JP6232598B2 - Method for producing synthetic resin material and recycled resin material - Google Patents
Method for producing synthetic resin material and recycled resin material Download PDFInfo
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- JP6232598B2 JP6232598B2 JP2016189667A JP2016189667A JP6232598B2 JP 6232598 B2 JP6232598 B2 JP 6232598B2 JP 2016189667 A JP2016189667 A JP 2016189667A JP 2016189667 A JP2016189667 A JP 2016189667A JP 6232598 B2 JP6232598 B2 JP 6232598B2
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- 239000011347 resin Substances 0.000 title claims description 139
- 229920005989 resin Polymers 0.000 title claims description 139
- 239000000463 material Substances 0.000 title claims description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920003002 synthetic resin Polymers 0.000 title description 3
- 239000000057 synthetic resin Substances 0.000 title description 3
- 230000006866 deterioration Effects 0.000 claims description 76
- 239000000155 melt Substances 0.000 claims description 53
- 238000006731 degradation reaction Methods 0.000 claims description 45
- 238000005259 measurement Methods 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 description 61
- 229920001684 low density polyethylene Polymers 0.000 description 28
- 239000004702 low-density polyethylene Substances 0.000 description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000003776 cleavage reaction Methods 0.000 description 17
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 17
- 239000004926 polymethyl methacrylate Substances 0.000 description 17
- 230000007017 scission Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 239000000654 additive Substances 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 14
- 229920001955 polyphenylene ether Polymers 0.000 description 13
- 238000001746 injection moulding Methods 0.000 description 12
- 238000010525 oxidative degradation reaction Methods 0.000 description 12
- 230000007423 decrease Effects 0.000 description 11
- 230000004913 activation Effects 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000003247 decreasing effect Effects 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 238000012668 chain scission Methods 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920006324 polyoxymethylene Polymers 0.000 description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010667 large scale reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
- Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
-
- 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
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Description
本発明は、合成樹脂材料及びリサイクル樹脂材料の劣化状態をメルトフローレイト試験により簡便に評価した樹脂材料を用いた成形品の製造方法に関する。 The present invention relates to a method for producing a molded article using a resin material in which the deterioration state of a synthetic resin material and a recycled resin material is simply evaluated by a melt flow rate test.
樹脂の劣化は、ヒドロ過酸化物を原因とする劣化と、安定な酸化物生成に由来する劣化とに分類される。熱や光により励起された状態にある分子の側鎖や末端が酸化などの化学反応による劣化を受けたり、主鎖が切断したりすることにより劣化が進む。樹脂の劣化は、成形加工段階や使用している間にも生じ、応力、温度、酸素、水分、放射線、オゾン、そして、薬品など種々の要因が関与して促進される。樹脂の劣化状態は、主鎖又は側鎖の切断による分子量の低下とこれに伴う強度の低下、架橋化による性能の低下、そして、外観の低下などにより確認される。樹脂材料の分子量を測定することが樹脂の主鎖切断による劣化を確認する上で重要であるが、分子量を分析できる樹脂でも、機械的強さは分子量に比例して低下するわけではなく、その樹脂材料の限界分子量以下にまで低下したときに強さが急激に低下する特性がある（非特許文献１）。一方、オレフィン系樹脂などでは、そもそも溶媒に難溶であるために分子量の測定が困難である。樹脂の劣化は、このように現象が複雑であるとともに、その状態を分析する手法が煩雑であった。 The degradation of the resin is classified into degradation caused by hydroperoxide and degradation derived from stable oxide generation. Deterioration progresses when the side chains and terminals of molecules excited by heat and light undergo degradation due to chemical reactions such as oxidation, or the main chain is cleaved. The deterioration of the resin also occurs during the molding process and during use, and is accelerated by various factors such as stress, temperature, oxygen, moisture, radiation, ozone, and chemicals. The deterioration state of the resin is confirmed by a decrease in molecular weight due to cleavage of the main chain or side chain, a decrease in strength associated therewith, a decrease in performance due to cross-linking, and a decrease in appearance. Measuring the molecular weight of the resin material is important in confirming degradation due to the main chain cleavage of the resin, but even with resins that can analyze the molecular weight, the mechanical strength does not decrease in proportion to the molecular weight. There is a characteristic that the strength sharply decreases when the molecular weight is reduced below the limit molecular weight of the resin material (Non-patent Document 1). On the other hand, olefin-based resins are hardly soluble in solvents in the first place, so it is difficult to measure molecular weight. The deterioration of the resin is complicated in this way, and the method for analyzing the state is complicated.
樹脂劣化の分析は、動的には酸化が生じている過渡状態をとらえることでなされる。一方、静的には酸化された後の反応生成物として酸化や分解が生じた状態の樹脂を分析してその状態を捉えることによりなされる。樹脂の劣化状態を把握し、適切な劣化防止対策をとるためには、特に劣化の過渡的な状態、すなわち劣化過程を把握できる動的な分析手法が重要である。 The analysis of the resin deterioration is performed by capturing a transient state in which oxidation occurs dynamically. On the other hand, statically, it is made by analyzing a resin in a state where oxidation or decomposition has occurred as a reaction product after being oxidized and capturing the state. In order to grasp the deterioration state of the resin and take appropriate measures for preventing the deterioration, a dynamic analysis method capable of grasping the transient state of the deterioration, that is, the deterioration process is particularly important.
動的な分析手法として、一般に樹脂材料の耐熱性を議論する際には熱重量測定を中心とした熱分析が行われる。この方法では、樹脂材料のガス化が発生するような、主鎖切断に伴う大規模な反応温度域での劣化を評価することになる。一方、主鎖の切断前に生じる側鎖や樹脂末端の酸化劣化初期過程については、樹脂を加熱した際の酸化による発光を測定し、劣化状態を推定するオキシルミネセンス法（特許文献１、非特許文献２）が提案されている。これらの分析法は有用であるが、熱重量測定では初期の酸化による微少な重量変化を測定できず、一方のオキシルミネセンス法では主鎖の切断を発光現象として定量的にとらえることができなかった。このような背景から、初期の樹脂劣化過程である、樹脂の酸化劣化初期過程を把握する簡便な分析手法の開発と、その後に生じる主鎖切断過程を簡便に評価する手法の開発が望まれていた。 As a dynamic analysis method, in general, when discussing the heat resistance of a resin material, a thermal analysis centering on thermogravimetry is performed. In this method, deterioration in a large-scale reaction temperature region accompanying main chain cleavage that causes gasification of the resin material is evaluated. On the other hand, with respect to the initial stage of oxidative degradation of side chains and resin ends that occur before the main chain is cleaved, luminescence is measured by oxidation when the resin is heated to estimate the degradation state (Patent Document 1, Non-Patent Document 1). Patent Document 2) has been proposed. Although these analytical methods are useful, thermogravimetry cannot measure minute weight changes due to initial oxidation, while the oxyluminescence method cannot quantitatively detect main chain cleavage as a luminescence phenomenon. It was. Against this background, the development of a simple analytical method for grasping the initial process of resin oxidative degradation, which is the initial resin degradation process, and the development of a method for simply evaluating the subsequent main chain scission process are desired. It was.
