JP6574081B1 - Plastic purity measurement method - Google Patents
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- JP6574081B1 JP6574081B1 JP2019506206A JP2019506206A JP6574081B1 JP 6574081 B1 JP6574081 B1 JP 6574081B1 JP 2019506206 A JP2019506206 A JP 2019506206A JP 2019506206 A JP2019506206 A JP 2019506206A JP 6574081 B1 JP6574081 B1 JP 6574081B1
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- 229920003023 plastic Polymers 0.000 title claims abstract description 102
- 239000004033 plastic Substances 0.000 title claims abstract description 102
- 238000000691 measurement method Methods 0.000 title description 4
- 239000004698 Polyethylene Substances 0.000 claims abstract description 121
- 229920000573 polyethylene Polymers 0.000 claims abstract description 120
- 239000004743 Polypropylene Substances 0.000 claims abstract description 119
- 229920001155 polypropylene Polymers 0.000 claims abstract description 118
- -1 polyethylene Polymers 0.000 claims abstract description 110
- 239000000126 substance Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000002329 infrared spectrum Methods 0.000 claims abstract description 29
- 238000004566 IR spectroscopy Methods 0.000 claims abstract description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 72
- 239000011118 polyvinyl acetate Substances 0.000 claims description 72
- 239000002904 solvent Substances 0.000 claims description 25
- 238000011088 calibration curve Methods 0.000 claims description 20
- 239000002699 waste material Substances 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 20
- 238000005259 measurement Methods 0.000 description 20
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 14
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004064 recycling Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005102 attenuated total reflection Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
本発明は、プラスチック中に含まれる、ＰＥ、ＰＰの量を簡便に求めることが可能な、プラスチックの純度測定方法を提供することを目的とする。本発明のプラスチックの純度測定方法は、ポリエチレンおよびポリプロピレンの少なくとも一方を含むプラスチックの純度測定方法であり、秤量した前記プラスチックに、秤量した内部標準物質を加える工程（Ａ）、内部標準物質が加えられたプラスチックを、赤外分光法で分析する工程（Ｂ）、前記工程（Ｂ）で得られたＩＲスペクトルから、プラスチックに含まれるポリエチレン量およびポリプロピレン量を求める工程（Ｃ）を有する。An object of this invention is to provide the purity measuring method of the plastics which can obtain | require the quantity of PE and PP contained in a plastic simply. The method for measuring the purity of a plastic according to the present invention is a method for measuring the purity of a plastic containing at least one of polyethylene and polypropylene. Step (A) of adding a weighed internal standard substance to the weighed plastic, and adding the internal standard substance. The step (B) of analyzing the plastic by infrared spectroscopy, and the step (C) for determining the amount of polyethylene and polypropylene contained in the plastic from the IR spectrum obtained in the step (B).
Description
本発明は、プラスチックの純度測定方法に関する。 The present invention relates to a method for measuring the purity of a plastic.
プラスチックは、主に炭素と水素とから成る高分子化合物であり、一般的に絶縁性に優れる、耐腐食性に優れる、金属や陶磁器と比べて軽量である、大量生産が可能、成形が容易等の様々な特徴を有しており、現代社会で幅広く用いられる材料である。 Plastic is a polymer compound mainly composed of carbon and hydrogen. Generally, it has excellent insulating properties, excellent corrosion resistance, is lighter than metals and ceramics, can be mass-produced, and can be easily molded. It is a material widely used in modern society.
プラスチックとしては、様々なものが実用化されているが、代表的なものとしてはポリエチレン、ポリプロピレン、塩化ビニル樹脂、ポリスチレン、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ＡＢＳ樹脂等が挙げられる。中でも、ポリエチレンおよびポリプロピレンは、それぞれプラスチック生産量の凡そ２０％を占めており、最も一般的なプラスチックである。 Various plastics have been put into practical use, but typical examples include polyethylene, polypropylene, vinyl chloride resin, polystyrene, polyethylene terephthalate (PET) resin, ABS resin, and the like. Among them, polyethylene and polypropylene each occupy about 20% of the plastic production, and are the most common plastics.
プラスチックは、大量に使用される材料であるため、廃棄されるプラスチック（廃プラスチック）の量もまた膨大である。廃棄されるプラスチックをリサイクルするための方法としては、大きく分けて、マテリアルリサイクル（材料リサイクル）、ケミカルリサイクル、サーマルリサイクル（エネルギー回収）の三つの方法がある。 Since plastic is a material used in large quantities, the amount of discarded plastic (waste plastic) is also enormous. There are three main methods for recycling discarded plastics: material recycling (material recycling), chemical recycling, and thermal recycling (energy recovery).
マテリアルリサイクルは、廃プラスチックを、他の製品か別のプラスチック材料として活用する方法である。ケミカルリサイクルは廃プラスチックを、化学的に処理し、化学原料として再生する方法である。サーマルリサイクルとは、廃プラスチックを熱源として利用する方法である。 Material recycling is a method of using waste plastic as another product or another plastic material. Chemical recycling is a method in which waste plastics are chemically treated and recycled as chemical raw materials. Thermal recycling is a method of using waste plastic as a heat source.
これらの方法で、廃プラスチックをリサイクルする際には、廃プラスチックの純度が問題となることがあるが、廃プラスチックの組成を簡便な方法で調べることは、一般に困難であった。 When recycling waste plastic by these methods, the purity of the waste plastic may be a problem, but it is generally difficult to examine the composition of the waste plastic by a simple method.
ところで、特許文献１には、ポリオレフィン樹脂組成物のプロピレン成分とエチレン成分との割合を定量する分析方法が開示されている。特許文献１に開示された方法は1Ｈ−ＮＭＲ法により行われる方法である。By the way, Patent Document 1 discloses an analysis method for quantifying a ratio of a propylene component and an ethylene component of a polyolefin resin composition. The method disclosed in Patent Document 1 is a method performed by 1 H-NMR method.
一般的な廃プラスチックとしては、ポリエチレンおよびポリプロピレンを主成分とする廃プラスチックがある。このようなポリエチレンおよびポリプロピレンを主成分とする廃プラスチックであっても、ポリエチレン、ポリプロピレン以外の成分（例えば、他の重合体、添加剤、汚れ（ゴミ）、水等）が含まれているのが通常であった。 As a general waste plastic, there is a waste plastic mainly composed of polyethylene and polypropylene. Even such waste plastics mainly composed of polyethylene and polypropylene contain components other than polyethylene and polypropylene (for example, other polymers, additives, dirt (dust), water, etc.). It was normal.
仮に廃プラスチック中の成分がポリエチレンおよびポリプロピレンのみであれば、赤外分光法で得られたＩＲスペクトルから、ポリエチレンおよびポリプロピレンそれぞれに特徴的なピークの、ピーク面積あるいはピーク高さから、その組成を知ることが可能である。しかしながら、ポリエチレン、ポリプロピレン以外の成分が含まれている場合には、このような方法では、その組成を知ることができなかった。 If the component in the waste plastic is only polyethylene and polypropylene, the composition is known from the peak area or peak height of each characteristic peak of polyethylene and polypropylene from the IR spectrum obtained by infrared spectroscopy. It is possible. However, in the case where components other than polyethylene and polypropylene are contained, the composition cannot be known by such a method.
