の残滓などの汚れや、混入した異物を取り除く。そして、洗浄された樹脂フレークを、必要に応じて乾かしてから、樹脂フレーク用に準備した固相重合槽（以下、「一次固相重合槽」という）に投入して、５０ｍｂａｒ以下、好ましくは２０ｍｂａｒ以下の減圧条件下で、ガラス転移点以上、溶融温度未満の範囲で加熱することによって、樹脂フレークを溶融させることなく、フレーク状の形態のまま固相重合反応を進行させる（一次固相重合工程）。 In this embodiment, the recovered polyester resin molded products are first crushed into flakes and washed by any washing means such as alkaline washing or hot water washing to remove dirt such as residues of contents remaining on the surface of the crushed resin flakes and foreign matter that has been mixed in. The washed resin flakes are then dried as necessary and placed in a solid-phase polymerization tank (hereinafter referred to as the "primary solid-phase polymerization tank") prepared for the resin flakes, and heated in a range between the glass transition point and the melting temperature under reduced pressure conditions of 50 mbar or less, preferably 20 mbar or less, to allow the solid-phase polymerization reaction to proceed in the flake-like form without melting the resin flakes (primary solid-phase polymerization process).
次に、一次固相重合工程を経た樹脂フレークを可塑化し、溶融混錬してペレット状に造粒することによって、樹脂ペレットを作製する（造粒工程）。 Next, the resin flakes that have undergone the primary solid-state polymerization process are plasticized, melt-kneaded, and granulated into pellets to produce resin pellets (granulation process).
造粒工程を行うには、例えば、内部に可塑化スクリューが配設された加熱シリンダと、加熱シリンダの先端に取り付けられた造粒用ダイスとを備え、加熱シリンダ内で可塑化され、溶融混錬されて、造粒用ダイスからストランド状に押し出された樹脂をペレット状に切断するように構成された造粒装置などを用いることができる。このような造粒装置にあっては、造粒用ダイスと加熱シリンダとの間に、異物除去のためのフィルターを介在させることができる。処理の効率化の観点から、一次固相重合工程を経た樹脂フレークが、一次固相重合槽から造粒装置に直接投入されるように、これらの装置を接続することによって、一次固相重合工程と造粒工程とが連続して行われるようにするのが好ましい。 To carry out the granulation process, for example, a granulation device can be used, which is equipped with a heating cylinder with a plasticizing screw disposed therein and a granulation die attached to the tip of the heating cylinder, and is configured to cut the resin that is plasticized and melt-kneaded in the heating cylinder and extruded in strand form from the granulation die into pellets. In such a granulation device, a filter for removing foreign matter can be interposed between the granulation die and the heating cylinder. From the viewpoint of efficient processing, it is preferable to connect these devices so that the resin flakes that have undergone the primary solid-state polymerization process are directly fed from the primary solid-state polymerization tank into the granulation device, thereby allowing the primary solid-state polymerization process and the granulation process to be carried out continuously.
その後、本実施形態では、造粒工程で作製された樹脂ペレットを、樹脂ペレット用に準備した固相重合槽（以下、「二次固相重合槽」という）に投入して、１００ｍｂａｒ以下、好ましくは２０ｍｂａｒ以下の減圧条件下で、１８０～２３０℃、好ましくは１９０～２１０℃の範囲で加熱することによって、再度、固相重合反応を進行させる（二次固相重合工程）。 In this embodiment, the resin pellets produced in the granulation process are then placed in a solid-state polymerization tank (hereinafter referred to as the "secondary solid-state polymerization tank") prepared for the resin pellets, and heated to a temperature range of 180 to 230°C, preferably 190 to 210°C, under reduced pressure conditions of 100 mbar or less, preferably 20 mbar or less, to allow the solid-state polymerization reaction to proceed again (secondary solid-state polymerization process).
二次固相重合工程を行うに際しては、例えば、１４０～１８０℃の温度で、固相重合反応が進行しない程度に樹脂ペレットを予熱して、造粒工程で非晶化した樹脂ペレットの表面の結晶化度を高めておくことにより、二次固相重合槽内での樹脂ペレットどうしのブロッキングが抑制されるようにするのが好ましい。 When carrying out the secondary solid-state polymerization step, it is preferable to preheat the resin pellets to a temperature of, for example, 140 to 180°C to the extent that the solid-state polymerization reaction does not proceed, and to increase the crystallinity of the surfaces of the resin pellets that have been amorphized in the granulation step, thereby suppressing blocking between the resin pellets in the secondary solid-state polymerization tank.