上述の如く、従来技術に係る課題は、樹脂の劣化を議論する際の酸化劣化初期過程と主鎖切断過程を網羅する同一の分析法が無いこと、更に、この分析法を基に樹脂の劣化過程を評価し、劣化過程の評価に基づき劣化過程を制御及び又は抑制された樹脂材料とリサイクル樹脂材料及び又は樹脂成形品、そして、リサイクル樹脂材料を適切に含んだ成形品が提供されていないことである。 As described above, the problems related to the prior art are that there is no identical analysis method covering the initial process of oxidative degradation and the main chain scission process when discussing resin degradation, and furthermore, resin degradation based on this analytical method. Resin material and recycled resin material and / or resin molded product whose degradation process is controlled and / or suppressed based on evaluation of degradation process, and molded product appropriately containing recycled resin material are not provided It is.
本発明は、このような点を鑑みてなされたものであり、その目的は、樹脂の劣化を議論する際の酸化劣化初期過程と主鎖切断過程とを網羅する分析法を提供し、この分析法により劣化過程を判断して、その劣化過程を適切に制御及び又は抑止するための酸化防止剤を加えた合成樹脂材料及び又は樹脂成形品を提供すること、更には、前記分析法により劣化を適切に制御及び又は劣化状態を把握されたリサイクル樹脂材料及び又はリサイクル樹脂材料を適切に含んだ成形品を提供することである。 The present invention has been made in view of the above points, and an object of the present invention is to provide an analysis method that covers the initial stage of oxidative degradation and the main chain scission process when discussing resin degradation. To provide a synthetic resin material and / or a resin molded product to which an antioxidant for appropriately controlling and / or suppressing the deterioration process is added. The object is to provide a recycled resin material and / or a molded article appropriately containing the recycled resin material whose control and / or deterioration state is properly grasped.
本発明の請求項１では、劣化状態を判定されたリサイクル樹脂材料を用いた樹脂成形品の製造方法であって、前記リサイクル樹脂材料の劣化状態を判定する工程として、第１の工程として、リサイクル樹脂材料の融点以上の少なくとも１つの温度におけるメルトフローレイトを測定する第１のメルトフローレイト測定工程と、第２の工程として、前記第１のメルトフローレイト測定工程によりメルトフローレイト値を与えた樹脂のメルトフローレイト値を更に測定する第２のメルトフローレイト測定工程と、第３の工程として、前記第２のメルトフローレイト測定工程によりメルトフローレイト値を与えた樹脂のメルトフローレイト値を更に測定する第３のメルトフローレイト測定工程と、第４の工程として、前記第１のメルトフローレイト測定工程により得られたメルトフローレイト値（第１ＭＦＲ値）と前記第２のメルトフローレイト測定工程により得られたメルトフローレイト値（第２ＭＦＲ値）と、前記第３のメルトフローレイト測定工程により得られたメルトフローレイト値（第３ＭＦＲ値）とを比較し、第１ＭＦＲ値 ＞ 第２ＭＦＲ値 ＞ 第３ＭＦＲ値 である場合には、当該リサイクル樹脂材料の劣化状態が初期の酸化劣化状態であると判定され、リサイクル樹脂材料として適正であり、成形に用いる当該リサイクル樹脂材料の混合割合を１ｗｔ％〜１００ｗｔ％まで任意に設定でき、第１ＭＦＲ値 ＜ 第２ＭＦＲ値 ＜ 第３ＭＦＲ値 である場合には、当該リサイクル樹脂材料の劣化状態が主鎖の切断が生じている状態であると判定され、リサイクル樹脂材料としてリサイクルするには不向きではあるが、成形に用いる当該リサイクル樹脂材料の混合割合を１ｗｔ％〜３０ｗｔ％まで任意に設定でき、第１ＭＦＲ値 ＞ 第２ＭＦＲ値 ＜ 第３ＭＦＲ値 である場合には、当該リサイクル樹脂材料の劣化状態が初期の酸化劣化状態ではあるが主鎖の切断を生じうる状態であると判定され、成形に用いる当該リサイクル樹脂材料の混合割合を１ｗｔ％〜８０ｗｔ％まで任意に設定でき、第１ＭＦＲ値と第２ＭＦＲ値と第３ＭＦＲ値との差異が０．４％以内である場合には、測定温度を上げて再度第１ＭＦＲ値、第２ＭＦＲ値、そして、第３ＭＦＲ値を測定し、樹脂の劣化状態を判定した後、第１から第３のメルトフローレイト値の大小関係を上記の関係に当てはめた混合割合に従って、成形品としてリサイクルするリサイクル工程を含むことを特徴とする劣化状態を判定されたリサイクル樹脂材料を用いた樹脂成形品の製造方法である。 According to claim 1 of the present invention, there is provided a method for manufacturing a resin molded article using a recycled resin material whose deterioration state has been determined, wherein the first step is recycling as the step of determining the deterioration state of the recycled resin material. A melt flow rate value was given by the first melt flow rate measurement step as a first melt flow rate measurement step for measuring the melt flow rate at at least one temperature equal to or higher than the melting point of the resin material, and the second step. A second melt flow rate measurement step for further measuring the melt flow rate value of the resin, and a third step of measuring the melt flow rate value of the resin given the melt flow rate value by the second melt flow rate measurement step. Further, a third melt flow rate measuring step for measuring and a fourth step as the first melt flow rate measuring step. The melt flow rate value (first MFR value) obtained by the fixing step, the melt flow rate value (second MFR value) obtained by the second melt flow rate measurement step, and the third melt flow rate measurement step The obtained melt flow rate value (third MFR value) is compared, and when the first MFR value> the second MFR value> the third MFR value, the deterioration state of the recycled resin material is the initial oxidation deterioration state. If it is determined and is appropriate as a recycled resin material, the mixing ratio of the recycled resin material used for molding can be arbitrarily set from 1 wt% to 100 wt%, and when the first MFR value <the second MFR value <the third MFR value, It is determined that the degradation state of the recycled resin material is a state in which the main chain is broken, and the recycled resin material is recycled. Although it is unsuitable for curling, the mixing ratio of the recycled resin material used for molding can be arbitrarily set from 1 wt% to 30 wt%, and when the first MFR value> the second MFR value <the third MFR value, It is determined that the deterioration state of the resin material is an initial oxidative deterioration state but a state in which the main chain can be broken, and the mixing ratio of the recycled resin material used for molding can be arbitrarily set from 1 wt% to 80 wt%, When the difference between the first MFR value, the second MFR value, and the third MFR value is within 0.4%, the measurement temperature is raised and the first MFR value, the second MFR value, and the third MFR value are measured again. after determining the state of deterioration, according to the mixing ratio of the magnitude relation fitted to the above relationship of a third melt flow rate value from the first, Lisa recycled as a molded article It is a manufacturing method of the resin molded product using the recycled resin material in which the deterioration state was determined characterized by including an icing process .