また、特許文献１に開示されたポリオレフィン樹脂組成物の分析方法では1Ｈ−ＮＭＲ法が採用されているが、ＮＭＲ測定を行うために用いられる核磁気共鳴装置は、一般に高価であり、その測定結果は、核磁気共鳴装置が置かれる環境の影響、例えば、温度変化、騒音、ノイズ、振動、磁場等の影響を受けるため、清潔な室内であることが求められる。また、樹脂をＮＭＲで測定する際には、数〜十数時間かかることが一般的であり、大量のサンプル（ポリオレフィン樹脂組成物）を分析することが難しかった。Moreover, although the 1 H-NMR method is adopted in the method for analyzing a polyolefin resin composition disclosed in Patent Document 1, a nuclear magnetic resonance apparatus used for performing NMR measurement is generally expensive, and the measurement The result is influenced by the environment in which the nuclear magnetic resonance apparatus is placed, for example, the influence of temperature change, noise, noise, vibration, magnetic field, etc., so that the room is required to be clean. Further, when the resin is measured by NMR, it usually takes several to tens of hours, and it is difficult to analyze a large amount of sample (polyolefin resin composition).
本発明は、従来の技術では難しかったプラスチック中に含まれる、ポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）の量を簡便に求めることが可能な、プラスチックの純度測定方法を提供することを目的とする。 An object of the present invention is to provide a method for measuring the purity of a plastic that can easily determine the amount of polyethylene (PE) or polypropylene (PP) contained in the plastic, which has been difficult with the prior art.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、プラスチックに内部標準物質を加えることにより、プラスチックの純度を効率的に測定することができることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have found that the purity of the plastic can be efficiently measured by adding an internal standard substance to the plastic, and the present invention has been completed. It was.
すなわち、本発明のプラスチックの純度測定方法は、例えば以下の［１］〜［５］に関する。 That is, the plastic purity measuring method of the present invention relates to the following [1] to [5], for example.
［１］ ポリエチレンおよびポリプロピレンの少なくとも一方を含むプラスチックの純度測定方法であり、秤量した前記プラスチックに、秤量した内部標準物質を加える工程（Ａ）、内部標準物質が加えられたプラスチックを、赤外分光法で分析する工程（Ｂ）、前記工程（Ｂ）で得られたＩＲスペクトルから、プラスチックに含まれるポリエチレン量およびポリプロピレン量を求める工程（Ｃ）を有する、プラスチックの純度測定方法。 [1] A method for measuring the purity of a plastic containing at least one of polyethylene and polypropylene, the step (A) of adding a weighed internal standard substance to the weighed plastic, and infrared spectroscopy of the plastic to which the internal standard substance has been added. A method for measuring the purity of a plastic, comprising a step (B) of analyzing by a method, and a step (C) for determining the amount of polyethylene and polypropylene contained in the plastic from the IR spectrum obtained in the step (B).
［２］ 前記内部標準物質が、ポリ酢酸ビニル、ポリアクリロニトリル、ポリピバリン酸ビニル、またはポリモノクロロ酢酸ビニルである、［１］に記載のプラスチックの純度測定方法。 [2] The plastic purity measuring method according to [1], wherein the internal standard substance is polyvinyl acetate, polyacrylonitrile, vinyl polypivalate, or polymonochlorovinyl acetate.
［３］ 秤量したポリエチレン、ポリプロピレンおよび内部標準物質を用い、内部標準物質に対するポリエチレンの量を定量する際に用いる検量線および、内部標準物質に対するポリプロピレンの量を定量する際に用いる検量線を作成する工程（α）を有する［１］または［２］に記載のプラスチックの純度測定方法。 [3] Using a weighed polyethylene, polypropylene, and internal standard, create a calibration curve used to quantify the amount of polyethylene relative to the internal standard and a calibration curve used to quantify the amount of polypropylene relative to the internal standard. The method for measuring the purity of a plastic according to [1] or [2], which comprises the step (α).
［４］ 前記工程（Ａ）中に、前記秤量したプラスチックと、前記秤量した内部標準物質とを、溶媒を用いて溶解する工程を有する、［１］〜［３］のいずれかに記載のプラスチックの純度測定方法。 [4] The plastic according to any one of [1] to [3], which includes a step of dissolving the weighed plastic and the weighed internal standard substance using a solvent in the step (A). Purity measurement method.
［５］ 前記プラスチックが廃プラスチックである、［１］〜［４］のいずれかに記載のプラスチックの純度測定方法。 [5] The plastic purity measuring method according to any one of [1] to [4], wherein the plastic is waste plastic.
本発明のプラスチックの純度測定方法は、プラスチック中のＰＥ量およびＰＰ量を簡便に求めることが可能である。 The method for measuring the purity of the plastic of the present invention can easily determine the amount of PE and PP in the plastic.
次に本発明について具体的に説明する。 Next, the present invention will be specifically described.
本発明の純度測定方法は、ポリエチレンおよびポリプロピレンの少なくとも一方を含むプラスチックの純度測定方法であり、秤量した前記プラスチックに、秤量した内部標準物質を加える工程（Ａ）、内部標準物質が加えられたプラスチックを、赤外分光法で分析する工程（Ｂ）、前記工程（Ｂ）で得られたＩＲスペクトルから、プラスチックに含まれるポリエチレン量およびポリプロピレン量を求める工程（Ｃ）を有する、プラスチックの純度測定方法である。 The purity measuring method of the present invention is a method for measuring the purity of a plastic containing at least one of polyethylene and polypropylene, the step (A) of adding a weighed internal standard substance to the weighed plastic, and the plastic in which the internal standard substance is added (B), and the step (C) for determining the amount of polyethylene and the amount of polypropylene contained in the plastic from the IR spectrum obtained in the step (B). It is.
本発明のプラスチックの純度測定方法（単に、純度測定方法とも記す）は、ポリエチレンおよびポリプロピレンの少なくとも一方を含むプラスチックに含まれる、ポリエチレン量およびポリプロピレン量を求めることが可能であり、前記プラスチックとしてはポリエチレンおよびポリプロピレンを含むプラスチックであることが好ましい。 The plastic purity measurement method of the present invention (also simply referred to as purity measurement method) can determine the amount of polyethylene and the amount of polypropylene contained in a plastic containing at least one of polyethylene and polypropylene. And plastics including polypropylene.
本発明の純度測定方法は、組成が不明なプラスチックにおいて、ポリエチレンやポリプロピレンの量を容易に求めることが可能であり、プラスチックとしては廃プラスチックが好ましい。廃プラスチックとしては、本発明の純度測定方法を行う前に、ポリスチレンを除去した廃プラスチックを用いてもよい。ポリスチレンを除去した廃プラスチックは、例えば、廃プラスチックを、ポリスチレンを溶解可能な溶媒（例えば、テトラヒドロフランとアセトンとの混合溶媒）を用いて加熱還流することにより、得ることができる。 According to the purity measuring method of the present invention, the amount of polyethylene or polypropylene can be easily determined in a plastic whose composition is unknown, and waste plastic is preferred as the plastic. As the waste plastic, waste plastic from which polystyrene has been removed may be used before performing the purity measuring method of the present invention. The waste plastic from which polystyrene is removed can be obtained, for example, by heating and refluxing the waste plastic using a solvent capable of dissolving polystyrene (for example, a mixed solvent of tetrahydrofuran and acetone).
本発明の純度測定方法は工程（Ａ）〜（Ｃ）を有しており、さらに工程（α）を有することが好ましい。以下工程（Ａ）〜（Ｃ）および（α）について説明する。 The purity measuring method of the present invention includes steps (A) to (C), and preferably further includes a step (α). Hereinafter, steps (A) to (C) and (α) will be described.