固相重合反応によって、劣化により分子鎖が切断されて重合度が低下したポリエステル系樹脂の末端基が再縮合し、これによって重合度が回復するにつれて、分子量に対応する固有粘度（ＩＶ）を回復させることができる。本実施形態にあっては、樹脂フレークの状態で固相重合反応を進行させて一次固相重合工程を行い、次いで、一次固相重合工程を経た樹脂フレークを可塑化し、溶融混錬してペレット状に造粒した後に、樹脂ペレットの状態で、再度、固相重合反応を進行させる二次固相重合工程を行うことによって、ポリエステル系樹脂の熱分解や解重合を抑制しつつ、ポリエステル系樹脂の固有粘度を効率よく回復させることができる。 The solid-state polymerization reaction re-condenses the end groups of the polyester resin, whose degree of polymerization has decreased due to the breakage of molecular chains caused by deterioration, and as the degree of polymerization is restored, the intrinsic viscosity (IV) corresponding to the molecular weight can be restored. In this embodiment, the solid-state polymerization reaction is carried out in the state of resin flakes to perform a primary solid-state polymerization process, and then the resin flakes that have undergone the primary solid-state polymerization process are plasticized, melt-kneaded, and granulated into pellets, and then the solid-state polymerization reaction is carried out again in the state of resin pellets to perform a secondary solid-state polymerization process, thereby efficiently restoring the intrinsic viscosity of the polyester resin while suppressing thermal decomposition and depolymerization of the polyester resin.
また、固相重合反応を減圧条件下で行うことによって、ポリエステル系樹脂の熱分解によって生じたアセトアルデヒド、ポリエステル系樹脂の解重合によって生じたＢＨＥＴ，ＭＨＥＴ，ＣＴ等のオリゴマー、重合前のモノマーに由来するＤＥＧ等のモノマー由来成分、内容物由来のリモネンなど低分子量の不純物や、樹脂に収着された水分を減圧下に揮発又は蒸発させて除去することができる。本実施形態では、樹脂ペレットに造粒する前に、樹脂フレークの状態で一次固相重合工程を行うことで、樹脂フレークの表面に残存するこれらの不純物などを除去しつつ、樹脂ペレット内に不純物が取り込まれてしまうのを抑制することができる。そして、樹脂フレークを可塑化し、溶融混錬してペレット状に造粒する過程で、樹脂ペレットの表面に滲出してきた不純物を、二次固相重合工程において効率よく除去することによって、最終的に得られる樹脂ペレットに残存する不純物の残存量をより良好に低減させることができる。
なお、固相重合反応を減圧条件下で行うことによって不純物を除去するに際しては、キャリアガスとしてＮ２ガスなどの不活性ガスを用いて、減圧状態を維持したまま固相重合槽内への流入と排気を所定の流量で継続的に行うのが好ましい。
In addition, by carrying out the solid-phase polymerization reaction under reduced pressure conditions, it is possible to remove low molecular weight impurities such as acetaldehyde generated by thermal decomposition of the polyester resin, oligomers such as BHET, MHET, and CT generated by depolymerization of the polyester resin, monomer-derived components such as DEG derived from the monomer before polymerization, limonene derived from the contents, and moisture sorbed in the resin by volatilization or evaporation under reduced pressure. In this embodiment, by carrying out the primary solid-phase polymerization process in the state of resin flakes before granulating into resin pellets, it is possible to remove these impurities remaining on the surface of the resin flakes while suppressing the incorporation of impurities into the resin pellets. In addition, by efficiently removing impurities that have seeped out onto the surface of the resin pellets during the process of plasticizing the resin flakes and granulating them into pellets in the secondary solid-phase polymerization process, it is possible to more effectively reduce the amount of impurities remaining in the resin pellets finally obtained.
When removing impurities by carrying out the solid-state polymerization reaction under reduced pressure conditions, it is preferable to use an inert gas such as N2 gas as a carrier gas and to continuously flow the gas into and out of the solid-state polymerization reactor at a predetermined flow rate while maintaining the reduced pressure state.