以上説明したように、従来では樹脂の劣化を議論する際に酸化劣化初期過程と主鎖切断過程を評価するためそれぞれ異なる分析法を用い実施してきたが、本願発明の請求項１においては、メルトフローレイトを測定することにより、使用されたり成形されたりした樹脂の劣化状態を判定し、この判定結果を基にしてリサイクル樹脂材料の成形品への混合割合を決定することができるため、リサイクル樹脂材料の適切な管理と利用が可能となる。 As described above, conventionally, when discussing the deterioration of the resin, different analysis methods have been used to evaluate the initial oxidation degradation process and the main chain cleavage process. By measuring the flow rate, it is possible to determine the deterioration state of used or molded resin, and based on this determination result, the mixing ratio of the recycled resin material to the molded product can be determined. Appropriate management and use of materials becomes possible.
以下、本発明の実施例及び実験例を、図面を参照しながら詳細に説明する。 Hereinafter, examples and experimental examples of the present invention will be described in detail with reference to the drawings.
本発明の実施の形態に係る第１の実験の例として、低密度ポリエチレン（ＬＤＰＥ、アルドリッチ社製）のペレットを用い、乾燥後メルトフローレイト試験を行った。メルトフローレイト試験にはメルトフローレイト自動化システム（東洋精機社製、完全自動化システム５２０）を用いた。試験条件は、温度２１０℃、２３０℃、２５０℃、荷重５．０ｋｇ、温度保持時間３００秒とした。結果を図８に示す。ここでの繰り返し回数とは、同一の樹脂材料についてメルトフローレイト試験を繰り返し行った回数である。ＬＤＰＥペレットのメルトフローレイト値は、繰り返し回数１（温度保持時間３００秒）で６．６９ｇ／１０分（ｍｉｎと表記することもできる）であったが、繰り返し回数２（温度保持時間６００秒）で６．１３ｇ／１０分と低下し、繰り返し回数３（温度処理時間９００秒）で５．５５ｇ／１０分とさらに低下した。本実験例１の結果、ＬＤＰＥ樹脂については、前記第１ＭＦＲ値が前記第２ＭＦＲ値より大きい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程が支配的であると判定された。もし主鎖切断による劣化が生じているとすれば後述する実験例２や実験例３と同様にメルトフローレイト値の増加が確認されるはずである。ここで観察されたメルトフローレイト値の低下が分子量の増加を示すのであれば、熱処理により樹脂内で酸化劣化初期過程に伴う何らかの反応が起きていると考えられる。本実験例１において、ＬＤＰＥ樹脂の初期の酸化劣化過程の反応速度定数ｋを当該所定温度毎に測定された前記第１ＭＦＲ値と第２ＭＦＲ値とメルトフローレイト測定工程数より、式１を用いて算出した。この工程より得られた反応速度定数ｋとそれぞれの反応速度定数ｋを測定した温度とから式２に示した式より活性化エネルギーを算出した。
（式１）Ｌｎ（（第１ＭＦＲ値）÷ （第２ＭＦＲ値））／（（ＭＦＲ測定工程数）−１）
＝ ｋ
（式２）Ｌｎ（ｋ）=Ｌｎ(頻度因子)−（活性化エネルギー）／（８．３１４Ｊ／ｍｏｌＫ×（温度））
反応速度定数は、２１０℃において０．０９８１／回、２３０℃において０．１５５７／回、２５０℃において０．３４８４／回、温度の逆数に対するｌｎ（ｋ）を図４のようにプロットし、直線の傾きから活性化エネルギーを６６ｋJ／ｍｏｌ（モルと記すこともある。）と求めた。また、図５に示したように、２３０℃において温度繰り返し回数を増やした場合、ＭＦＲ値の増加が確認され、酸化劣化初期過程に続く主鎖切断過程が生じていることが確認された。実験例１の分析結果を図８に示した。本実験例１では、樹脂の劣化過程の評価を図６に示したフローチャートを用いて行った。
As an example of a first experiment according to an embodiment of the present invention, low-density polyethylene (LDPE, manufactured by Aldrich) pellets were used, and a post-drying melt flow rate test was performed. A melt flow rate automation system (manufactured by Toyo Seiki Co., Ltd., fully automated system 520) was used for the melt flow rate test. The test conditions were a temperature of 210 ° C., 230 ° C., 250 ° C., a load of 5.0 kg, and a temperature holding time of 300 seconds. The results are shown in FIG. Here, the number of repetitions is the number of times that the melt flow rate test was repeatedly performed on the same resin material. The melt flow rate value of the LDPE pellet was 6.69 g / 10 minutes (may be expressed as min) at a repetition number of 1 (temperature holding time of 300 seconds), but the number of repetitions was 2 (temperature holding time of 600 seconds). At 6.13 g / 10 min, and further decreased to 5.55 g / 10 min at 3 repetitions (temperature treatment time 900 seconds). As a result of Experimental Example 1, since the first MFR value was larger than the second MFR value for the LDPE resin, it was determined that the initial oxidation deterioration process was dominant in the deterioration process of the resin material. If deterioration due to main chain breakage has occurred, an increase in melt flow rate value should be confirmed as in Experimental Examples 2 and 3 described later. If the observed decrease in the melt flow rate value indicates an increase in molecular weight, it is considered that some kind of reaction has occurred in the resin during the initial stage of oxidative degradation due to heat treatment. In Experimental Example 1, the reaction rate constant k in the initial oxidative degradation process of the LDPE resin is calculated from the first MFR value, the second MFR value, and the number of melt flow rate measurement steps measured for each predetermined temperature, using Equation 1. Calculated. The activation energy was calculated from the equation shown in Equation 2 from the reaction rate constant k obtained from this step and the temperature at which each reaction rate constant k was measured.
(Formula 1) Ln ((first MFR value) ÷ (second MFR value)) / ((number of MFR measurement steps) −1)
= K
(Formula 2) Ln (k) = Ln (frequency factor) − (activation energy) / (8.314 J / molK × (temperature))
The reaction rate constant was 0.0981 / time at 210 ° C., 0.1557 / time at 230 ° C., 0.3484 / time at 250 ° C., and ln (k) against the reciprocal of temperature was plotted as shown in FIG. From the slope, the activation energy was determined to be 66 kJ / mol (sometimes referred to as mole). Further, as shown in FIG. 5, when the number of temperature repetitions was increased at 230 ° C., an increase in MFR value was confirmed, and it was confirmed that a main chain scission process following the initial process of oxidative degradation occurred. The analysis result of Experimental Example 1 is shown in FIG. In Experimental Example 1, the deterioration process of the resin was evaluated using the flowchart shown in FIG.