［工程（Ａ）］
本発明の工程（Ａ）は、秤量したプラスチックに、秤量した内部標準物質を加える工程である。[Step (A)]
Step (A) of the present invention is a step of adding a weighed internal standard substance to a weighed plastic.
工程（Ａ）では、分析対象であるプラスチックに、内部標準物質を加える。工程（Ａ）では、プラスチックおよび内部標準物質については、秤量を行うことが必要である。秤量の際には、電子天秤等を用いることができる。 In step (A), an internal standard substance is added to the plastic to be analyzed. In the step (A), it is necessary to weigh the plastic and the internal standard substance. An electronic balance or the like can be used for weighing.
なお、ポリエチレンおよびポリプロピレンの純度を正確に求めるためには、工程（Ａ）では、プラスチックと内部標準物質とを均一に混合することが好ましい。プラスチックと内部標準物質とを均一に混合するための方法としては、プラスチックと内部標準物質とを溶媒を用いて溶解することが好ましい。すなわち、工程（Ａ）中に、秤量したプラスチックと、秤量した内部標準物質とを、溶媒を用いて溶解する工程を有することが好ましい。 In addition, in order to obtain | require the purity of polyethylene and polypropylene correctly, it is preferable to mix a plastic and an internal standard substance uniformly at a process (A). As a method for uniformly mixing the plastic and the internal standard substance, it is preferable to dissolve the plastic and the internal standard substance using a solvent. In other words, the step (A) preferably includes a step of dissolving the weighed plastic and the weighed internal standard substance using a solvent.
工程（Ａ）の例としては、秤量したプラスチックおよび内部標準物質を、溶媒を用いて、適宜加熱を行うことにより溶解し、その後溶解後の試料を乾燥させる工程が挙げられる。このようにして、プラスチックと内部標準物質が均一に混合された試料（内部標準物質が加えられたプラスチック）を得ることができる。 An example of the step (A) includes a step of dissolving a weighed plastic and an internal standard substance by appropriately heating using a solvent, and then drying the sample after dissolution. In this way, a sample (plastic added with an internal standard) in which the plastic and the internal standard are uniformly mixed can be obtained.
内部標準物質としては、ＩＲスペクトルを測定した際に、ポリエチレンおよびポリプロピレンとピークが重ならない波長にピークが観察される物質であり、且つ、プラスチックと均一に混合可能なものであればよく、特に限定はされない。内部標準物質としては均一に混合するために、高沸点であり、試料を調製する際に分解せず、かつ溶媒に溶けるものが好ましい。また、内部標準物質は安価であることが好ましい。内部標準物質の具体例としては、ポリ酢酸ビニル、ポリアクリロニトリル、ポリピバリン酸ビニル、またはポリモノクロロ酢酸ビニル等が挙げられる。 The internal standard substance is not particularly limited as long as it is a substance in which a peak is observed at a wavelength at which the peak does not overlap with polyethylene and polypropylene when an IR spectrum is measured and can be uniformly mixed with plastic. Not done. As the internal standard substance, a substance having a high boiling point, which does not decompose when preparing a sample, and is soluble in a solvent is preferable for uniform mixing. The internal standard substance is preferably inexpensive. Specific examples of the internal standard substance include polyvinyl acetate, polyacrylonitrile, vinyl polypivalate, and polymonochlorovinyl acetate.
また、前記溶媒としては、プラスチックおよび内部標準物質を溶解することができればよく、特に限定はされない。溶媒としては例えば、１，１，２，２−テトラクロロエタン、１，１，１，２−テトラクロロエタン、ジクロロベンゼン等を用いることができる。また、溶媒としては、トルエン、シクロヘキサン等を用いることもできる。溶媒としては、１，１，２，２−テトラクロロエタン、トルエンが好ましい。溶媒は一種単独でも二種以上を用いてもよい。 The solvent is not particularly limited as long as it can dissolve the plastic and the internal standard substance. As the solvent, for example, 1,1,2,2-tetrachloroethane, 1,1,1,2-tetrachloroethane, dichlorobenzene and the like can be used. Moreover, toluene, cyclohexane, etc. can also be used as a solvent. As the solvent, 1,1,2,2-tetrachloroethane and toluene are preferable. The solvent may be used alone or in combination of two or more.
［工程（Ｂ）］
本発明の工程（Ｂ）は、内部標準物質が加えられたプラスチックを、赤外分光法で分析する工程である。該工程により、分析対象であるプラスチックのＩＲスペクトルが得られる。[Step (B)]
The step (B) of the present invention is a step of analyzing the plastic added with the internal standard substance by infrared spectroscopy. By this step, an IR spectrum of the plastic to be analyzed is obtained.
赤外分光法は、通常はフーリエ変換赤外分光分析装置が用いられる。赤外分光法で分析する際の方法としては、プラスチックを分析できる方法であればよく、特に限定は無いが、減衰全反射法（ＡＴＲ法）で行うことが好ましい。 For infrared spectroscopy, a Fourier transform infrared spectrometer is usually used. The method for analysis by infrared spectroscopy is not particularly limited as long as it is a method capable of analyzing plastics, but is preferably performed by the attenuated total reflection method (ATR method).
［工程（Ｃ）］
本発明の工程（Ｃ）は、前記工程（Ｂ）で得られたＩＲスペクトルから、プラスチックに含まれるポリエチレン量およびポリプロピレン量を求める工程である。[Step (C)]
The step (C) of the present invention is a step for obtaining the amount of polyethylene and the amount of polypropylene contained in the plastic from the IR spectrum obtained in the step (B).
工程（Ｂ）で得られるＩＲスペクトルは、内部標準物質のスペクトル、プラスチック中のポリエチレン、ポリプロピレン、その他の物質のスペクトルが、その含有量に応じて重ね合わされたスペクトルである。得られたＩＲスペクトルからプラスチックに含まれるポリエチレン量およびポリプロピレン量を求める方法としては、特に限定は無いが、通常はポリエチレン、ポリプロピレン、および内部標準物質の特性吸収帯の面積比を利用して求めることが好ましい。 The IR spectrum obtained in the step (B) is a spectrum in which the spectrum of the internal standard substance and the spectra of polyethylene, polypropylene and other substances in the plastic are superimposed according to the content. The method for obtaining the amount of polyethylene and polypropylene contained in the plastic from the obtained IR spectrum is not particularly limited, but it is usually obtained using the area ratio of the characteristic absorption band of polyethylene, polypropylene, and internal standard substance. Is preferred.
なお、ポリエチレン、ポリプロピレン、および内部標準物質の特性吸収帯としては、各成分の吸収が重ならない範囲であればよく、内部標準物質の種類によってもことなる。例えば、内部標準物質として、ポリ酢酸ビニルを使用する場合には、ポリエチレンの特性吸収帯として７１７ｃｍ-1、ポリプロピレンの特性吸収帯として８４１ｃｍ-1、ポリ酢酸ビニルの特性吸収帯として１７３０ｃｍ-1を使用することができる。The characteristic absorption band of polyethylene, polypropylene, and the internal standard substance may be in a range where the absorption of each component does not overlap, and may vary depending on the type of the internal standard substance. For example, as an internal standard, when using polyvinyl acetate, using the 1730 cm -1 as 841cm -1, characteristic absorption band of polyvinyl acetate as 717cm -1, characteristic absorption band of polypropylene as a characteristic absorption band of polyethylene can do.