以上のような本実施形態によれば、回収されたポリエステル系樹脂成形品をメカニカルリサイクルによるリサイクル材料として再利用するに際し、ポリエステル系樹脂が良好に再生されることにより、リサイクル材料として好適に再利用することができる。特に、本実施形態において、再生されたポリエステル系樹脂からなる樹脂ペレットは、これを可塑化し、溶融混錬して、射出成形又は圧縮成形により有底筒状のプリフォームを作製し、次いで、かかるプリフォームをブロー成形することによって、ＰＥＴボトルなどの合成樹脂製容器を製造するためのリサイクル材料として好適であり、二次固相重合工程における熱結晶化により、当該樹脂ペレットの第一融点ピークが低温側から高温側にシフトしていることから、プリフォーム成形前の乾燥処理時にブロッキングするなどの不具合が生じることもない。 According to the present embodiment as described above, when the collected polyester resin molded products are reused as recycled materials by mechanical recycling, the polyester resin is well regenerated and can be suitably reused as recycled materials. In particular, in this embodiment, the resin pellets made of the recycled polyester resin are plasticized, melt-kneaded, and injection-molded or compression-molded to produce bottomed cylindrical preforms, which are then blow-molded to produce synthetic resin containers such as PET bottles. Since the first melting point peak of the resin pellets is shifted from the low-temperature side to the high-temperature side due to thermal crystallization in the secondary solid-phase polymerization process, there is no problem such as blocking during the drying process before preform molding.
以下、具体的な実施例を挙げて、本発明をより詳細に説明する。 The present invention will be explained in more detail below with specific examples.
［実施例１］
回収された使用済みのＰＥＴボトルをフレーク状に粉砕するとともに、洗浄された樹脂フレークを用意した。用意した樹脂フレークを一次固相重合槽に投入し、２０ｍｂａｒ以下の減圧条件下で、２１０℃前後に加熱して、樹脂フレークを溶融させることなく、フレーク状の形態のまま固相重合反応を進行させた。そして、樹脂フレークが、一次固相重合槽内に６０～９０分滞留した後に造粒装置に投入されるようにして、一次固相重合工程を経た樹脂フレークを可塑化し、溶融混錬してペレット状に造粒した。次いで、樹脂ペレットを二次固相重合槽に投入し、１０ｍｂａｒ以下の減圧条件下で、２００℃に加熱することによって、再度、固相重合反応を進行させ、樹脂ペレットを二次固相重合槽内に６時間滞留させて二次固相重合工程を行った後に排出した。
なお、二次固相重合工程を行うに際しては、二次固相重合槽内へのＮ２ガスの流入と排気を３ｍ３／Ｌの流量で継続的に行った。
[Example 1]
The collected used PET bottles were crushed into flakes, and washed resin flakes were prepared. The prepared resin flakes were charged into a first solid-state polymerization tank and heated to about 210°C under reduced pressure conditions of 20 mbar or less, and the solid-state polymerization reaction proceeded while the resin flakes were in the flake form without melting them. The resin flakes were then plasticized and melt-kneaded to pelletize the resin flakes that had undergone the first solid-state polymerization step, so that the resin flakes were charged into a granulator after staying in the first solid-state polymerization tank for 60 to 90 minutes. The resin pellets were then charged into a second solid-state polymerization tank and heated to 200°C under reduced pressure conditions of 10 mbar or less, and the solid-state polymerization reaction proceeded again. The resin pellets were then discharged after staying in the second solid-state polymerization tank for 6 hours to carry out the second solid-state polymerization step.
During the secondary solid-state polymerization step, N 2 gas was continuously introduced into and exhausted from the secondary solid-state polymerization tank at a flow rate of 3 m 3 /L.
二次固相重合工程後の樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
なお、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量は、次のようにして測定した。
The resin pellets after the secondary solid-state polymerization step were measured for intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT. The results are shown in Table 1.
The intrinsic viscosity (IV), the degree of crystallinity, the melting point (Tm), and the remaining amounts of acetaldehyde (AA), BHET, MHET, and CT were measured as follows.