本発明の実施の形態に係る第２の実験の例として、主鎖がポリエチレンと同様でその側鎖の炭素に酸素が結合しているポリメチルメタアクリレート（ＰＭＭＡ）について、劣化過程の分析、劣化反応速度定数、劣化反応の活性化エネルギーを求めた。乾燥させたペレットを用いて、温度２３０℃、荷重５．０ｋｇ、温度保持時間３００秒の条件でメルトフロー試験を繰り返し行った。メルトフローレイト試験にはメルトフローレイト自動化システム（東洋精機社製、完全自動化システム５２０）を用いた。結果を図８に示す。測定されたＭＦＲ値は、繰り返し回数１（温度保持時間３００秒）で９．０４ｇ／１０分であったが、繰り返し回数２（温度保持時間６００秒）で９．００ｇ／１０分と低下し、繰り返し回数３（温度保持時間９００秒）で８．９６ｇ／１０分とさらに低下した。このときの劣化反応過程は、前記第１ＭＦＲ値が前記第２ＭＦＲ値より大きい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程が支配的であると判定された。上述した式（１）により、温度２３０℃の酸化劣化過程の反応速度定数は、０．００４４／回とされた。また、温度を２４０℃とした以外は、すべて同じ条件で実験を行った場合、やはり前記第１ＭＦＲ値が前記第２ＭＦＲ値より大きい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程が支配的であると判定された。また、温度２４０℃の酸化劣化過程の反応速度定数は、０．００５８／回とされた。また、温度を２５０℃とした以外は、すべて同じ条件で実験を行った場合、第１ＭＦＲ値が前記第２ＭＦＲ値より小さい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程を含んだとしても支配的では無く主鎖の切断を伴う主鎖切断過程が支配的であると判断された。また、２５０℃における主鎖の切断を伴う主鎖切断過程の反応速度定数は、０．０３１２／回とされた。以上から、上述した実験例１と同様の方法により、ＰＭＭＡについては、２３０℃から２４０℃までの酸化劣化過程の活性化エネルギーは、５９ｋJ／モルと算出された。実験例２の分析結果を図８に示す。本実験例２では、樹脂の劣化過程の評価を図６に示したフローチャートを用いて行った。このように、メルトフローレイトを繰り返し測定する樹脂の劣化状態を判定する方法においては、同一樹脂であっても温度の違いにより異なる分解過程が生じることを確認できた。 As an example of the second experiment according to the embodiment of the present invention, analysis of degradation process and degradation of polymethyl methacrylate (PMMA) in which the main chain is similar to polyethylene and oxygen is bonded to carbon of the side chain. The reaction rate constant and the activation energy of the degradation reaction were determined. Using the dried pellets, the melt flow test was repeated under the conditions of a temperature of 230 ° C., a load of 5.0 kg, and a temperature holding time of 300 seconds. A melt flow rate automation system (manufactured by Toyo Seiki Co., Ltd., fully automated system 520) was used for the melt flow rate test. The results are shown in FIG. The measured MFR value was 9.04 g / 10 minutes at a repetition number 1 (temperature holding time 300 seconds), but decreased to 9.00 g / 10 minutes at a repetition number 2 (temperature holding time 600 seconds). When the number of repetitions was 3 (temperature holding time: 900 seconds), it further decreased to 8.96 g / 10 minutes. Since the deterioration reaction process at this time is a case where the first MFR value is larger than the second MFR value, it was determined that the initial stage of oxidation deterioration was dominant in the deterioration process of the resin material. From the above equation (1), the reaction rate constant in the oxidative deterioration process at a temperature of 230 ° C. was set to 0.0044 / time. In addition, when the experiments were performed under the same conditions except that the temperature was 240 ° C., the first MFR value was still larger than the second MFR value. It was determined to be dominant. The reaction rate constant in the oxidative deterioration process at a temperature of 240 ° C. was set to 0.0058 / time. In addition, when the experiment was performed under the same conditions except that the temperature was 250 ° C., the first MFR value was smaller than the second MFR value, and therefore the deterioration process of the resin material included an initial stage of oxidation deterioration. However, it was judged that the main chain cutting process accompanied by main chain breakage was dominant. Moreover, the reaction rate constant of the main chain cleavage process accompanied by main chain cleavage at 250 ° C. was set to 0.0312 / times. From the above, the activation energy in the oxidative degradation process from 230 ° C. to 240 ° C. was calculated to be 59 kJ / mol for PMMA by the same method as in Experimental Example 1 described above. The analysis result of Experimental Example 2 is shown in FIG. In Experimental Example 2, the degradation process of the resin was evaluated using the flowchart shown in FIG. As described above, in the method for determining the deterioration state of the resin by repeatedly measuring the melt flow rate, it was confirmed that even if the same resin is used, different decomposition processes occur due to temperature differences.