具体的には、工程（α）を工程（Ａ）〜（Ｃ）の前あるいは途中に行い、工程（α）によって作成した検量線を利用して、工程（Ｃ）においてプラスチックに含まれるポリエチレン量、ポリプロピレン量を求めることが好ましい。 Specifically, the step (α) is performed before or during the steps (A) to (C), and the amount of polyethylene contained in the plastic in the step (C) is obtained using the calibration curve created in the step (α). It is preferable to determine the amount of polypropylene.
［工程（α）］
本発明の工程（α）は、秤量したポリエチレン、ポリプロピレンおよび内部標準物質を用い、内部標準物質に対するポリエチレンの量を定量する際に用いる検量線および、内部標準物質に対するポリプロピレンの量を定量する際に用いる検量線を作成する工程である。[Step (α)]
The step (α) of the present invention uses a weighed polyethylene, polypropylene, and internal standard substance, a calibration curve used for quantifying the amount of polyethylene relative to the internal standard substance, and a quantity of polypropylene relative to the internal standard substance This is a step of creating a calibration curve to be used.
検量線の作成は、例えば、秤量したポリエチレン、ポリプロピレンおよび内部標準物質を均一に混合し、赤外分光法で分析し、得られたＩＲスペクトルにおける、ポリエチレン、ポリプロピレンおよび内部標準物質の特性吸収帯のピーク面積を求め、該ピーク面積と、各成分の重量との関係を求めることにより行われる。 The calibration curve is prepared by, for example, uniformly mixing a weighed polyethylene, polypropylene, and internal standard substance, and analyzing them by infrared spectroscopy. In the obtained IR spectrum, the characteristic absorption bands of polyethylene, polypropylene, and internal standard substance are measured. This is done by determining the peak area and determining the relationship between the peak area and the weight of each component.
具体例としては、秤量したポリエチレン、ポリプロピレンおよび内部標準物質を均一に混合した試料を、ポリエチレンとポリプロピレンとの割合を変えて複数用意する。この際、ポリエチレンおよびポリプロピレンの合計量に対する内部標準物質の量をできるだけ一定にすることが好ましい。また、試料としては、ポリエチレンを含まない物、ポリプロピレンを含まない物も用意することが好ましい。次いで、各試料についてＩＲスペクトルを得る。次に各ＩＲスペクトルにおけるポリエチレンの特性吸収帯と、内部標準試料の特性吸収帯とのピーク面積比および、各試料におけるポリエチレンと、内部標準試料との重量比をプロットし、内部標準物質に対するポリエチレンの量を定量する際に用いる検量線を作成し、同様に、各ＩＲスペクトルにおけるポリプロピレンの特性吸収帯と、内部標準試料の特性吸収帯とのピーク面積比および、各試料におけるポリプロピレンと、内部標準試料との重量比をプロットし、内部標準物質に対するポリプロピレンの量を定量する際に用いる検量線を作成する方法が挙げられる。なお、前記具体例においては、検量線を作成する際の試料としては、ポリエチレン、ポリプロピレンおよび内部標準物質を含有する試料を用いる場合を挙げたが、試料としては、ポリエチレンおよび内部標準物質を含有する試料と、ポリプロピレンおよび内部標準物質を含有する試料を用いて、各試料において、ポリエチレンと内部標準物質との重量比、またはポリプロピレンと内部標準物質との重量比を変えた試料を複数用意して、検量線を作成してもよい。 As a specific example, a plurality of samples in which weighed polyethylene, polypropylene, and an internal standard substance are uniformly mixed are prepared by changing the ratio of polyethylene and polypropylene. At this time, it is preferable to make the amount of the internal standard substance as constant as possible with respect to the total amount of polyethylene and polypropylene. Moreover, it is preferable to prepare the sample which does not contain polyethylene and the thing which does not contain polypropylene as a sample. An IR spectrum is then obtained for each sample. Next, the peak area ratio between the characteristic absorption band of polyethylene and the characteristic absorption band of the internal standard sample in each IR spectrum and the weight ratio of polyethylene and internal standard sample in each sample are plotted. A calibration curve used for quantifying the amount is prepared. Similarly, the peak area ratio between the characteristic absorption band of polypropylene and the characteristic absorption band of the internal standard sample in each IR spectrum, and the polypropylene in each sample and the internal standard sample And plotting a weight ratio with the internal standard substance to prepare a calibration curve for use in quantifying the amount of polypropylene relative to the internal standard. In the above specific example, the case of using a sample containing polyethylene, polypropylene, and an internal standard as the sample for preparing the calibration curve was mentioned, but the sample contains polyethylene and the internal standard. Using a sample and a sample containing polypropylene and an internal standard substance, in each sample, prepare a plurality of samples in which the weight ratio between polyethylene and the internal standard substance or the weight ratio between polypropylene and the internal standard substance is changed, A calibration curve may be created.
工程（α）で作成した検量線を、工程（Ｃ）で利用することにより、プラスチックに含まれるポリエチレン量およびポリプロピレン量を容易に求めることができる。 By using the calibration curve created in the step (α) in the step (C), the amount of polyethylene and the amount of polypropylene contained in the plastic can be easily obtained.
本発明の純度測定方法は、前述の工程（Ａ）〜（Ｃ）を有し、工程（α）を有することが好ましい。また、本発明の目的の範囲内で別途任意の工程を設けてもよい。 The purity measuring method of the present invention includes the steps (A) to (C) described above, and preferably includes the step (α). Moreover, you may provide an arbitrary process separately within the scope of the object of the present invention.
次に本発明について実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。 EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
〔実験例１〕
〔１〕検量線の作成
検量線作成に用いたポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、内部標準物質であるポリ酢酸ビニル（ＰＶＡｃ）を表１にまとめる。[Experimental Example 1]
[1] Preparation of calibration curve Table 1 summarizes polyethylene (PE), polypropylene (PP), and polyvinyl acetate (PVAc), which is an internal standard substance, used for the calibration curve.
ＰＥ、ＰＰ、ＰＶＡｃの特性吸収帯は、各重合体のみで測定したＩＲスペクトルに基づき、表２に記載の通り決定した。なお、表１に記載のＰＥ、ＰＰ、ＰＶＡｃのＩＲスペクトルを図１〜３に示す。 The characteristic absorption bands of PE, PP, and PVAc were determined as described in Table 2 based on the IR spectrum measured only for each polymer. In addition, the IR spectrum of PE, PP, and PVAc described in Table 1 is shown in FIGS.
〔１−１〕試料の秤量
フード付き電子天秤を用い、５０ｍｌのサンプル管瓶に、前記ＰＥおよびＰＰを、後述の表３に記載の割合かつ合計約３０ｍｇとなるように秤量した。また、ＰＶＡｃを約１５ｍｇ秤量した。[1-1] Weighing Sample Using a hooded electronic balance, the PE and PP were weighed in a 50-ml sample tube bottle so as to have a ratio shown in Table 3 described later and a total of about 30 mg. Moreover, about 15 mg of PVAc was weighed.
前記秤量に当たっては、秤量後６０秒間静置し、値が一定になったのを確認した。 In weighing, it was allowed to stand for 60 seconds after weighing and it was confirmed that the value became constant.