＜固有粘度＞
樹脂ペレットを１５０℃にて１時間真空乾燥させ、０．２ｇ秤量した。これに１，１，２，２－テトラクロロエタンとフェノールの混合溶媒（重量比１／１）を加えて１．００ｇ／ｄＬの濃度に調整し、１２０℃で２０分間撹拌して完全に溶解させた。溶解後の溶液を室温まで冷却し、３０℃に温調された相対粘度計（Ｖｉｓｃｏｔｅｋ，Ｙ５０１）を用いて相対粘度を求め、固有粘度を決定した。
<Intrinsic Viscosity>
The resin pellets were vacuum dried at 150° C. for 1 hour and weighed out at 0.2 g. A mixed solvent of 1,1,2,2-tetrachloroethane and phenol (weight ratio 1/1) was added to the pellets to adjust the concentration to 1.00 g/dL, and the pellets were completely dissolved by stirring at 120° C. for 20 minutes. The dissolved solution was cooled to room temperature, and the relative viscosity was measured using a relative viscometer (Viscotek, Y501) adjusted to 30° C., to determine the intrinsic viscosity.
＜結晶化度＞
密度法により次式から結晶化度を求めた。
結晶化度χｃ＝｛［ρｃ×（ρ－ρａ）］／［ρ×（ρｃ－ρａ）］｝
ρ：測定密度（ｇ／ｃｍ３）
ρａ：非晶密度（１．３３５ｇ／ｃｍ３）
ρｃ：結晶密度（１．４５５ｇ／ｃｍ３）
なお、密度測定は硝酸カルシウム溶液系密度勾配管（株式会社柴山科学器械製作所）により、２３℃の条件下にて行った。
<Crystallization degree>
The crystallinity was calculated by the density method using the following formula:
Crystallinity χ c = {[ρc×(ρ−ρa)]/[ρ×(ρc−ρa)]}
ρ: Measured density (g/cm 3 )
ρa: amorphous density (1.335g/cm 3 )
ρc: Crystal density (1.455g/cm 3 )
The density measurement was carried out at 23° C. using a calcium nitrate solution-based density gradient tube (Shibayama Scientific Instruments Manufacturing Co., Ltd.).
＜融点＞
樹脂ペレット８ｍｇを試料に用いて、示差走査熱量計（ＰＥＲＫＩＮ ＥＬＭＡＲ社製ＤＳＣ８５００）を用いてＤＳＣ測定を行った。
試料温度は、
（１）４０℃で３分間保持
（２）４０℃から３００℃に１０℃／ｍｉｎで昇温
の順で走査し、（２）における融点ピークを融点とした。低温側の融点ピークを第一融点ピーク、高温側の融点ピークを第二融点ピークとした。
<Melting Point>
Using 8 mg of the resin pellets as a sample, DSC measurement was carried out using a differential scanning calorimeter (DSC8500 manufactured by PERKIN ELMAR).
The sample temperature is
(1) Hold at 40°C for 3 minutes, (2) Raise the temperature from 40°C to 300°C at 10°C/min, and the melting point peak in (2) was taken as the melting point. The melting point peak on the low temperature side was taken as the first melting point peak, and the melting point peak on the high temperature side was taken as the second melting point peak.
＜アセトアルデヒドの残存量＞
冷凍粉砕装置にて粉砕した樹脂ペレットの粉砕試料をガラス瓶に１．０ｇ秤量し、５．０ｍＬの純水を加えて密封した。この懸濁液を１２０℃に温調したオーブン内にて６０分間加熱した後、氷水中にて冷却した。懸濁液の上澄みを１．０ｍＬ採取し、これに濃度０．１％の２，４－ジニトロフェニルヒドラジン・リン酸溶液を０．２ｍＬ加え、３０分間放置したものを高速液体クロマトグラフィーにて測定した。同時に標準溶液の測定も行い、得られた検量線をもとに樹脂ペレット中のアセトアルデヒド含有量を計算した。
<Residual amount of acetaldehyde>
1.0 g of the resin pellets crushed by a freeze crushing device was weighed into a glass bottle, and 5.0 mL of pure water was added and sealed. This suspension was heated for 60 minutes in an oven controlled at 120°C, and then cooled in ice water. 1.0 mL of the supernatant of the suspension was taken, to which 0.2 mL of 0.1% 2,4-dinitrophenylhydrazine-phosphate solution was added, and the mixture was left for 30 minutes and measured by high performance liquid chromatography. At the same time, the standard solution was also measured, and the acetaldehyde content in the resin pellets was calculated based on the obtained calibration curve.