本発明の実施の形態に係る第３の実験の例として、主鎖に酸素を含むポリオキシメチレン（ＰＯＭ）について、劣化過程の分析、劣化反応の速度、劣化反応の活性化エネルギーを求めた。乾燥させたペレットを用いて、温度２００℃、荷重２．１６ｋｇ、温度保持時間３００秒の条件でメルトフローレイト試験を繰り返し行った。メルトフローレイト試験にはメルトフローレイト自動化システム（東洋精機社製、完全自動化システム５２０）を用いた。結果を図８に示す。測定されたＭＦＲ値は、繰り返し回数１（温度保持時間３００秒）で２０．９６ｇ／１０分であったが、繰り返し回数２（温度保持時間６００秒）で２１．３１ｇ／１０分と増加し、繰り返し回数３（温度保持時間９００秒）で２１．９４ｇ／１０分とさらに増加した。第１ＭＦＲ値が第２ＭＦＲ値より小さい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程を含んだとしても支配的では無く主鎖の切断を伴う分解過程が支配的であると判断された。また、２００℃における主鎖の切断を伴う主鎖切断過程の速度定数は、０．０１７０／回と算出された。また、温度を２１０℃とした以外は、すべて同じ条件で実験を行った場合、第１ＭＦＲ値が第２ＭＦＲ値より小さい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程を含んだとしても支配的では無く主鎖の切断を伴う分解過程が支配的であると判断された。また、２１０℃における主鎖の切断を伴う主鎖切断過程の速度定数は、０．０６１９／回と算出された。また、温度を２３０℃とした以外は、すべて同じ条件で実験を行った場合、第１ＭＦＲ値が第２ＭＦＲ値より小さい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程を含んだとしても支配的では無く主鎖の切断を伴う分解過程が支配的であると判断された。また、２３０℃における主鎖の切断を伴う主鎖切断過程の速度定数は、０．１００１／回と算出された。以上から、ＰＯＭについては、２００℃から２３０℃までの主鎖切断に伴う活性化エネルギーは、１０８ｋJ／モルと算出された。実験例３の分析結果を図８に示した。本実験例３では、樹脂の劣化過程の評価を図６に示したフローチャートを用いて行った。 As an example of the third experiment according to the embodiment of the present invention, the analysis of the deterioration process, the speed of the deterioration reaction, and the activation energy of the deterioration reaction were obtained for polyoxymethylene (POM) containing oxygen in the main chain. Using the dried pellets, the melt flow rate test was repeatedly performed under the conditions of a temperature of 200 ° C., a load of 2.16 kg, and a temperature holding time of 300 seconds. A melt flow rate automation system (manufactured by Toyo Seiki Co., Ltd., fully automated system 520) was used for the melt flow rate test. The results are shown in FIG. The measured MFR value was 20.96 g / 10 minutes at the number of repetitions 1 (temperature holding time 300 seconds), but increased to 21.31 g / 10 minutes at the number of repetitions 2 (temperature holding time 600 seconds), When the number of repetitions was 3 (temperature holding time 900 seconds), the number further increased to 21.94 g / 10 minutes. Since the first MFR value is smaller than the second MFR value, the degradation process of the resin material is not dominant even if it includes the initial oxidation degradation process, and it is determined that the degradation process involving main chain scission is dominant. It was. Moreover, the rate constant of the main chain cutting process accompanied by main chain cleavage at 200 ° C. was calculated to be 0.0170 / time. In addition, when the experiment was performed under the same conditions except that the temperature was 210 ° C., the first MFR value was smaller than the second MFR value, so that the deterioration process of the resin material included the initial stage of oxidation deterioration. However, it was judged that the degradation process accompanied by the main chain breakage was dominant. Moreover, the rate constant of the main chain cutting process accompanied by main chain cleavage at 210 ° C. was calculated to be 0.0619 / time. In addition, when the experiment was performed under the same conditions except that the temperature was 230 ° C., the first MFR value was smaller than the second MFR value, and therefore the initial deterioration process of the resin material was included in the deterioration process of the resin material. However, it was judged that the degradation process accompanied by the main chain breakage was dominant. Further, the rate constant of the main chain cleavage process accompanied by main chain cleavage at 230 ° C. was calculated to be 0.1001 / time. From the above, for POM, the activation energy accompanying main chain cleavage from 200 ° C. to 230 ° C. was calculated to be 108 kJ / mol. The analysis result of Experimental Example 3 is shown in FIG. In Experimental Example 3, the deterioration process of the resin was evaluated using the flowchart shown in FIG.
本発明の実施の形態に係る第４の実験の例として、前記第１から第３の実験の形態を基に、樹脂の劣化過程について解析を行った。結果を図１に示す。実験例１より側鎖、主鎖ともに酸素を含まないＬＤＰＥの劣化過程は、当該樹脂の側鎖や末端が酸化される酸化劣化初期過程として観測された。また、実験例２より側鎖に酸素を含むＰＭＭＡの劣化過程は、一部酸化劣化初期過程が見られたが、主鎖切断過程も観測された。一方、実験例３より主鎖に酸素を含むＰＯＭの劣化過程は、主鎖切断過程が支配的であると観測された。これらから、樹脂のメルトフローレイトを繰り返し測定することは、初期の樹脂劣化過程である樹脂の酸化劣化初期過程を把握する簡便な分析手法並びにその後に生じる主鎖切断過程を簡便に評価する手法として有用であることが示された。 As an example of the fourth experiment according to the embodiment of the present invention, the degradation process of the resin was analyzed based on the first to third experiments. The results are shown in FIG. From Experimental Example 1, the degradation process of LDPE containing no oxygen in both the side chain and the main chain was observed as an initial stage of oxidation degradation in which the side chain and terminal of the resin were oxidized. In addition, from the experimental example 2, the deterioration process of PMMA containing oxygen in the side chain was partially observed in the initial stage of oxidative deterioration, but the main chain breaking process was also observed. On the other hand, it was observed from Experimental Example 3 that the degradation process of POM containing oxygen in the main chain was dominant in the main chain cleavage process. From these results, repeated measurement of the melt flow rate of the resin is a simple analytical method for grasping the initial process of oxidative degradation of the resin, which is the initial process of resin degradation, as well as a method for simply evaluating the subsequent main chain scission process. It has been shown to be useful.
本発明の第１の実施の形態に係る分析と樹脂の劣化過程防止の例として、前記実験例１の形態に係る分析条件のうち、ＬＤＰＥに添加剤として、酸化防止剤Ｉｒｇａｎｏｘ１０１０（商標登録）をＬＤＰＥに対し１ｗｔ％と成るように添加した以外は全て同一の条件でＬＤＰＥのメルトフローレイト値を測定した。温度２１０℃における添加剤を入れたＬＤＰＥのメルトフローレイト値は、繰り返し回数１（温度保持時間３００秒）で６．６０ｇ／１０分であったが、繰り返し回数２（温度保持時間６００秒）で６．４８ｇ／１０分と低下し、繰り返し回数３（温度処理時間９００秒）で６．２９ｇ／１０分とさらに低下した。本実験例５のＬＤＰＥ樹脂については、前記第１ＭＦＲ値が前記第２ＭＦＲ値より大きい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程が支配的であると判定された。また、２３０℃、２５０℃においても添加剤を加えたＬＤＰＥについて、劣化過程を初期の酸化劣化過程であると評価した。本実験例５において、添加剤を加えたＬＤＰＥ樹脂の初期の酸化劣化過程の反応速度定数を２１０℃において０．０１８３／回、２３０℃において０．０２５０／回、２５０℃において０．０５４９／回、活性化エネルギーを５８ｋJ／ｍｏｌと求めることができた。実験例１で実験した添加剤を加えていないＬＤＰＥに比べ、本実施例１で行った添加剤を加えたＬＤＰＥでは酸化劣化過程を、２１０℃において１８％、２３０℃において１６％、２５０℃において１６％にそれぞれ低下することができ、樹脂を長寿命化できることが確認された。実施例１において分析された結果を図８に示す。本実施例１では、樹脂の劣化過程の評価を図６に示したフローチャートを用いて行った。 As an example of the analysis according to the first embodiment of the present invention and prevention of the deterioration process of the resin, among the analysis conditions according to the form of Experimental Example 1, the antioxidant Irganox 1010 (registered trademark) was added as an additive to LDPE. The melt flow rate value of LDPE was measured under the same conditions except that it was added to 1 wt% with respect to LDPE. The melt flow rate value of LDPE with an additive at a temperature of 210 ° C. was 6.60 g / 10 min at 1 repetition (temperature holding time 300 seconds), but at 2 repetitions (temperature holding time 600 seconds). It decreased to 6.48 g / 10 min, and further decreased to 6.29 g / 10 min at 3 repetitions (temperature treatment time: 900 seconds). With respect to the LDPE resin of Experimental Example 5, since the first MFR value is greater than the second MFR value, it was determined that the initial oxidation deterioration process is dominant in the deterioration process of the resin material. Moreover, the deterioration process was evaluated as an initial oxidation deterioration process for LDPE to which an additive was added even at 230 ° C. and 250 ° C. In Experimental Example 5, the reaction rate constant of the initial oxidative degradation process of the LDPE resin to which the additive was added was 0.0183 / time at 210 ° C., 0.0250 / time at 230 ° C., and 0.0549 / time at 250 ° C. The activation energy was found to be 58 kJ / mol. Compared with the LDPE not added with the additive tested in Experimental Example 1, the LDPE added with the additive carried out in Example 1 shows the oxidative deterioration process at 210 ° C, 18% at 230 ° C, 16% at 230 ° C, and at 250 ° C. It could be reduced to 16%, respectively, and it was confirmed that the life of the resin could be extended. The results analyzed in Example 1 are shown in FIG. In Example 1, the degradation process of the resin was evaluated using the flowchart shown in FIG.