各サンプルに、ＰＥ、ＰＰおよびＰＶＡｃの秤量したｍｇ数を、小数点以下第１位まで測定し、記録し、表３に記載のＰＥ：ＰＰ重量比率、ＰＥ／ＰＶＡｃ重量比、およびＰＰ／ＰＶＡｃ重量比の算出に使用した。 For each sample, the weighed mg of PE, PP and PVAc was measured to the first decimal place and recorded, and the PE: PP weight ratio, PE / PVAc weight ratio, and PP / PVAc weight listed in Table 3 Used to calculate the ratio.
〔１−２〕溶媒の添加
前記１−１において、ＰＥ、ＰＰおよびＰＶＡｃが秤量された５０ｍｌサンプル管瓶に、１，１，２，２−テトラクロロエタン約４．５ｇを加えた。なお、溶液濃度が１％になるように、ＰＥ、ＰＰおよびＰＶＡｃの合計重量の１００倍量の１，１，２，２−テトラクロロエタンを使用した。[1-2] Addition of solvent In the above 1-1, about 4.5 g of 1,1,2,2-tetrachloroethane was added to a 50 ml sample tube bottle in which PE, PP and PVAc were weighed. In addition, 1,1,2,2-tetrachloroethane, which is 100 times the total weight of PE, PP, and PVAc, was used so that the solution concentration was 1%.
〔１−３〕試料の溶解
前記１−２で溶媒が加えられたサンプル管瓶を、２００〜２２０℃の範囲に保ちながら３０分間加熱を行い、均一溶液を調製した。[1-3] Dissolution of sample The sample tube bottle to which the solvent was added in 1-2 was heated for 30 minutes while maintaining the temperature in the range of 200 to 220 ° C. to prepare a uniform solution.
〔１−４〕試料の乾燥
前記１−３で溶解させた試料を、乾燥、固形化させるために、ドラフト内で溶媒を均一に蒸発させた。乾燥の仕上げとしてロータリーポンプを用いて真空乾燥を行い、溶媒を蒸発、除去した。[1-4] Drying of sample In order to dry and solidify the sample dissolved in 1-3, the solvent was uniformly evaporated in a fume hood. As a drying finish, vacuum drying was performed using a rotary pump to evaporate and remove the solvent.
〔１−５〕試料の採取
前記１−４で得られたサンプル管瓶中の乾燥された試料を、スパーテルで採取し、メノウ乳鉢で混合し、ＦＴ−ＩＲ測定試料とした。[1-5] Collection of sample The dried sample in the sample tube bottle obtained in the above 1-4 was collected with a spatula and mixed with an agate mortar to obtain an FT-IR measurement sample.
〔１−６〕ＦＴ−ＩＲ測定
前記１−５で調製したＦＴ−ＩＲ測定試料のＩＲスペクトルを、それぞれフーリエ変換赤外分光分析装置 Ｓｐｅｃｔｒｕｍ１００（株式会社パーキンエルマージャパン製）を用いて測定した。[1-6] FT-IR Measurement The IR spectrum of the FT-IR measurement sample prepared in 1-5 above was measured using a Fourier transform infrared spectrometer Spectrum 100 (manufactured by PerkinElmer Japan Co., Ltd.).
得られたＩＲスペクトルの前記特性吸収帯の面積に基づき、ＰＥとＰＶＡｃとの面積比およびＰＰとＰＶＡｃとの面積比を算出した。 Based on the area of the characteristic absorption band of the obtained IR spectrum, the area ratio of PE and PVAc and the area ratio of PP and PVAc were calculated.
なお、ＩＲスペクトルの測定は、各試料について２０点測定を行い、２０点について各特性吸収帯のピーク面積を求め、上下５点を除外した１０点に基づき、平均を算出し、各特性吸収帯の面積とした。 The IR spectrum is measured at 20 points for each sample, the peak area of each characteristic absorption band is obtained for 20 points, the average is calculated based on 10 points excluding the upper and lower 5 points, and each characteristic absorption band is calculated. Area.
各試料のＰＥ：ＰＰ重量比率、ＰＥとＰＶＡｃとの面積比、ＰＥとＰＶＡｃとの重量比、ＰＰとＰＶＡｃとの面積比、ＰＰとＰＶＡｃとの重量比を表３に示す。 Table 3 shows the PE: PP weight ratio, the area ratio of PE and PVAc, the weight ratio of PE and PVAc, the area ratio of PP and PVAc, and the weight ratio of PP and PVAc of each sample.
なお、ＰＥ：ＰＰ重量比率としては、秤量予定の重量比率および実際に秤量した重量に基づき計算した重量比（実測値）の両方を示す。 In addition, as PE: PP weight ratio, both the weight ratio planned to be weighed and the weight ratio (actually measured value) calculated based on the actually weighed weight are shown.
表３の結果を基に作成した、ＰＥとＰＶＡｃとの、重量比（実測値）と、面積比との関係を図４に示し、ＰＰとＰＶＡｃとの、重量比（実測値）と、面積比との関係を図５に示す。 The relationship between the weight ratio (measured value) and area ratio of PE and PVAc, created based on the results of Table 3, is shown in FIG. 4. The weight ratio (measured value) and area of PP and PVAc The relationship with the ratio is shown in FIG.
表３および図４に示した結果から、プラスチック中のＰＥの重量は、以下のように求めることができる。 From the results shown in Table 3 and FIG. 4, the weight of PE in the plastic can be determined as follows.
ＰＥ重量（ｍｇ）／ＰＶＡｃ重量（ｍｇ）＝１８．２４ＰＥ面積／ＰＶＡｃ面積
ここで、上記式の相関係数は、０．８６５７であった。PE weight (mg) / PVAc weight (mg) = 18.24 PE area / PVAc area Here, the correlation coefficient of the above formula was 0.8657.
ＰＥ重量（ｍｇ）＝１８．２４ＰＥ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
また、プラスチック中のＰＥ純度（％）は試料全体の重量をＳＷ（ｍｇ）とすると、以下のように求めることができる。PE weight (mg) = 18.24 PE area / PVAc area × PVAc weight (mg)
The PE purity (%) in the plastic can be determined as follows, assuming that the weight of the entire sample is SW (mg).
ＰＥ純度（％）＝ＰＥ重量（ｍｇ）／ＳＷ（ｍｇ）×１００
表３および図５に示した結果から、プラスチック中のＰＰの重量は、以下のように求めることができる。PE purity (%) = PE weight (mg) / SW (mg) × 100
From the results shown in Table 3 and FIG. 5, the weight of PP in the plastic can be determined as follows.
ＰＰ重量（ｍｇ）／ＰＶＡｃ重量（ｍｇ）＝７１．１１ＰＰ面積／ＰＶＡｃ面積
ここで、上記式の相関係数は、０．９７１４であった。PP weight (mg) / PVAc weight (mg) = 71.11 PP area / PVAc area Here, the correlation coefficient of the above formula was 0.9714.
ＰＰ重量（ｍｇ）＝７１．１１ＰＰ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
また、プラスチック中のＰＰ純度（％）は試料全体の重量をＳＷ（ｍｇ）とすると、以下のように求めることができる。PP weight (mg) = 71.11PP area / PVAc area × PVAc weight (mg)
The PP purity (%) in the plastic can be determined as follows, assuming that the weight of the entire sample is SW (mg).
ＰＰ純度（％）＝ＰＰ重量（ｍｇ）／ＳＷ（ｍｇ）×１００
〔実験例２〕
実験例１で得た検量線の妥当性を検討するために、以下の実験を行った。PP purity (%) = PP weight (mg) / SW (mg) × 100
[Experimental example 2]
In order to examine the validity of the calibration curve obtained in Experimental Example 1, the following experiment was performed.