＜ＢＨＥＴ、ＭＨＥＴ、ＣＴの残存量＞
樹脂ペレットを０．２ｇ秤量し、これにヘキサフルオロイソプロパノールとクロロホルムの混合溶媒（重量比１／１）を１ｍＬ加えて完全に溶解した。溶液に４ｍＬのクロロホルムを加えた後、５ｍＬのアセトニトリルを徐々に加え、３時間放置してＰＥＴポリマーを析出させた。この懸濁液から１ｍＬ採取し、細孔径０．４５μｍのメンブレンフィルターにて濾過し、濾液を高速液体クロマトグラフィーにて測定した。同時に標準溶液の測定も行い、得られた検量線をもとにペレット中のＭＨＥＴ、ＢＨＥＴ及びＣＴの含有量を計算した。
<Remaining Amounts of BHET, MHET, and CT>
0.2 g of resin pellets were weighed, and 1 mL of a mixed solvent of hexafluoroisopropanol and chloroform (weight ratio 1/1) was added to completely dissolve the pellets. After adding 4 mL of chloroform to the solution, 5 mL of acetonitrile was gradually added and the mixture was left for 3 hours to precipitate the PET polymer. 1 mL of the suspension was taken and filtered through a membrane filter with a pore size of 0.45 μm, and the filtrate was measured by high performance liquid chromatography. At the same time, the standard solution was also measured, and the contents of MHET, BHET and CT in the pellets were calculated based on the obtained calibration curve.
［実施例２］
二次固相重合工程において、加熱温度を１９５℃にした以外は、実施例１と同様の操作を行い、二次固相重合工程後の樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
[Example 2]
The same operations as in Example 1 were carried out except that the heating temperature in the secondary solid-state polymerization step was 195° C., and the intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the resin pellets after the secondary solid-state polymerization step. The results are shown in Table 1.
［比較例１］
回収された使用済みのＰＥＴボトルをフレーク状に粉砕するとともに、洗浄された樹脂フレークを用意し、固相重合反応を進行させることなく、１６０℃の温度で１００分前後加熱することによって乾燥させた後に、造粒装置に投入してペレット状に造粒した。得られた樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
[Comparative Example 1]
The collected used PET bottles were crushed into flakes, and the washed resin flakes were prepared and dried by heating at a temperature of 160°C for about 100 minutes without proceeding with the solid-state polymerization reaction, and then fed into a granulator to be granulated into pellets. The intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the obtained resin pellets. The results are shown in Table 1.
［比較例２］
比較例１で得られた樹脂ペレットを固相重合槽に投入し、樹脂ペレットの滞留時間を６時間とした以外は、実施例１と同様に、１０ｍｂａｒ以下の減圧条件下で、２００℃に加熱することによって、固相重合反応を進行させた。固相重合後の樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
実施例１，２に比べて結晶化度が向上しているのは、樹脂ペレットの滞留時間が長いことに起因すると考えられるが、それ以外は、実施例１，２のいずれにも及ばない結果となった。
[Comparative Example 2]
The resin pellets obtained in Comparative Example 1 were charged into a solid-state polymerization tank, and the solid-state polymerization reaction was carried out by heating to 200° C. under reduced pressure conditions of 10 mbar or less, in the same manner as in Example 1, except that the residence time of the resin pellets was set to 6 hours. The intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the resin pellets after solid-state polymerization. The results are shown in Table 1.
The improvement in crystallinity compared to Examples 1 and 2 is believed to be due to the longer residence time of the resin pellets. However, other than that, the results were inferior to those of Examples 1 and 2.
［比較例３］
回収された使用済みのＰＥＴボトルをフレーク状に粉砕するとともに、洗浄された樹脂フレークを用意した。用意した樹脂フレークを固相重合槽に投入し、１０ｍｂａｒ以下の減圧条件下で、１９０℃前後に加熱して、樹脂フレークを溶融させることなく、フレーク状の形態のまま固相重合反応を進行させた。そして、樹脂フレークが、固相重合槽内に９０分前後滞留した後に造粒装置に投入されるようして、ペレット状に造粒した。得られた樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
本比較例で得られた樹脂ペレットは、第一融点ピークが１６０～１９０℃付近にあり、プリフォーム成形前の乾燥処理時にブロッキングするなどの不具合が生じた。
[Comparative Example 3]
The collected used PET bottles were crushed into flakes, and washed resin flakes were prepared. The prepared resin flakes were put into a solid-state polymerization tank and heated to about 190° C. under reduced pressure of 10 mbar or less, so that the solid-state polymerization reaction proceeded without melting the resin flakes in the flake form. The resin flakes were then pelletized by being put into a pelletizer after staying in the solid-state polymerization tank for about 90 minutes. The intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the obtained resin pellets. The results are shown in Table 1.