本発明の第２の実施の形態に係る分析と樹脂の劣化過程防止の例として、前記実験例２の形態に係る分析条件のうち、ＰＭＭＡに添加剤として、酸化防止剤Ｉｒｇａｎｏｘ１０１０（商標登録）をＰＭＭＡに対し１ｗｔ％と成るように添加した以外は全て同一の条件でＰＭＭＡのメルトフローレイト値を測定した。温度２５０℃における添加剤を入れたＰＭＭＡのメルトフローレイト値は、繰り返し回数１（温度保持時間３００秒）で３１．０６ｇ／１０分であったが、繰り返し回数２（温度保持時間６００秒）で２８．７１ｇ／１０分と低下し、繰り返し回数３（温度処理時間９００秒）で２８．８８ｇ／１０分とさらに低下した。本実験例６のＰＭＭＡについては、前記第１ＭＦＲ値が前記第２ＭＦＲ値より大きい場合であるため、当該樹脂材料の劣化過程において酸化劣化初期過程が支配的であると判定された。一方、実験例２で実験した添加剤を加えていないＰＭＭＡでは、２５０℃では、当該樹脂材料の劣化過程において酸化劣化初期過程を含んだとしても支配的では無く主鎖の切断を伴う分解過程が支配的であると判断されたため、本実施例２で行った添加剤を加えたＰＭＭＡにおいて、樹脂を長寿命化できたことが確認された。本実施例２において分析された結果を図８に示す。本実施例２では、樹脂の劣化過程の評価を図６に示したフローチャートを用いて行った。 As an example of analysis according to the second embodiment of the present invention and prevention of deterioration process of the resin, among the analysis conditions according to the form of Experimental Example 2, the antioxidant Irganox 1010 (registered trademark) is used as an additive to PMMA. The melt flow rate value of PMMA was measured under the same conditions except that it was added at 1 wt% with respect to PMMA. The melt flow rate value of PMMA containing an additive at a temperature of 250 ° C. was 31.06 g / 10 min at 1 repetition (temperature holding time 300 seconds), but at 2 repetitions (temperature holding time 600 seconds). It decreased to 28.71 g / 10 minutes, and further decreased to 28.88 g / 10 minutes after 3 repetitions (temperature treatment time: 900 seconds). Regarding PMMA in this Experimental Example 6, since the first MFR value is larger than the second MFR value, it was determined that the initial stage of oxidation deterioration was dominant in the deterioration process of the resin material. On the other hand, in PMMA not added with the additive tested in Experimental Example 2, at 250 ° C., the degradation process of the resin material is not dominant even if the degradation process of the resin material includes the initial stage of oxidative degradation, and the degradation process accompanied by the cleavage of the main chain occurs. Since it was determined to be dominant, it was confirmed that the resin life could be extended in the PMMA to which the additive used in Example 2 was added. The result analyzed in Example 2 is shown in FIG. In Example 2, the degradation process of the resin was evaluated using the flowchart shown in FIG.
本発明の第３の実施の形態に係る分析の例として、ポリスチレン（ＰＳ）とポリフェニレンエーテル（ＰＰＥ）の混合樹脂射出成型品について繰り返し射出成形回数毎のメルトフローレイト試験と分子量分布測定を実施した。射出成形は、卓上型の射出成形機を用いてダンベル状の引張試験片を作成した。メルトフローレイト試験にはメルトフローレイト自動化システム（東洋精機社製、完全自動化システム５２０）を用い、分子量分布測定には分子量分布測定システム（島津製作所社製、Ｄ５２８０ ＬＣＳ Ｍ−ＰＤＡ）を用いた。繰り返し射出成形回数毎のメルトフローレイト値と重量平均分子量を図９及び図２に示す。繰り返し射出成形回数が増加するとメルトフローレイト値は増加した。繰り返し射出成形回数毎にメルトフローレイト値を繰り返し測定した場合、本実施例１のＰＳ−ＰＰＥ混合樹脂については、第１ＭＦＲ値 ＜ 第２ＭＦＲ値 ＜ 第３ＭＦＲ値であるため当該樹脂材料の劣化状態が主鎖の切断が生じている状態であると判定された。重量平均分子量の低下は、樹脂の主鎖切断によると考えられ、射出成形回数が増すに従い樹脂の重量平均分子量が低下していることから、本願発明の樹脂材料の劣化状態が主鎖の切断を伴っているという判定を肯定することが確認された。また、図３に示したように、重量平均分子量の低下に伴い、メルトフローレイト値は増加した。これらのことから、繰り返し射出成形回数に対するメルトフローレイト値の増加は、樹脂の主鎖切断による低分子量化を観測できていることが確認できた。本実施例３では、樹脂の劣化過程の評価を図７に示したフローチャートを用いて行った。 As an example of the analysis according to the third embodiment of the present invention, a melt flow rate test and a molecular weight distribution measurement were repeatedly performed for each injection molding of a mixed resin injection molded product of polystyrene (PS) and polyphenylene ether (PPE). . In the injection molding, a dumbbell-shaped tensile test piece was prepared using a desktop injection molding machine. A melt flow rate automation system (manufactured by Toyo Seiki Co., Ltd., fully automated system 520) was used for the melt flow rate test, and a molecular weight distribution measurement system (D5280 LCS M-PDA, manufactured by Shimadzu Corporation) was used for the molecular weight distribution measurement. 9 and 2 show the melt flow rate value and the weight average molecular weight for each repeated injection molding. As the number of repeated injection moldings increased, the melt flow rate value increased. When the melt flow rate value is repeatedly measured for each number of repeated injection moldings, the PS-PPE mixed resin of Example 1 has the first MFR value <the second MFR value <the third MFR value, so the deterioration state of the resin material is It was determined that the main chain was broken. The decrease in the weight average molecular weight is thought to be due to the main chain cleavage of the resin, and the weight average molecular weight of the resin decreases as the number of injection molding increases, so the degradation state of the resin material of the present invention causes the main chain to break. It was confirmed that the determination of being accompanied was affirmed. Moreover, as shown in FIG. 3, the melt flow rate value increased as the weight average molecular weight decreased. From these facts, it was confirmed that the increase in the melt flow rate value with respect to the number of repeated injection moldings was able to observe a decrease in the molecular weight due to the main chain cleavage of the resin. In Example 3, the deterioration process of the resin was evaluated using the flowchart shown in FIG.