減容再生されたポリエチレンを主成分とするＰＥとＰＰとの混合リサイクル材および、減容再生されたポリプロピレンを主成分とするＰＥとＰＰとの混合リサイクル材について、以下の方法でＩＲスペクトルおよび1Ｈ−ＮＭＲスペクトルを得て、各スペクトルから導かれる結果を対比した。Regarding the mixed recycled material of PE and PP mainly composed of reduced volume recycled polyethylene and the mixed recycled material of PE and PP mainly composed of volume reduced recycled polypropylene, the IR spectrum and 1 H-NMR spectra were obtained and the results derived from each spectrum were compared.
なお、減容再生されたポリエチレンを主成分とするＰＥとＰＰとの混合リサイクル材をＰＥ混合リサイクル材とも記し、減容再生されたポリプロピレンを主成分とするＰＥとＰＰとの混合リサイクル材をＰＰ混合リサイクル材とも記す。 Note that PE / PP mixed recycled material mainly composed of polyethylene whose volume has been reduced and recycled is also referred to as PE mixed recycled material, and PE / PP mixed recycled material whose main component is volume reduced and recycled is PP. Also referred to as mixed recycled material.
〔２−１〕試料の前処理
各混合リサイクル材を、冷凍粉砕機（型式：ＪＦＣ−３００、吉田製作所製）を用いて細かく粉砕した。[2-1] Sample Pretreatment Each mixed recycled material was finely pulverized using a freeze pulverizer (model: JFC-300, manufactured by Yoshida Seisakusho).
フード付き電子天秤を用い、５０ｍｌのサンプル管瓶に、粉砕された混合リサイクル材を約３０ｍｇ、ＰＶＡｃを約１５ｍｇとなるように精秤量した。 Using a hooded electronic balance, weighed accurately in a 50 ml sample tube bottle so that the pulverized mixed recycled material was about 30 mg and PVAc was about 15 mg.
前記秤量に当たっては、秤量後６０秒間静置し、値が一定になったのを確認した。 In weighing, it was allowed to stand for 60 seconds after weighing and it was confirmed that the value became constant.
各サンプルに、混合リサイクル材およびＰＶＡｃの秤量したｍｇ数を、小数点以下第１位まで測定し、記録し、検量線に基づき、ＰＥ重量を算出する際、ＰＰ重量を算出する際の試料全体の重量、ＰＶＡｃの重量として使用した。 For each sample, the number of mg of the mixed recycled material and PVAc weighed is measured and recorded to the first decimal place, and when calculating the PE weight based on the calibration curve, the entire sample when calculating the PP weight Weight, PVAc weight.
〔２−２〕溶媒の添加
前記２−１において、混合リサイクル材およびＰＶＡｃが秤量された５０ｍｌサンプル管瓶に、１，１，２，２−テトラクロロエタン約４．５ｇを加えた。なお、溶液の濃度が１％になるように１，１，２，２−テトラクロロエタンを加えた。[2-2] Addition of solvent In the above 2-1, about 4.5 g of 1,1,2,2-tetrachloroethane was added to a 50 ml sample tube bottle in which the mixed recycle material and PVAc were weighed. In addition, 1,1,2,2-tetrachloroethane was added so that the concentration of the solution was 1%.
〔２−３〕試料の溶解
前記２−２で溶媒が加えられたサンプル管瓶を、２００〜２２０℃の範囲に保ちながら３０分間加熱を行い、均一溶液を調製した。[2-3] Dissolution of sample The sample tube bottle to which the solvent was added in 2-2 was heated for 30 minutes while maintaining the temperature in the range of 200 to 220 ° C to prepare a uniform solution.
〔２−４〕試料の乾燥
前記２−３で溶解させた試料を、乾燥、固形化させるために、ドラフト内で溶媒を蒸発させた。乾燥の仕上げとしてロータリーポンプを用いて真空乾燥を行い、溶媒を蒸発、除去した。[2-4] Drying of sample In order to dry and solidify the sample dissolved in 2-3, the solvent was evaporated in a fume hood. As a drying finish, vacuum drying was performed using a rotary pump to evaporate and remove the solvent.
〔２−５〕試料の採取
前記２−４で得られたサンプル管瓶中の乾燥された試料を、スパーテルで採取し、メノウ乳鉢で混合し、ＦＴ−ＩＲ測定試料とした。[2-5] Collection of sample The dried sample in the sample tube bottle obtained in 2-4 was collected with a spatula and mixed with an agate mortar to obtain a sample for FT-IR measurement.
〔２−６〕ＦＴ−ＩＲ測定
前記２−５で調製したＦＴ−ＩＲ測定試料のＩＲスペクトルを、それぞれフーリエ変換赤外分光分析装置 Ｓｐｅｃｔｒｕｍ１００（株式会社パーキンエルマージャパン製）を用いて測定した。[2-6] FT-IR Measurement The IR spectrum of the FT-IR measurement sample prepared in 2-5 above was measured using a Fourier transform infrared spectroscopic apparatus Spectrum 100 (manufactured by Perkin Elmer Japan Co., Ltd.).
得られたＩＲスペクトルの前記特性吸収帯の面積に基づき、ＰＥとＰＶＡｃとの面積比およびＰＰとＰＶＡｃとの面積比を算出した。 Based on the area of the characteristic absorption band of the obtained IR spectrum, the area ratio of PE and PVAc and the area ratio of PP and PVAc were calculated.
該面積比およびＰＶＡｃの重量、並びに実験例１で得た検量線から、以下のように、ＰＥ混合リサイクル材についてはＰＥ純度を算出し、ＰＰ混合リサイクル材についてはＰＰ純度を算出した。 From the area ratio, the weight of PVAc, and the calibration curve obtained in Experimental Example 1, the PE purity was calculated for the PE mixed recycled material and the PP purity was calculated for the PP mixed recycled material as follows.
（ＰＥ混合リサイクル材のＰＥ純度）
ＰＥ重量（ｍｇ）＝１８．２４ＰＥ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
＝１８．２４×０．６２６１／７．３８１×１４．９
＝２３．０５
ＰＥ純度（％）＝ＰＥ重量（ｍｇ）／ＳＷ（ｍｇ）×１００
＝２３．０５／３０．３×１００
＝７６．１％
（ＰＰ混合リサイクル材のＰＰ純度）
ＰＰ重量（ｍｇ）＝７１．１１ＰＰ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
＝７１．１１×０．１４７１／５．９８１×１５．１
＝２６．４１
ＰＰ純度（％）＝ＰＰ重量（ｍｇ）／ＳＷ（ｍｇ）×１００
＝２６．４１／３０．６×１００
＝８６．３％
〔２−７〕1Ｈ−ＮＭＲ測定
ＰＥ混合リサイクル材および、ＰＰ混合リサイクル材について、1Ｈ−ＮＭＲ測定および1Ｈ−ＮＭＲ測定に基づく成分組成の評価を実施した。結果を表４に示す。
1Ｈ−ＮＭＲ測定は、以下の条件で行った。
・装置：日本電子株式会社製核磁気共鳴装置「ＥＣＡ５００」（５００ＭＨｚ）
・溶媒：重水素化１，１，２，２−テトラクロロエタン
・試料：不溶解分を除去した試料（ＰＥ混合リサイクル材、ＰＰ混合リサイクル材）を使用
・試料量：約２０ｍｇ
・測定核種：1Ｈ
・測定温度：１２０℃(PE purity of PE mixed recycling material)
PE weight (mg) = 18.24 PE area / PVAc area × PVAc weight (mg)
= 18.24 × 0.6261 / 7.381 × 14.9
= 23.05
PE purity (%) = PE weight (mg) / SW (mg) × 100
= 23.05 / 30.3 × 100
= 76.1%
(PP purity of PP mixed recycled material)
PP weight (mg) = 71.11PP area / PVAc area × PVAc weight (mg)
= 71.11 × 0.1471 / 5.981 × 15.1
= 26.41
PP purity (%) = PP weight (mg) / SW (mg) × 100
= 26.41 / 30.6 × 100
= 86.3%
[2-7] 1 H-NMR Measurement With respect to the PE mixed recycled material and the PP mixed recycled material, the component composition was evaluated based on the 1 H-NMR measurement and the 1 H-NMR measurement. The results are shown in Table 4.
1 H-NMR measurement was performed under the following conditions.
・ Device: Nuclear magnetic resonance apparatus “ECA500” (500 MHz) manufactured by JEOL Ltd.
・ Solvent: Deuterated 1,1,2,2-tetrachloroethane ・ Sample: Samples from which insolubles have been removed (PE mixed recycled material, PP mixed recycled material) are used. ・ Sample amount: about 20 mg
・ Measurement nuclide: 1 H
・ Measurement temperature: 120 ℃
〔２−８〕ＦＴ−ＩＲ測定結果と、1Ｈ−ＮＭＲ測定結果との対比
前記２−６で求めたＰＥ純度およびＰＰ純度、並びに２−７で求めたＰＥ純度およびＰＰ純度を対比した結果を表５に示す。[2-8] Comparison between FT-IR measurement results and 1 H-NMR measurement results Results of comparing PE purity and PP purity determined in 2-6 above, and PE purity and PP purity determined in 2-7 Is shown in Table 5.
表５の結果より、本発明の内部標準物質を用いて、赤外分光法によってＩＲスペクトルを得ることにより、プラスチックの純度を測定する方法と、1Ｈ−ＮＭＲによって、プラスチックの純度を測定する方法とでは、その結果の差が小さく、産業上有用であることが分かった。ＮＭＲ測定と比べてＩＲ測定は簡便な装置で測定を実施することが可能であるため、本発明の方法は簡便であり、有用であることが確認できた。From the results of Table 5, using the internal standard substance of the present invention, a method of measuring the purity of the plastic by obtaining an IR spectrum by infrared spectroscopy, and a method of measuring the purity of the plastic by 1 H-NMR And the difference of the result was small, and it turned out that it is industrially useful. Compared with NMR measurement, IR measurement can be carried out with a simple apparatus, so that it was confirmed that the method of the present invention is simple and useful.
〔実験例３〕
〔３〕検量線の作成
実験例１と同様のポリエチレン（ＰＥ）、ポリプロピレン（ＰＰ）、内部標準物質であるポリ酢酸ビニル（ＰＶＡｃ）を検量線作成に用いた。[Experimental Example 3]
[3] Preparation of calibration curve The same polyethylene (PE), polypropylene (PP) and polyvinyl acetate (PVAc) as an internal standard substance were used for the preparation of the calibration curve as in Experimental Example 1.
ＰＥ、ＰＰ、ＰＶＡｃの特性吸収帯についても実験例１と同様にした。 The characteristic absorption bands of PE, PP, and PVAc were the same as in Experimental Example 1.
〔３−１〕試料の秤量
フード付き電子天秤を用い、５０ｍｌのサンプル管瓶に、前記ＰＥおよびＰＰを、後述の表６に記載の割合かつ合計約３０ｍｇとなるように秤量した。また、ＰＶＡｃを約１５ｍｇ秤量した。[3-1] Weighing Sample Using a hooded electronic balance, the PE and PP were weighed in a 50 ml sample tube bottle so that the ratio was as described in Table 6 below and the total was about 30 mg. Moreover, about 15 mg of PVAc was weighed.
前記秤量に当たっては、秤量後６０秒間静置し、値が一定になったのを確認した。 In weighing, it was allowed to stand for 60 seconds after weighing and it was confirmed that the value became constant.
各サンプルに、ＰＥ、ＰＰおよびＰＶＡｃの秤量したｍｇ数を、小数点以下第１位まで測定し、記録し、表６に記載のＰＥ：ＰＰ重量比率、ＰＥ／ＰＶＡｃ重量比、およびＰＰ／ＰＶＡｃ重量比の算出に使用した。 For each sample, the weighed mg of PE, PP and PVAc was measured and recorded to the first decimal place, and the PE: PP weight ratio, PE / PVAc weight ratio, and PP / PVAc weight listed in Table 6 were recorded. Used to calculate the ratio.
〔３−２〕溶媒の添加
前記３−１において、ＰＥ、ＰＰおよびＰＶＡｃが秤量された５０ｍｌサンプル管瓶に、トルエン約４．５ｇを加えた。なお、溶液濃度が１％になるように、ＰＥ、ＰＰおよびＰＶＡｃの合計重量の１００倍量のトルエンを使用した。[3-2] Addition of solvent In the above 3-1, about 4.5 g of toluene was added to a 50 ml sample tube bottle in which PE, PP and PVAc were weighed. In addition, 100 times the amount of toluene as the total weight of PE, PP, and PVAc was used so that the solution concentration might be 1%.
〔３−３〕試料の溶解
前記３−２で溶媒が加えられたサンプル管瓶を、１５０〜１７０℃の範囲に保ちながら２０分間加熱を行い、均一溶液を調製した。[3-3] Dissolution of sample The sample tube bottle to which the solvent was added in 3-2 was heated for 20 minutes while maintaining the temperature in the range of 150 to 170 ° C to prepare a uniform solution.
〔３−４〕試料の乾燥
前記３−３で溶解させた試料を、乾燥、固形化させるために、ドラフト内で溶媒を均一に蒸発させた。乾燥の仕上げとしてロータリーポンプを用いて真空乾燥を行い、溶媒を蒸発、除去した。[3-4] Drying of sample In order to dry and solidify the sample dissolved in 3-3, the solvent was uniformly evaporated in a fume hood. As a drying finish, vacuum drying was performed using a rotary pump to evaporate and remove the solvent.
〔３−５〕試料の採取
前記３−４で得られたサンプル管瓶中の乾燥された試料を、スパーテルで採取し、メノウ乳鉢で混合し、ＦＴ−ＩＲ測定試料とした。[3-5] Collection of sample The dried sample in the sample tube bottle obtained in 3-4 was collected with a spatula and mixed in an agate mortar to obtain a sample for FT-IR measurement.
〔３−６〕ＦＴ−ＩＲ測定
前記３−５で調製したＦＴ−ＩＲ測定試料のＩＲスペクトルを、それぞれフーリエ変換赤外分光分析装置Fｒｏｎｔｉｅｒ ＦＴ ＩＲ（株式会社パーキンエルマージャパン製）を用いて測定した。[3-6] FT-IR Measurement The IR spectrum of the FT-IR measurement sample prepared in 3-5 above was measured using a Fourier transform infrared spectroscopic apparatus Frontier FT IR (manufactured by PerkinElmer Japan Co., Ltd.). .
得られたＩＲスペクトルの前記特性吸収帯の面積に基づき、ＰＥとＰＶＡｃとの面積比およびＰＰとＰＶＡｃとの面積比を算出した。 Based on the area of the characteristic absorption band of the obtained IR spectrum, the area ratio of PE and PVAc and the area ratio of PP and PVAc were calculated.
なお、ＩＲスペクトルの測定は、各試料について２０点測定を行い、２０点について各特性吸収帯のピーク面積を求め、全平均を算出し、各特性吸収帯の面積とした。 In addition, the measurement of IR spectrum performed 20 points | pieces about each sample, calculated | required the peak area of each characteristic absorption band about 20 points, calculated the total average, and made it the area of each characteristic absorption band.
各試料のＰＥ：ＰＰ重量比率、ＰＥとＰＶＡｃとの面積比、ＰＥとＰＶＡｃとの重量比、ＰＰとＰＶＡｃとの面積比、ＰＰとＰＶＡｃとの重量比を表６に示す。 Table 6 shows the PE: PP weight ratio, the area ratio of PE and PVAc, the weight ratio of PE and PVAc, the area ratio of PP and PVAc, and the weight ratio of PP and PVAc of each sample.
なお、ＰＥ：ＰＰ重量比率としては、秤量予定の重量比率および実際に秤量した重量に基づき計算した重量比（実測値）の両方を示す。 In addition, as PE: PP weight ratio, both the weight ratio planned to be weighed and the weight ratio (actually measured value) calculated based on the actually weighed weight are shown.
表６の結果を基に作成した、ＰＥとＰＶＡｃとの、重量比（実測値）と、面積比との関係を図６に示し、ＰＰとＰＶＡｃとの、重量比（実測値）と、面積比との関係を図７に示す。 The relationship between the weight ratio (measured value) and area ratio of PE and PVAc, created based on the results of Table 6, is shown in FIG. 6, and the weight ratio (measured value) and area of PP and PVAc The relationship with the ratio is shown in FIG.
表６および図６に示した結果から、プラスチック中のＰＥの重量は、以下のように求めることができる。 From the results shown in Table 6 and FIG. 6, the weight of PE in the plastic can be obtained as follows.
ＰＥ重量（ｍｇ）／ＰＶＡｃ重量（ｍｇ）＝１３．３２ＰＥ面積／ＰＶＡｃ面積
ここで、上記式の相関係数は、０．８９８５であった。PE weight (mg) / PVAc weight (mg) = 13.32 PE area / PVAc area Here, the correlation coefficient of the above formula was 0.8985.
ＰＥ重量（ｍｇ）＝１３．３２ＰＥ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
また、プラスチック中のＰＥ純度（％）は試料全体の重量をＳＷ（ｍｇ）とすると、以下のように求めることができる。PE weight (mg) = 13.32 PE area / PVAc area × PVAc weight (mg)
The PE purity (%) in the plastic can be determined as follows, assuming that the weight of the entire sample is SW (mg).
ＰＥ純度（％）＝ＰＥ重量（ｍｇ）／ＳＷ（ｍｇ）×１００
表６および図７に示した結果から、プラスチック中のＰＰの重量は、以下のように求めることができる。PE purity (%) = PE weight (mg) / SW (mg) × 100
From the results shown in Table 6 and FIG. 7, the weight of PP in the plastic can be determined as follows.
ＰＰ重量（ｍｇ）／ＰＶＡｃ重量（ｍｇ）＝３２．５２ＰＰ面積／ＰＶＡｃ面積
ここで、上記式の相関係数は、０．９５５１であった。PP weight (mg) / PVAc weight (mg) = 32.52 PP area / PVAc area Here, the correlation coefficient of the above formula was 0.9551.
ＰＰ重量（ｍｇ）＝３２．５２ＰＰ面積／ＰＶＡｃ面積×ＰＶＡｃ重量（ｍｇ）
また、プラスチック中のＰＰ純度（％）は試料全体の重量をＳＷ（ｍｇ）とすると、以下のように求めることができる。PP weight (mg) = 32.52PP area / PVAc area × PVAc weight (mg)
The PP purity (%) in the plastic can be determined as follows, assuming that the weight of the entire sample is SW (mg).
ＰＰ純度（％）＝ＰＰ重量（ｍｇ）／ＳＷ（ｍｇ）×１００ PP purity (%) = PP weight (mg) / SW (mg) × 100
Claims (4)
秤量した前記プラスチックに、秤量した内部標準物質を加える工程（Ａ）、
内部標準物質が加えられたプラスチックを、赤外分光法で分析する工程（Ｂ）、
前記工程（Ｂ）で得られたＩＲスペクトルから、プラスチックに含まれるポリエチレン量およびポリプロピレン量を求める工程（Ｃ）を有し、
前記内部標準物質が、ポリ酢酸ビニル、ポリアクリロニトリル、ポリピバリン酸ビニル、またはポリモノクロロ酢酸ビニルである、プラスチックの純度測定方法。 A method for measuring the purity of a plastic containing at least one of polyethylene and polypropylene,
Adding a weighed internal standard substance to the weighed plastic (A),
Analyzing the plastic to which the internal standard substance is added by infrared spectroscopy (B),
From the IR spectrum obtained in the step (B), it has a step (C) to obtain the polyethylene amounts and polypropylene content in the plastic,
A method for measuring the purity of a plastic, wherein the internal standard substance is polyvinyl acetate, polyacrylonitrile, vinyl polypivalate, or polymonochlorovinyl acetate .
内部標準物質に対するポリエチレンの量を定量する際に用いる検量線および、
内部標準物質に対するポリプロピレンの量を定量する際に用いる検量線を作成する工程（α）を有する請求項１に記載のプラスチックの純度測定方法。 Using weighed polyethylene, polypropylene and internal standard,
A calibration curve used to quantify the amount of polyethylene relative to the internal standard, and
The method for measuring the purity of a plastic according to claim 1, further comprising a step (α) of preparing a calibration curve used for quantifying the amount of polypropylene with respect to the internal standard substance.
The method for measuring the purity of a plastic according to any one of claims 1 to 3 , wherein the plastic is waste plastic.
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- 2019-01-31 JP JP2019506206A patent/JP6574081B1/en active Active
- 2019-01-31 WO PCT/JP2019/003348 patent/WO2019167535A1/en active Application Filing
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| JPH09138194A (en) * | 1995-11-13 | 1997-05-27 | Toyota Central Res & Dev Lab Inc | High speed identification method of resin by infrared spectroscopic analysis method and its system |
| JP2001074729A (en) * | 1999-09-08 | 2001-03-23 | Kawasaki Steel Corp | Method for analyzing plastic and dechlorination method |
| JP2003227793A (en) * | 2001-11-28 | 2003-08-15 | Matsushita Ecotechnology Center:Kk | Method for identifying plastic |
| JP2004074151A (en) * | 2003-07-29 | 2004-03-11 | Mitsubishi Heavy Ind Ltd | Plastic material identification apparatus |
| JP2005249624A (en) * | 2004-03-05 | 2005-09-15 | Japan Science & Technology Agency | Polymer group discriminating method by optical spectrum |
| JP2013064726A (en) * | 2011-08-26 | 2013-04-11 | Mitsubishi Electric Corp | Resin identification device and method |
| JP2013166921A (en) * | 2012-01-20 | 2013-08-29 | Toray Ind Inc | Fiber-reinforced polypropylene-based resin composition |
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| WO2019167535A1 (en) | 2019-09-06 |
| JPWO2019167535A1 (en) | 2020-04-16 |
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