The resin pellets obtained in this comparative example had a first melting point peak in the vicinity of 160 to 190° C., and problems such as blocking occurred during the drying treatment prior to preform molding.
［比較例４］
回収された使用済みのＰＥＴボトルをフレーク状に粉砕するとともに、洗浄された樹脂フレークを用意した。用意した樹脂フレークを固相重合槽に投入し、１０ｍｂａｒ以下の減圧条件下で、１９０℃前後に加熱して、樹脂フレークを溶融させることなく、フレーク状の形態のまま固相重合反応を進行させた。そして、樹脂フレークが、固相重合槽内に１２０分前後滞留した後に造粒装置に投入されるようして、ペレット状に造粒した。得られた樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
[Comparative Example 4]
The collected used PET bottles were crushed into flakes, and washed resin flakes were prepared. The prepared resin flakes were put into a solid-state polymerization tank and heated to about 190° C. under reduced pressure of 10 mbar or less, so that the solid-state polymerization reaction proceeded without melting the resin flakes in the flake form. The resin flakes were pelletized by being put into a pelletizer after staying in the solid-state polymerization tank for about 120 minutes. The intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the obtained resin pellets. The results are shown in Table 1.
［比較例５］
比較例４で得られた樹脂ペレットを常圧下で、１６０℃の温度で６時間加熱処理した。加熱処理後の樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
比較例４との対比から、本比較例のような１６０℃の加熱処理では固有粘度、結晶化度に大きな変化は認められなかった。
[Comparative Example 5]
The resin pellets obtained in Comparative Example 4 were heat-treated at 160° C. for 6 hours under normal pressure. The intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the resin pellets after the heat treatment. The results are shown in Table 1.
In comparison with Comparative Example 4, no significant changes in the intrinsic viscosity and the degree of crystallinity were observed in the heat treatment at 160° C. as in this Comparative Example.
［比較例６］
二次固相重合工程において、二次固相重合槽内の圧力を１００～２００ｍｂａｒに調整し、加熱温度を１９７℃、Ｎ２ガスの流量を２００ｍ３／Ｌとした以外は、実施例１と同様の操作を行い、二次固相重合工程後の樹脂ペレットについて、固有粘度（ＩＶ）、結晶化度、融点（Ｔｍ）及びアセトアルデヒド（ＡＡ），ＢＨＥＴ，ＭＨＥＴ，ＣＴの残存量を測定した。その結果を表１に示す。
実施例１，２と同等に固有粘度が向上しているものの、それ以外は、実施例１，２のいずれにも及ばない結果となった。
[Comparative Example 6]
In the second solid-state polymerization step, the pressure in the second solid-state polymerization tank was adjusted to 100 to 200 mbar, the heating temperature was set to 197° C., and the flow rate of N2 gas was set to 200 m3 /L, but the same operations as in Example 1 were carried out, and the intrinsic viscosity (IV), crystallinity, melting point (Tm), and residual amounts of acetaldehyde (AA), BHET, MHET, and CT were measured for the resin pellets after the second solid-state polymerization step. The results are shown in Table 1.
Although the intrinsic viscosity was improved to the same extent as in Examples 1 and 2, the results were otherwise inferior to those of Examples 1 and 2.
本発明に係る再生ポリエステル系樹脂は、以上のような再生方法により再生された再生ポリエステル系樹脂であって、固有粘度が０．７８～０．９５ｄｌ／ｇ、結晶化度が４０～６０％、第一融点ピークが２００～２４５℃、アセトアルデヒドの残存量が０．１～２．０ｐｐｍ、ビスヒドロキシエチルテレフタレートの残存量が５～１８ｐｐｍ、モノヒドロキシエチルテレフタレートの残存量が５～１８ｐｐｍ、サイクリックトリマーの残存量が４，０００～７，０００ｐｐｍとなるように、回収されたポリエステル系樹脂成形品から良好に再生される。 The recycled polyester resin of the present invention is a recycled polyester resin that has been recycled by the above-mentioned recycling method, and is well recycled from recovered polyester resin molded products so that the intrinsic viscosity is 0.78-0.95 dl/g, the crystallinity is 40-60%, the first melting point peak is 200-245°C, the amount of acetaldehyde remaining is 0.1-2.0 ppm, the amount of bishydroxyethyl terephthalate remaining is 5-18 ppm, the amount of monohydroxyethyl terephthalate remaining is 5-18 ppm, and the amount of cyclic trimer remaining is 4,000-7,000 ppm.