本発明の第４の実施の形態に係る分析の例として、第３の実施の形態に係る分析で測定したＰＳ−ＰＰＥ混合樹脂のメルトフローレイト値に対する重量平均分子量のプロットを図３に示す。この結果より、メルトフローレイト値と重量平均分子量には相関があり、繰り返し射出成形回数が多くなるにつれて傾きが小さくなることがわかる。ＰＰＥは高軟化点を持ち機械的特性、電気的特性に優れた代表的なエンジニアリングプラスチックであるが、溶融温度が高いため成形性に劣る。そのためＰＰＥと相溶性を持つＰＳをブレンドして混合樹脂とすることで溶融流動特性を改善したのがＰＳ−ＰＰＥ混合樹脂である。ＰＳのみのメルトフローレイト値を測定した結果を、図８に示す。ＰＳでは、繰り返し測定回数が少ない場合でもメルトフローレイト値の増加が確認された。これらのことから、ＰＳ−ＰＰＥ混合樹脂における繰り返し測定回数が少ない段階での劣化は主にＰＳの分解によると判断される。このように、混合された樹脂についてもメルトフローレイト試験を繰り返し行うことで、混合された樹脂毎に主鎖の切断を伴う劣化過程と劣化反応速度を評価可能であることが示された。 As an example of the analysis according to the fourth embodiment of the present invention, a plot of the weight average molecular weight with respect to the melt flow rate value of the PS-PPE mixed resin measured in the analysis according to the third embodiment is shown in FIG. This result shows that there is a correlation between the melt flow rate value and the weight average molecular weight, and the slope decreases as the number of repeated injection moldings increases. PPE is a typical engineering plastic having a high softening point and excellent mechanical and electrical characteristics, but has poor moldability due to its high melting temperature. Therefore, PS-PPE mixed resin has improved melt flow characteristics by blending PS compatible with PPE into a mixed resin. The result of measuring the melt flow rate value of only PS is shown in FIG. In PS, an increase in melt flow rate value was confirmed even when the number of repeated measurements was small. From these facts, it is judged that the deterioration at the stage where the number of repeated measurements in the PS-PPE mixed resin is small is mainly due to the decomposition of PS. Thus, it was shown that the deterioration process and the deterioration reaction rate accompanied by the main chain breakage can be evaluated for each mixed resin by repeatedly performing the melt flow rate test on the mixed resin.
本発明の第５の実施の形態に係る分析の例として、２７０℃で３０分間熱処理したＬＤＰＥ、太陽光と同様の波長分布を持つキセノンランプによる光を屋外での換算で約６ヶ月間照射したＬＤＰＥ及びＰＭＭＡの３種類の劣化樹脂をリサイクル樹脂材料として作成した。これらのリサイクル樹脂材料の劣化状態は、本願発明の樹脂の劣化状態の評価法により、キセノンランプ光により劣化させたＬＤＰＥでは、第１ＭＦＲ値 ＜ 第２ＭＦＲ値 ＜ 第３ＭＦＲ値 であったため、当該リサイクル樹脂材料の劣化状態が主鎖の切断が生じている状態であると判定された。２７０℃で３０分間熱処理したＬＤＰＥは、第１ＭＦＲ値 ＞ 第２ＭＦＲ値 ＜ 第３ＭＦＲ値 であったため、当該リサイクル樹脂材料の劣化状態が初期の酸化劣化過程ではあるが主鎖の切断を生じうる状態であると判定された。キセノンランプ光により劣化させたＰＭＭＡでは、第１ＭＦＲ値 ＞ 第２ＭＦＲ値 ＞ 第３ＭＦＲ値 であったため、当該リサイクル樹脂材料の劣化状態が初期の酸化劣化過程であると判定された。本実施例５では、樹脂の劣化過程の評価を図７に示したフローチャートを用いて行った。 As an example of analysis according to the fifth embodiment of the present invention, LDPE heat-treated at 270 ° C. for 30 minutes and light from a xenon lamp having a wavelength distribution similar to sunlight were irradiated for about 6 months in terms of outdoor conversion. Three types of degraded resins, LDPE and PMMA, were prepared as recycled resin materials. The degradation state of these recycled resin materials is such that the first MFR value <the second MFR value <the third MFR value in the LDPE degraded by the xenon lamp light according to the evaluation method of the degradation state of the resin of the present invention. It was determined that the deterioration state of the material was a state in which the main chain was broken. Since LDPE heat-treated at 270 ° C. for 30 minutes was 1st MFR value> 2nd MFR value <3rd MFR value, the degradation state of the recycled resin material was an initial oxidative degradation process, but could cause main chain breakage. It was determined that there was. In the PMMA deteriorated by the xenon lamp light, since the first MFR value> the second MFR value> the third MFR value, the deterioration state of the recycled resin material was determined to be the initial oxidation deterioration process. In Example 5, the degradation process of the resin was evaluated using the flowchart shown in FIG.
実施例５において作成されたキセノンランプ光により劣化させたＬＤＰＥを劣化させていないＬＤＰＥと混合し、０ｗｔ％、３０ｗｔ％、５０ｗｔ％、８０ｗｔ％、そして、１００ｗｔ％（この場合、すべて劣化させたＬＤＰＥを利用）の割合で含ませた樹脂材料を作成した。ＬＤＰＥの射出成形品として、卓上型射出成形機を用いダンベル状の引張試験片を作成し、引張試験を実施した。リサイクル樹脂材料の割合が０ｗｔ％の試験片の引張強度を１００とした場合、３０ｗｔ％では９５、５０ｗｔ％では８０、８０ｗｔ％では６０、そして、１００ｗｔ％では５０の引張強度がそれぞれ得られた。これらの結果から、主鎖切断過程を生じている状態のリサイクル樹脂については、混合割合を１から３０ｗｔ％以下にすることにより、強度については良好な結果が得られることが確認された。また、混入量を３０ｗｔ％より多く含む場合には、強度低下が生じるため、用途が限定されることが確認された。しかし、添加剤を加えることにより、引張強度が添加剤を加えない場合に比べ向上することが確認された。 The LDPE deteriorated by the xenon lamp light produced in Example 5 was mixed with the undegraded LDPE, and 0 wt%, 30 wt%, 50 wt%, 80 wt%, and 100 wt% (in this case, all deteriorated LDPE) The resin material contained at a ratio of (utilized) was prepared. A dumbbell-shaped tensile test piece was prepared as an LDPE injection-molded product using a desktop injection molding machine, and a tensile test was performed. When the tensile strength of a test piece having a recycled resin material ratio of 0 wt% was taken as 100, a tensile strength of 95 was obtained at 30 wt%, 80 at 80 wt%, 60 at 80 wt%, and 50 at 100 wt%. From these results, it was confirmed that, with respect to the recycled resin in a state in which the main chain cleavage process occurs, by setting the mixing ratio to 1 to 30 wt% or less, good results can be obtained in terms of strength. Further, when the mixing amount is more than 30 wt%, the strength is reduced, and it has been confirmed that the application is limited. However, it was confirmed that the addition of the additive improves the tensile strength as compared with the case where the additive is not added.
実施例５において作成された２７０℃で３０分間の熱処理により劣化させたＬＤＰＥを劣化させていないＬＤＰＥと混合し、０ｗｔ％、３０ｗｔ％、５０ｗｔ％、８０ｗｔ％、そして、１００ｗｔ％（この場合、すべて劣化させたＬＤＰＥを利用）の割合で含んだ樹脂材料を作成した。ＬＤＰＥの射出成形品として、ダンベル状の引張試験片を作成し、引張試験を実施した。リサイクル樹脂材料を０ｗｔ％の試験片の引張強度を１００とした場合、３０ｗｔ％では９８、５０ｗｔ％では９５、８０ｗｔ％では９０、１００ｗｔ％では８０の引張強度がそれぞれ得られた。これらの結果から、樹脂材料の劣化状態が初期の酸化劣化過程ではあるが主鎖の切断を生じうる主鎖切断過程を生じている状態の場合、混合割合を１ｗｔ％以上８０ｗｔ％以下にすることにより、良好な結果が得られることが確認された。また、混入量を８０ｗｔ％より多く含む場合には、強度低下が生じるため、用途が限定されることが確認された。しかし、添加剤を加えることにより、引張強度が添加剤を加えない場合に比べ向上することが確認された。 The LDPE prepared in Example 5 that was deteriorated by heat treatment at 270 ° C. for 30 minutes was mixed with undegraded LDPE, and 0 wt%, 30 wt%, 50 wt%, 80 wt%, and 100 wt% (in this case, all A resin material containing a ratio of (using deteriorated LDPE) was prepared. A dumbbell-shaped tensile test piece was prepared as an LDPE injection-molded product, and a tensile test was performed. When the tensile strength of the 0 wt% test piece was 100%, the tensile strength of 98 was obtained at 30 wt%, 95 at 50 wt%, 90 at 80 wt%, and 80 at 100 wt%. From these results, when the deterioration state of the resin material is an initial oxidative deterioration process but a main chain cutting process that can cause the main chain to break, the mixing ratio should be 1 wt% or more and 80 wt% or less. Thus, it was confirmed that good results were obtained. Further, when the mixing amount is more than 80 wt%, the strength is reduced, and it has been confirmed that the application is limited. However, it was confirmed that the addition of the additive improves the tensile strength as compared with the case where the additive is not added.
実施例５において作成された当該キセノンランプ光により劣化させたＰＭＭＡを劣化させていないＰＭＭＡと混合し、０ｗｔ％、３０ｗｔ％、５０ｗｔ％、８０ｗｔ％、そして、１００ｗｔ％（この場合、すべて劣化させたＰＭＭＡを利用）の割合で含んだ樹脂材料を作成した。ＰＭＭＡの射出成形品として、ダンベル状の引張試験片を作成し、引張試験を実施した。リサイクル樹脂材料の割合が０ｗｔ％の試験片の引張強度を１００とした場合、３０ｗｔ％では９９、５０ｗｔ％では９９、８０ｗｔ％では９８、１００ｗｔ％では９６の引張強度がそれぞれ得られた。これらの結果から、樹脂材料の劣化状態が初期の酸化劣化過程であると判断された場合、混合割合１ｗｔ％から１００ｗｔ％において良好な結果が得られることが確認された。 The PMMA deteriorated by the xenon lamp light produced in Example 5 was mixed with undegraded PMMA, 0 wt%, 30 wt%, 50 wt%, 80 wt%, and 100 wt% (in this case, all were deteriorated) A resin material containing PMMA was used. As an injection molded product of PMMA, a dumbbell-shaped tensile test piece was prepared and a tensile test was performed. When the tensile strength of a test piece having a recycled resin material ratio of 0 wt% was taken as 100, 99 tensile strength was obtained at 30 wt%, 99 at 50 wt%, 98 at 80 wt%, and 96 tensile strength at 100 wt%. From these results, it was confirmed that when the deterioration state of the resin material was determined to be the initial oxidation deterioration process, good results were obtained at a mixing ratio of 1 wt% to 100 wt%.
以上、本発明の実施の形態を説明したが、本発明の範囲はこれに限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。 Although the embodiment of the present invention has been described above, the scope of the present invention is not limited to this, and it goes without saying that various modifications can be made without departing from the scope of the present invention.
従来技術では、樹脂劣化を議論するために酸化劣化初期過程と主鎖切断過程を網羅するには、複数の分析手法を用いる必要があった。本発明により、樹脂の流れ性を測定するメルトフローレイト試験を行うことで酸化劣化初期過程と主鎖切断過程を網羅する樹脂の劣化過程を得ることが可能となった。本発明により、今後、市場拡大が期待できる樹脂材料において、そのリサイクル性や耐候性の評価が従来と比べて低コストでできるようになる。また、操作も簡便で作業の標準化が容易であることから、産業上の利用可能性は大きい。 In the prior art, it was necessary to use a plurality of analytical methods to cover the initial stage of oxidation degradation and the main chain scission process in order to discuss resin degradation. According to the present invention, it is possible to obtain a deterioration process of a resin covering an initial stage of oxidation deterioration and a main chain cutting process by performing a melt flow rate test for measuring the flowability of the resin. According to the present invention, it is possible to evaluate the recyclability and weather resistance of resin materials that can be expected to expand in the future at a lower cost than conventional ones. Moreover, since the operation is simple and the standardization of work is easy, the industrial applicability is great.
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