以上、本発明について、好ましい実施形態を示して説明したが、本発明は、前述した実施形態にのみ限定されるものではなく、本発明の範囲で種々の変更実施が可能であることはいうまでもない。
Although the present invention has been described above by showing preferred embodiments, it goes without saying that the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the present invention.
Claims (3)
前記一次固相重合工程を経た前記樹脂フレークを可塑化し、溶融混錬してペレット状に造粒する造粒工程と、
前記造粒工程で作製された樹脂ペレットを、２０ｍｂａｒ以下の減圧条件下で、１８０～２３０℃の範囲内の固相重合反応が進行する温度で加熱して、再度、固相重合反応を進行させる二次固相重合工程と
を含むことを特徴とするポリエステル系樹脂の再生方法。 a primary solid-state polymerization step in which the resin flakes obtained by crushing the recovered polyester resin molded articles into flakes are heated under reduced pressure conditions of 50 mbar or less at a temperature at which a solid-state polymerization reaction proceeds within a range of not less than the glass transition point and not more than the melting temperature , thereby proceeding with a solid-state polymerization reaction while the resin flakes remain in the flake-like form without melting the resin flakes ;
a granulation step in which the resin flakes that have undergone the primary solid-phase polymerization step are plasticized, melt-kneaded, and granulated into pellets;
and a secondary solid-state polymerization step of heating the resin pellets produced in the granulation step under reduced pressure conditions of 20 mbar or less at a temperature in the range of 180 to 230°C at which a solid-state polymerization reaction proceeds, thereby causing the solid-state polymerization reaction to proceed again .
固有粘度が０．７８～０．９５ｄｌ／ｇ、結晶化度が４０～６０％、第一融点ピークが２００～２４５℃、アセトアルデヒドの残存量が０．１～２．０ｐｐｍ、ビスヒドロキシエチルテレフタレートの残存量が５～１８ｐｐｍ、モノヒドロキシエチルテレフタレートの残存量が５～１８ｐｐｍ、サイクリックトリマーの残存量が４，０００～７，０００ｐｐｍであることを特徴とする再生ポリエチレンテレフタレート系樹脂。
A recycled polyethylene terephthalate resin regenerated by the method for regenerating a polyester resin according to claim 1,
A recycled polyethylene terephthalate resin having an intrinsic viscosity of 0.78 to 0.95 dl/g, a degree of crystallinity of 40 to 60%, a first melting point peak of 200 to 245°C, a residual amount of acetaldehyde of 0.1 to 2.0 ppm, a residual amount of bishydroxyethyl terephthalate of 5 to 18 ppm, a residual amount of monohydroxyethyl terephthalate of 5 to 18 ppm, and a residual amount of cyclic trimer of 4,000 to 7,000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020203010A JP7615646B2 (en) | 2020-12-07 | 2020-12-07 | Method for recycling polyester resin and method for manufacturing synthetic resin container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020203010A JP7615646B2 (en) | 2020-12-07 | 2020-12-07 | Method for recycling polyester resin and method for manufacturing synthetic resin container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022090549A JP2022090549A (en) | 2022-06-17 |
| JP7615646B2 true JP7615646B2 (en) | 2025-01-17 |
Family
ID=81992023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020203010A Active JP7615646B2 (en) | 2020-12-07 | 2020-12-07 | Method for recycling polyester resin and method for manufacturing synthetic resin container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP7615646B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024128083A1 (en) * | 2022-12-12 | 2024-06-20 | 東洋製罐株式会社 | Method for producing preform and preform |
| WO2024143102A1 (en) * | 2022-12-26 | 2024-07-04 | 東洋製罐株式会社 | Method for manufacturing preform |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000000873A (en) | 1998-06-18 | 2000-01-07 | Toyobo Co Ltd | Label-mounted resin bottle and method of recycling the same |
| JP2001058620A (en) | 1999-08-20 | 2001-03-06 | Toyobo Co Ltd | Resin-made bottle with label stuck thereon and its recycling method |
| JP2002011719A (en) | 2000-06-29 | 2002-01-15 | Mitsui Chemicals Engineering Co Ltd | Method for recycling pet bottle |
| JP2006052307A (en) | 2004-08-11 | 2006-02-23 | Toyo Seikan Kaisha Ltd | Polyester resin for compression molding, method for producing preform, and preform |
| JP2018043773A (en) | 2016-09-15 | 2018-03-22 | 三菱瓦斯化学株式会社 | Multilayer container and method for producing recycled polyester |
| US20200283596A1 (en) | 2017-01-03 | 2020-09-10 | Alpla Werke Alwin Lehner Gmbh & Co. Kg | Pet regranulate having high intrinsic viscosity and method for the production thereof |
-
2020
- 2020-12-07 JP JP2020203010A patent/JP7615646B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000000873A (en) | 1998-06-18 | 2000-01-07 | Toyobo Co Ltd | Label-mounted resin bottle and method of recycling the same |
| JP2001058620A (en) | 1999-08-20 | 2001-03-06 | Toyobo Co Ltd | Resin-made bottle with label stuck thereon and its recycling method |
| JP2002011719A (en) | 2000-06-29 | 2002-01-15 | Mitsui Chemicals Engineering Co Ltd | Method for recycling pet bottle |
| JP2006052307A (en) | 2004-08-11 | 2006-02-23 | Toyo Seikan Kaisha Ltd | Polyester resin for compression molding, method for producing preform, and preform |
| JP2018043773A (en) | 2016-09-15 | 2018-03-22 | 三菱瓦斯化学株式会社 | Multilayer container and method for producing recycled polyester |
| US20200283596A1 (en) | 2017-01-03 | 2020-09-10 | Alpla Werke Alwin Lehner Gmbh & Co. Kg | Pet regranulate having high intrinsic viscosity and method for the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022090549A (en) | 2022-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111138641B (en) | Method for preparing bottle-grade slices by recycling waste polyester bottles | |
| KR102163351B1 (en) | Manufacturing method of recycled PET chip for manufacturing high strength polyester long fiber | |
| JP3756520B2 (en) | Method for producing polyester articles with low acetaldehyde content | |
| US20050187306A1 (en) | Process for controlled polymerization of a mixed polymer | |
| EP0994146B1 (en) | Solid state polymerization of PET flakes | |
| JP7615646B2 (en) | Method for recycling polyester resin and method for manufacturing synthetic resin container | |
| JP2003055300A (en) | Process for producing bis-β-hydroxyethyl terephthalate | |
| EP3320017B1 (en) | Process for the production of glycol-modified polyethylene therephthalate from recycled raw materials | |
| CN112759746A (en) | Preparation method of high-cleanness food grade recycled bottle flakes | |
| CN117795139A (en) | Chemically recycled PET fibers, rubber-fiber composites, conveyor belts, hoses and tires | |
| JP2025515562A (en) | Process for producing polyester resins and fibers containing recycled bis(2-hydroxyethyl) terephthalate | |
| CZ327395A3 (en) | Process for preparing poly(ethylenenaphthalate)polymer or copolymer with high molecular weight | |
| TW201604220A (en) | Process and system for the production of PET pellets | |
| KR101748408B1 (en) | Method for preparing polyalkylenecarbonate | |
| JP4014356B2 (en) | How to recycle plastic bottles | |
| CA2248268A1 (en) | Process for forming articles directly from melt polymerization | |
| EP4421116A1 (en) | Production of recycled polyesters from polyester waste through chemical recycling methodology | |
| CN1210547A (en) | Dimensional stabilization method for polyethylene terephthalate containers | |
| JP2023175425A (en) | Molded object, manufacturing method thereof, crushed product thereof, and recycling method using the same | |
| JP5288677B2 (en) | Polyethylene terephthalate resin | |
| CN114806093A (en) | Polyester mist mask and manufacturing method thereof | |
| CN119136960A (en) | Method for recycling polyester containers | |
| EP4198075A1 (en) | Process for producing recycled pet resin and method for producing moulded articles | |
| KR20010053261A (en) | Process for crystallising polyethylene naphthalate copolymers in the absence of a devolatilization step | |
| JP2004323664A (en) | Method for recycling polyalkylene terephthalate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20231114 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20240814 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240820 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20241010 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20241203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20241216 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 7615646 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |