JP4473225B2 - Recycled polyvinyl chloride compound manufacturing method. - Google Patents

Recycled polyvinyl chloride compound manufacturing method. Download PDF

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JP4473225B2
JP4473225B2 JP2006011251A JP2006011251A JP4473225B2 JP 4473225 B2 JP4473225 B2 JP 4473225B2 JP 2006011251 A JP2006011251 A JP 2006011251A JP 2006011251 A JP2006011251 A JP 2006011251A JP 4473225 B2 JP4473225 B2 JP 4473225B2
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polyvinyl chloride
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JP2007191586A (en
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昇明 井出
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Shinko Pantec Co Ltd
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Kobelco Eco Solutions Co Ltd
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Description

本発明は、再生ポリ塩化ビニルコンパウンド製造方法に関し、特に軟質ポリ塩化ビニルコンパウンドから鉛安定剤を除去して再生する再生ポリ塩化ビニルコンパウンド製造方法に関する。   The present invention relates to a method for producing a reclaimed polyvinyl chloride compound, and more particularly to a method for producing a reclaimed polyvinyl chloride compound in which a lead stabilizer is removed from a soft polyvinyl chloride compound for regeneration.

昨今の環境意識の高まりにより、鉛系化合物を安定剤として用いたポリ塩化ビニルコンパウンドの使用は抑えられつつあり、再生されたポリ塩化ビニルコンパウンドも鉛化合物が混入していないものが求められている。そのため、金属化合物、特に鉛系化合物を含むポリ塩化ビニル製の下水道パイプ、電線被覆材などからポリ塩化ビニルコンパウンドを再生するためには、再生ポリ塩化ビニルコンパウンドの製造プロセスにおいて鉛系化合物を除去する工程を追加する必要がある。   Due to the recent increase in environmental awareness, the use of polyvinyl chloride compounds using lead-based compounds as stabilizers is being suppressed, and regenerated polyvinyl chloride compounds that are free of lead compounds are also required. . Therefore, in order to recycle polyvinyl chloride from sewer pipes made of polyvinyl chloride containing metal compounds, especially lead compounds, and wire covering materials, lead compounds are removed in the manufacturing process of recycled polyvinyl chloride compounds. It is necessary to add a process.

一般的に有機溶媒中から金属化合物を除去する方法として、遠心分離等の比重分別法、溶媒抽出法等が挙げられる。下記特許文献１には、この溶媒抽出法により樹脂中から顔料を除去する方法が記載されている。   Generally, methods for removing metal compounds from organic solvents include specific gravity fractionation methods such as centrifugation, solvent extraction methods, and the like. Patent Document 1 listed below describes a method for removing a pigment from a resin by this solvent extraction method.

この溶媒抽出法によれば、例えば、水系有機溶媒にポリ塩化ビニルコンパウンドを溶解したポリ塩化ビニルコンパウンド溶液の中にさらに非水系有機溶媒を添加し、その後、酸性水溶液を添加しポリ塩化ビニルコンパウンドを溶解している有機溶媒相と鉛安定剤を溶解している水相とに相分離させて鉛安定剤を選択的に除去させることができ、比重分別法に比べて効率よく鉛化合物を除去することが可能である。   According to this solvent extraction method, for example, a non-aqueous organic solvent is further added to a polyvinyl chloride compound solution in which a polyvinyl chloride compound is dissolved in an aqueous organic solvent, and then an acidic aqueous solution is added to add the polyvinyl chloride compound. The lead stabilizer can be selectively removed by phase separation into the dissolved organic solvent phase and the aqueous phase in which the lead stabilizer is dissolved, and lead compounds are removed more efficiently than the specific gravity fractionation method. It is possible.

しかし実際は、特に軟質のポリ塩化ビニルコンパウンドにこの溶媒抽出法を適用しようとしても鉛安定剤の除去が不充分で、しかも、得られる再生ポリ塩化ビニルコンパウンドの熱安定性が悪くなることから、この溶媒抽出法はポリ塩化ビニルコンパウンドの再生に殆ど用いられてはいない。
すなわち、従来の再生ポリ塩化ビニルコンパウンドの製造方法においては、熱安定性などの特性低下を抑制しつつ低鉛化あるいは無鉛化の要望を十分満足させ得る再生ポリ塩化ビニルコンパウンドを得ることが困難であるという問題を有している。
米国特許 第３０４３７８５号 However, in practice, even if this solvent extraction method is applied to a soft polyvinyl chloride compound, the lead stabilizer is not sufficiently removed, and the thermal stability of the resulting recycled polyvinyl chloride compound is deteriorated. Solvent extraction is rarely used to regenerate polyvinyl chloride compounds.
That is, it is difficult to obtain a recycled polyvinyl chloride compound that can sufficiently satisfy the demand for low lead or lead-free while suppressing deterioration in characteristics such as thermal stability in the conventional method for producing recycled polyvinyl chloride compound. There is a problem that there is.
U.S. Pat. No. 3,043,785

本発明は、上記問題を鑑みてなされたもので、特性低下を抑制しつつ低鉛化あるいは無鉛化の要望を十分満足させ得る再生ポリ塩化ビニルコンパウンド製造方法を提供することを課題とする。   This invention is made | formed in view of the said problem, and makes it a subject to provide the reproduction | regeneration polyvinyl chloride compound manufacturing method which can fully satisfy the request | requirement of lead-free or lead-free, suppressing a characteristic fall.

本発明者は、ポリ塩化ビニルコンパウンドの溶媒抽出法による鉛化合物の除去について鋭意検討を行い、可塑剤としてエステル化合物が用いられたポリ塩化ビニルコンパウンドを溶媒抽出法により鉛化合物を除去する場合には、酸性水溶液を添加したときに前記エステル化合物が分解して、有機酸やアルコールに転化すること、ならびに、この有機酸やアルコールが相分離の界面に存在して相分離を阻害することにより、鉛化合物の除去効率を低下させていることを見出した。また、この有機酸が再生ポリ塩化ビニルコンパウンド中に残存して、再生ポリ塩化ビニルコンパウンドの熱安定性を低下させていることを見出して本発明の完成に到ったのである。   The present inventor has intensively studied the removal of lead compounds by a solvent extraction method of polyvinyl chloride compound, and in the case of removing a lead compound from a polyvinyl chloride compound using an ester compound as a plasticizer by a solvent extraction method. When the acidic aqueous solution is added, the ester compound is decomposed and converted into an organic acid or alcohol, and the presence of the organic acid or alcohol at the interface of phase separation inhibits phase separation. It was found that the compound removal efficiency was lowered. In addition, the present inventors have found that this organic acid remains in the recycled polyvinyl chloride compound to reduce the thermal stability of the recycled polyvinyl chloride compound, thereby completing the present invention.

すなわち、本発明は、上記課題を解決すべくなされたもので、再生ポリ塩化ビニルコンパウンド製造方法にかかる請求項１記載の発明は、エステル化合物を含む可塑剤、鉛安定剤およびポリ塩化ビニルレジンが含有されてなるポリ塩化ビニルコンパウンドを、前記鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な溶媒に溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程と、該溶解工程で作製された前記ポリ塩化ビニルコンパウンド溶液と鉛安定剤を溶解可能な酸性水溶液とを混合してポリ塩化ビニルコンパウンド溶液と酸性水溶液とを相分離させることによりポリ塩化ビニルコンパウンド溶液から鉛安定剤を除去する鉛安定剤除去工程とを実施した後に、該鉛安定剤除去工程で鉛安定剤が除去されたポリ塩化ビニルコンパウンド溶液からポリ塩化ビニルコンパウンドを再生させる再生ポリ塩化ビニルコンパウンドの製造方法であって、前記鉛安定剤除去工程前に前記可塑剤を除去する可塑剤除去工程をさらに実施することを特徴としている。   That is, the present invention has been made to solve the above problems, and the invention according to claim 1 relating to a method for producing a recycled polyvinyl chloride compound comprises a plasticizer containing an ester compound, a lead stabilizer, and a polyvinyl chloride resin. A polyvinyl chloride compound prepared by dissolving the lead stabilizer in a solvent capable of forming a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer, and preparing the polyvinyl chloride compound solution by the dissolution step The lead stabilizer is removed from the polyvinyl chloride compound solution by mixing the prepared polyvinyl chloride compound solution and an acidic aqueous solution capable of dissolving the lead stabilizer and phase-separating the polyvinyl chloride compound solution and the acidic aqueous solution. After the lead stabilizer removal step, the polyvinyl chloride from which the lead stabilizer has been removed in the lead stabilizer removal step A method of manufacturing a reproduction polyvinyl chloride compound to regenerate the polyvinyl chloride compound from compound solution, is characterized by further carrying out the plasticizer removing step of removing the plasticizer before the lead stabilizer removing step.

また、再生ポリ塩化ビニルコンパウンド製造方法にかかる請求項２記載の発明は、請求項１記載の発明において、前記溶解工程、前記可塑剤除去工程および前記鉛安定剤除去工程として、下記ａ〜ｃに示す工程を実施することを特徴としている。
ａ．鉛安定剤を溶解可能な酸性水溶液との相分離状態が形成可能で且つ前記ポリ塩化ビニルコンパウンドを溶解可能な第一溶媒にポリ塩化ビニルコンパウンドを溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程。
ｂ．前記ポリ塩化ビニルコンパウンド溶液と相分離状態を形成可能で、しかも、前記第一溶媒よりも前記可塑剤の溶解性が高く、前記第一溶媒よりも前記塩化ビニルレジンの溶解性が低い第二溶媒と、前記ポリ塩化ビニルコンパウンド溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記二溶媒とを相分離させることにより前記ポリ塩化ビニルコンパウンド溶液から前記可塑剤を除去する可塑剤除去工程。
ｃ．前記可塑剤が除去された前記ポリ塩化ビニルコンパウンド溶液と、前記鉛安定剤を溶解可能な酸性水溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記酸性水溶液とを相分離させることにより前記鉛安定剤を除去する鉛安定剤除去工程。 Further, the invention according to claim 2 according to the method for producing a regenerated polyvinyl chloride compound is as follows. In the invention according to claim 1, as the dissolving step, the plasticizer removing step and the lead stabilizer removing step, It is characterized by carrying out the steps shown.
a. Dissolution step of producing a polyvinyl chloride compound solution by dissolving the polyvinyl chloride compound in a first solvent capable of forming a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer and capable of dissolving the polyvinyl chloride compound. .
b. A second solvent capable of forming a phase-separated state with the polyvinyl chloride compound solution, and having a higher solubility of the plasticizer than the first solvent and a lower solubility of the vinyl chloride resin than the first solvent; A plasticizer removing step of removing the plasticizer from the polyvinyl chloride compound solution by mixing the polyvinyl chloride compound solution and phase separating the polyvinyl chloride compound solution and the two solvents.
c. By mixing the polyvinyl chloride compound solution from which the plasticizer has been removed and an acidic aqueous solution capable of dissolving the lead stabilizer, the polyvinyl chloride compound solution and the acidic aqueous solution are phase-separated to thereby stabilize the lead. Lead stabilizer removal process to remove the agent.

また、再生ポリ塩化ビニルコンパウンド製造方法にかかる請求項３記載の発明は、請求項１または２に記載の発明において、前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒よりも塩化ビニルレジンの溶解性が高く且つ鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な第三溶媒を、前記可塑剤除去工程後、前記鉛安定剤除去工程前の前記ポリ塩化ビニルコンパウンド溶液に添加する溶媒添加工程をさらに実施することを特徴としている。   The invention according to claim 3 relating to the method for producing a regenerated polyvinyl chloride compound is the invention according to claim 1 or 2, wherein the vinyl chloride resin is dissolved more than the solvent used for dissolving the polyvinyl chloride compound in the dissolving step. A third solvent capable of forming a phase separation state with an acidic aqueous solution that is highly soluble and capable of dissolving the lead stabilizer is added to the polyvinyl chloride compound solution after the plasticizer removing step and before the lead stabilizer removing step. The solvent addition step is further performed.

また、再生ポリ塩化ビニルコンパウンド製造方法にかかる請求項４記載の発明は、請求項１乃至３のいずれか１項に記載の発明において、前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒には、水系有機溶媒と非水系有機溶媒とが混在する混合系有機溶媒が用いられることを特徴とし、請求項５記載の発明は、請求項４に記載の発明において、前記混合系有機溶媒は、水系有機溶媒と非水系有機溶媒が質量比で（水系有機溶媒／非水系有機溶媒）＝５／９５〜５０／５０となる割合で混在していることを特徴としている。また、請求項６記載の発明は、請求項４または５に記載の発明において、水系有機溶媒がメチルエチルケトンであり、且つ、非水系有機溶媒がトルエンであることを特徴としている。   The invention according to claim 4 relating to the method for producing a regenerated polyvinyl chloride compound is the solvent according to any one of claims 1 to 3, wherein the solvent is used for dissolving the polyvinyl chloride compound in the dissolving step. Is a mixed organic solvent in which an aqueous organic solvent and a non-aqueous organic solvent are mixed, and the invention according to claim 5 is the invention according to claim 4, wherein the mixed organic solvent is: The aqueous organic solvent and the non-aqueous organic solvent are mixed at a mass ratio of (aqueous organic solvent / non-aqueous organic solvent) = 5/95 to 50/50. The invention described in claim 6 is characterized in that, in the invention described in claim 4 or 5, the aqueous organic solvent is methyl ethyl ketone and the non-aqueous organic solvent is toluene.

さらに、再生ポリ塩化ビニルコンパウンド製造方法にかかる請求項７記載の発明は、請求項２乃至６のいずれか１項に記載の発明において、前記第二溶媒にはジメチルスルホキシドが用いられていることを特徴とし、請求項８記載の発明は、請求項３乃至７のいずれか１項に記載の発明において前記第三溶媒には、メチルエチルケトン、シクロヘキサノンおよびテトラヒドロフランのいずれかが用いられることを特徴としている。   Furthermore, in the invention according to claim 7 according to the method for producing a regenerated polyvinyl chloride compound, in the invention according to any one of claims 2 to 6, dimethyl sulfoxide is used as the second solvent. The invention according to claim 8 is characterized in that in the invention according to any one of claims 3 to 7, any of methyl ethyl ketone, cyclohexanone and tetrahydrofuran is used as the third solvent.

本発明によれば、エステル化合物を含む可塑剤、鉛安定剤およびポリ塩化ビニルレジンが含有されてなるポリ塩化ビニルコンパウンドを、前記鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な溶媒に溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程と、該溶解工程で作製された前記ポリ塩化ビニルコンパウンド溶液と鉛安定剤を溶解可能な酸性水溶液とを混合してポリ塩化ビニルコンパウンド溶液と酸性水溶液とを相分離させることによりポリ塩化ビニルコンパウンド溶液から鉛安定剤を除去する鉛安定剤除去工程とを実施した後に、該鉛安定剤除去工程で鉛安定剤が除去されたポリ塩化ビニルコンパウンド溶液からポリ塩化ビニルコンパウンドを再生させる再生ポリ塩化ビニルコンパウンド製造方法において、前記鉛安定剤除去工程前に前記可塑剤を除去する可塑剤除去工程をさらに実施することから、ポリ塩化ビニルコンパウンド溶液から鉛安定剤を除去すべくポリ塩化ビニルコンパウンド溶液に酸性水溶液を接触させた際に、エステル化合物の分解生成物である有機酸やアルコールが生成されて相分離が阻害されることを抑制させ得る。したがって、鉛安定剤の除去効率を向上させ得る。   According to the present invention, a polyvinyl chloride compound containing a plasticizer containing an ester compound, a lead stabilizer and a polyvinyl chloride resin can form a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer. A polyvinyl chloride compound solution prepared by mixing a polyvinyl chloride compound solution prepared by dissolving in a solvent and an acidic aqueous solution capable of dissolving a lead stabilizer. The lead stabilizer is removed from the polyvinyl chloride compound solution by phase-separating the aqueous solution and the acidic aqueous solution, and the lead stabilizer is removed in the lead stabilizer removal step. In a method for producing a regenerated polyvinyl chloride compound for regenerating a polyvinyl chloride compound from a compound solution, Since the plasticizer removing step of removing the plasticizer before the lead stabilizer removing step is further performed, an acidic aqueous solution was brought into contact with the polyvinyl chloride compound solution to remove the lead stabilizer from the polyvinyl chloride compound solution. In this case, it can be suppressed that the organic acid or alcohol which is a decomposition product of the ester compound is generated and phase separation is inhibited. Therefore, the removal efficiency of the lead stabilizer can be improved.

また、エステル化合物の分解生成物である有機酸やアルコールが再生ポリ塩化ビニルコンパウンド中に残存することを抑制するため、再生ポリ塩化ビニルコンパウンドの熱安定性が低下することも抑制し得る。
さらには、再生ポリ塩化ビニルコンパウンドへの有機酸の残存や、再生ポリ塩化ビニルコンパウンドの熱安定性の低下が抑制されることから、再生ポリ塩化ビニルコンパウンドの混練を行う混練機などの設備が、この有機酸やポリ塩化ビニルコンパウンドからの脱塩酸により腐食されることも抑制させることができる。 Moreover, since it suppresses that the organic acid and alcohol which are decomposition products of an ester compound remain | survive in a reproduction | regeneration polyvinyl chloride compound, it can also suppress that the thermal stability of a reproduction | regeneration polyvinyl chloride compound falls.
Furthermore, since the remaining of the organic acid in the recycled polyvinyl chloride compound and the decrease in the thermal stability of the recycled polyvinyl chloride compound are suppressed, facilities such as a kneader for kneading the recycled polyvinyl chloride compound are provided. Corrosion due to dehydrochlorination from this organic acid or polyvinyl chloride compound can also be suppressed.

また、前記溶解工程、前記可塑剤除去工程および前記鉛安定剤除去工程として、ａ）鉛安定剤を溶解可能な酸性水溶液との相分離状態が形成可能で且つ前記ポリ塩化ビニルコンパウンドを溶解可能な第一溶媒にポリ塩化ビニルコンパウンドを溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程、ｂ）前記ポリ塩化ビニルコンパウンド溶液と相分離状態を形成可能で、しかも、前記第一溶媒よりも前記可塑剤の溶解性が高く、前記第一溶媒よりも前記塩化ビニルレジンの溶解性が低い第二溶媒と、前記ポリ塩化ビニルコンパウンド溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記二溶媒とを相分離させることにより前記ポリ塩化ビニルコンパウンド溶液から前記可塑剤を除去する可塑剤除去工程、ｃ）前記可塑剤が除去された前記ポリ塩化ビニルコンパウンド溶液と、前記鉛安定剤を溶解可能な酸性水溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記酸性水溶液とを相分離させることにより前記鉛安定剤を除去する鉛安定剤除去工程を実施する場合には、溶液化されたポリ塩化ビニルコンパウンドに可塑剤の溶解性が高い溶媒を接触させて相分離により可塑剤を除去することから、可塑剤の除去効率をより向上させることができる。したがって、エステル化合物の分解生成物の形成がさらに抑制され、鉛安定剤の除去効率をさらに向上させ得るとともに再生ポリ塩化ビニルコンパウンドの特性低下をさらに抑制させ得る。   Further, as the dissolving step, the plasticizer removing step, and the lead stabilizer removing step, a) a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer can be formed, and the polyvinyl chloride compound can be dissolved. A dissolving step in which a polyvinyl chloride compound is dissolved in a first solvent to prepare a polyvinyl chloride compound solution; b) a phase separation state can be formed with the polyvinyl chloride compound solution, and the plasticity is higher than that of the first solvent. A second solvent having a higher solubility of the agent and a lower solubility of the vinyl chloride resin than the first solvent, and the polyvinyl chloride compound solution are mixed, and the polyvinyl chloride compound solution and the two solvents are combined. A plasticizer removing step of removing the plasticizer from the polyvinyl chloride compound solution by separating; c) removing the plasticizer Lead that removes the lead stabilizer by mixing the polyvinyl chloride compound solution and an acidic aqueous solution capable of dissolving the lead stabilizer, and phase-separating the polyvinyl chloride compound solution and the acidic aqueous solution When carrying out the stabilizer removal step, the plasticizer is removed by phase separation by bringing a solvent in which the plasticizer is highly soluble into contact with the solution of polyvinyl chloride compound. Can be improved. Therefore, the formation of the decomposition product of the ester compound can be further suppressed, the removal efficiency of the lead stabilizer can be further improved, and the deterioration of the properties of the recycled polyvinyl chloride compound can be further suppressed.

また、前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒よりも塩化ビニルレジンの溶解性が高く且つ鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な第三溶媒を、前記可塑剤除去工程後、前記鉛安定剤除去工程前の前記ポリ塩化ビニルコンパウンド溶液に添加する溶媒添加工程をさらに実施する場合には、可塑剤が除去されてポリ塩化ビニルコンパウンド溶液に対する溶解性の低下した塩化ビニルレジンの溶解性を再び高めることができ、鉛安定剤除去工程時にポリ塩化ビニルレジンが析出することを抑制させ得る。   A third solvent capable of forming a phase separation state with an acidic aqueous solution having a higher solubility of vinyl chloride resin and capable of dissolving a lead stabilizer than the solvent used for dissolving the polyvinyl chloride compound in the dissolving step; When the solvent addition step of adding to the polyvinyl chloride compound solution after the plasticizer removal step and before the lead stabilizer removal step is further performed, the plasticizer is removed and the solubility in the polyvinyl chloride compound solution is reduced. Thus, the solubility of the vinyl chloride resin can be increased again, and the precipitation of the polyvinyl chloride resin during the lead stabilizer removal step can be suppressed.

また、前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒には、水系有機溶媒と非水系有機溶媒とが混在する混合系有機溶媒が用いられる場合には、ポリ塩化ビニルコンパウンドに含まれる可塑剤の量や、そのエステル化合物の種類、その他の配合物などから、可塑剤除去や鉛安定剤除去あるいは相分離の形成に適した混在状態に溶媒を調整することが容易であるという効果を奏する。さらに、この前記混合系有機溶媒を、水系有機溶媒と非水系有機溶媒が質量比で（水系有機溶媒／非水系有機溶媒）＝５／９５〜５０／５０となる割合で混在しているものを用いることで、ポリ塩化ビニルコンパウンドの溶解性を高めつつ鉛安定剤除去工程での安定した相分離状態が形成される。
特に、水系有機溶媒がメチルエチルケトンであり、且つ、非水系有機溶媒がトルエンである場合には、ポリ塩化ビニルコンパウンドの溶解性を高めつつ鉛安定剤除去工程での安定した相分離状態が形成される効果をより顕著に奏する。 In the case where a mixed organic solvent in which an aqueous organic solvent and a non-aqueous organic solvent are mixed is used as the solvent used for dissolving the polyvinyl chloride compound in the dissolving step, the plastic contained in the polyvinyl chloride compound is used. From the amount of the agent, the type of the ester compound, and other blends, it is possible to easily adjust the solvent to a mixed state suitable for plasticizer removal, lead stabilizer removal, or phase separation formation. . Further, the mixed organic solvent is a mixture of an aqueous organic solvent and a non-aqueous organic solvent in a mass ratio of (aqueous organic solvent / non-aqueous organic solvent) = 5/95 to 50/50. By using, the stable phase-separation state in a lead stabilizer removal process is formed, improving the solubility of a polyvinyl chloride compound.
In particular, when the aqueous organic solvent is methyl ethyl ketone and the non-aqueous organic solvent is toluene, a stable phase separation state is formed in the lead stabilizer removal step while increasing the solubility of the polyvinyl chloride compound. The effect is more remarkable.

また、前記第二溶媒にはジメチルスルホキシドが用いられている場合には、多くのエステル化合物に対して優れた溶解性を示し、ポリ塩化ビニルコンパウンド溶液中からより多くの可塑剤を除去することができ、鉛安定剤除去工程でのエステル化合物の分解生成物の形成がさらに抑制され、鉛安定剤の除去効率をさらに向上させ得るとともに再生ポリ塩化ビニルコンパウンドの特性低下をさらに抑制させ得る。
また、前記第三溶媒には、メチルエチルケトン、シクロヘキサノンおよびテトラヒドロフランのいずれかが用いられる場合には、鉛安定剤除去工程時に安定したポリ塩化ビニルコンパウンド溶液と酸性水溶液との安定した相分離状態を形成させつつ、ポリ塩化ビニルレジンが析出することをさらに抑制させる効果を奏する。 In addition, when dimethyl sulfoxide is used as the second solvent, it exhibits excellent solubility in many ester compounds, and more plasticizer can be removed from the polyvinyl chloride compound solution. In addition, the formation of the decomposition product of the ester compound in the lead stabilizer removal step can be further suppressed, and the removal efficiency of the lead stabilizer can be further improved and the characteristic deterioration of the recycled polyvinyl chloride compound can be further suppressed.
In addition, when any of methyl ethyl ketone, cyclohexanone and tetrahydrofuran is used as the third solvent, a stable phase separation state between a stable polyvinyl chloride compound solution and an acidic aqueous solution is formed during the lead stabilizer removal step. However, it has the effect of further suppressing the precipitation of the polyvinyl chloride resin.

以下、本発明の実施形態について図を参照して説明する。
図１は、エステル化合物を含む可塑剤、鉛安定剤が含有されている廃ポリ塩化ビニルコンパウンドから鉛安定剤を除去して再生させる再生方法を説明するためのブロック図である。 Embodiments of the present invention will be described below with reference to the drawings.
FIG. 1 is a block diagram for explaining a regeneration method in which a lead stabilizer is removed from a waste polyvinyl chloride compound containing a plasticizer and a lead stabilizer containing an ester compound and regenerated.

本実施形態においては、まず、ポリ塩化ビニルコンパウンドに水系有機溶媒、非水系有機溶媒を添加して混合し、ポリ塩化ビニルコンパウンドを溶解する溶解工程を実施する。
なお、水系有機溶媒、非水系有機溶媒との用語は、本明細書中においては、水と相溶するものを水系有機溶媒水と相溶しないものを非水系有機溶媒と意図して用いており、前記水系有機溶媒としてはメチルエチルケトン、アセトン、テトラヒドロフラン、シクロヘキサノンなどが挙げられる。
また、前記非水系有機溶媒としては、トルエン、ベンゼン、キシレン、ｎ−ヘキサン、イソヘキサン、ｎ−ペンタン、ｎ−ブタンなどが挙げられる。
中でも、塩化ビニルレジンの溶解性が高くポリ塩化ビニルコンパウンドの溶解性を高めつつ鉛安定剤除去工程で安定した相分離状態を形成され得る点、および、沸点が低いことから、可塑剤や鉛安定剤を除去したポリ塩化ビニルコンパウンド溶液から減圧蒸留や加熱により溶媒を容易に除去し得る点において前記水系有機溶媒にメチルエチルケトン、前記非水系有機溶媒にトルエンを用いることが好ましい。 In the present embodiment, first, a dissolving step is performed in which an aqueous organic solvent and a nonaqueous organic solvent are added to and mixed with a polyvinyl chloride compound to dissolve the polyvinyl chloride compound.
In the present specification, the terms water-based organic solvent and non-aqueous organic solvent are intended to use those that are compatible with water and those that are not compatible with water-based organic solvent water. Examples of the aqueous organic solvent include methyl ethyl ketone, acetone, tetrahydrofuran, and cyclohexanone.
Examples of the non-aqueous organic solvent include toluene, benzene, xylene, n-hexane, isohexane, n-pentane, and n-butane.
Among them, plasticizers and lead stabilizers have a high solubility of vinyl chloride resin and can form a stable phase separation in the lead stabilizer removal process while increasing the solubility of polyvinyl chloride compounds, and the low boiling point. It is preferable to use methyl ethyl ketone as the aqueous organic solvent and toluene as the non-aqueous organic solvent in that the solvent can be easily removed from the polyvinyl chloride compound solution from which water has been removed by vacuum distillation or heating.

通常、上記に挙げた非水系有機溶媒であるトルエン、ベンゼン、キシレン、ｎ−ヘキサン、イソヘキサン等はポリ塩化ビニルコンパウンドを溶解しにくいが、水系有機溶媒であるメチルエチルケトン、アセトン、テトラヒドロフラン、シクロヘキサノンを混合することによりポリ塩化ビニルコンパウンドに対する溶解性を高めることができる。また、非水系有機溶媒と水系有機溶媒とが混在した混合系有機溶媒によりポリ塩化ビニルコンパウンドの溶解を行う場合には、このようにポリ塩化ビニルコンパウンドの溶解性を制御しやすいのみならず、ポリ塩化ビニルコンパウンドに含まれる可塑剤の量や、そのエステル化合物の種類、その他の配合物などから、可塑剤除去や鉛安定剤除去あるいは相分離の形成に適したポリ塩化ビニル溶液を容易に調整することができる。   Usually, toluene, benzene, xylene, n-hexane, isohexane, etc., which are the non-aqueous organic solvents mentioned above, are difficult to dissolve polyvinyl chloride compound, but are mixed with aqueous organic solvents, methyl ethyl ketone, acetone, tetrahydrofuran, cyclohexanone. Therefore, the solubility with respect to the polyvinyl chloride compound can be enhanced. When the polyvinyl chloride compound is dissolved in a mixed organic solvent in which a non-aqueous organic solvent and an aqueous organic solvent are mixed, not only the solubility of the polyvinyl chloride compound is easily controlled in this way, Easily prepare a polyvinyl chloride solution suitable for plasticizer removal, lead stabilizer removal, or phase separation formation based on the amount of plasticizer contained in the vinyl chloride compound, the type of ester compound, and other compounds. be able to.

ここで、非水系有機溶媒及び水系有機溶媒の割合は、後段において説明する可塑剤除去工程での効率の点から、水系有機溶媒／非水系有機溶媒の質量比を５／９５〜５０／５０とすることが好ましい。水系有機溶媒の割合が前記割合よりも少なくなると、ポリ塩化ビニルコンパウンドの溶解性が悪くなり、溶解工程において、十分にポリ塩化ビニルコンパウンドを溶解させ難くなる。また、水系有機溶媒の混合割合が前記割合よりも高くなると、可塑剤除去工程における可塑剤の除去によりポリ塩化ビニルコンパウンド溶液からポリ塩化ビニルレジンが析出するおそれがある。したがって、非水系有機溶媒及び水系有機溶媒を混合添加する割合が上記範囲外の場合には、可塑剤除去工程での効率低下を招くおそれを有する。   Here, the ratio of the non-aqueous organic solvent and the aqueous organic solvent is such that the mass ratio of the aqueous organic solvent / non-aqueous organic solvent is 5/95 to 50/50 from the viewpoint of efficiency in the plasticizer removing step described later. It is preferable to do. When the proportion of the aqueous organic solvent is less than the above proportion, the solubility of the polyvinyl chloride compound is deteriorated, and it is difficult to sufficiently dissolve the polyvinyl chloride compound in the dissolving step. If the mixing ratio of the aqueous organic solvent is higher than the above ratio, the polyvinyl chloride resin may be precipitated from the polyvinyl chloride compound solution by removing the plasticizer in the plasticizer removing step. Therefore, when the ratio of mixing and adding the non-aqueous organic solvent and the aqueous organic solvent is outside the above range, the efficiency in the plasticizer removing step may be reduced.

次に、前記溶解工程にて溶液化されたポリ塩化ビニルコンパウンドに、このポリ塩化ビニルコンパウンド溶液との相分離状態を形成可能で、しかも、前記混合系有機溶媒（水系有機溶媒／非水系有機溶媒）よりも前記可塑剤の溶解性が高く且つ前記混合系有機溶媒よりも前記ポリ塩化ビニルレジンの溶解性が低い第二溶媒を、前記ポリ塩化ビニルコンパウンド溶液に混合して、前記可塑剤を第二溶媒に移行させて前記ポリ塩化ビニルコンパウンド溶液と前記第二溶媒とを相分離させた後に、この第二溶媒に同伴させて可塑剤を除去する可塑剤除去工程を実施する。
この第二溶媒としては、ポリ塩化ビニルコンパウンドに用いられるエステル化合物に対する溶解性が高く、前記混合系有機溶媒よりも鉛安定剤とポリ塩化ビニルレジンの溶解性が低いものであり、かつ、ポリ塩化ビニルコンパウンド溶液、さらには、前記溶解工程で用いた非水系有機溶媒とも相分離状態を形成するものが好ましく、ジメチルスルホキシド（ＤＭＳＯ）、スルホラン、ジメチルホルムアシド（ＤＭＦ）などを例示することができる。
中でも、多くのエステル化合物に対して優れた溶解性を示し、ポリ塩化ビニルコンパウンド溶液中からより多くの可塑剤を除去することができ、しかもトルエンなどの非水系有機溶媒とも相分離状態を形成させやすく、ポリ塩化ビニルコンパウンド溶液中から非水系有機溶媒を移行させることを抑制しつつ可塑剤を選択的に除去させ得る点においてジメチルスルホキシドが好ましい。 Next, a phase separation state with the polyvinyl chloride compound solution can be formed in the polyvinyl chloride compound that has been made into a solution in the dissolution step, and the mixed organic solvent (aqueous organic solvent / non-aqueous organic solvent). ) And a second solvent having a solubility of the polyvinyl chloride resin lower than that of the mixed organic solvent is mixed with the polyvinyl chloride compound solution, and the plasticizer is added to the second solution. After shifting to a solvent and phase-separating the polyvinyl chloride compound solution and the second solvent, a plasticizer removing step of removing the plasticizer with the second solvent is performed.
As this second solvent, the solubility to the ester compound used in the polyvinyl chloride compound is high, the solubility of the lead stabilizer and the polyvinyl chloride resin is lower than that of the mixed organic solvent, and the polyvinyl chloride. The compound solution, and further, those that form a phase-separated state with the non-aqueous organic solvent used in the dissolution step are preferred, and examples thereof include dimethyl sulfoxide (DMSO), sulfolane, and dimethylformacid (DMF).
Above all, it exhibits excellent solubility in many ester compounds, can remove more plasticizers from the polyvinyl chloride compound solution, and can also form a phase separation state with non-aqueous organic solvents such as toluene. Dimethyl sulfoxide is preferred because it is easy to selectively remove the plasticizer while suppressing the transfer of the non-aqueous organic solvent from the polyvinyl chloride compound solution.

なお、可塑剤やポリ塩化ビニルレジンに対する溶解性とは、通常、溶解度パラメータの比較により判断することができ、可塑剤やポリ塩化ビニルレジンの溶解度パラメータに比べてより近い値の溶解度パラメータを有する溶媒を可塑剤やポリ塩化ビニルレジンに対してより溶解性の高い溶媒として用いることができる。   The solubility in a plasticizer or polyvinyl chloride resin can usually be judged by comparing the solubility parameters. A solvent having a solubility parameter closer to that of the plasticizer or polyvinyl chloride resin is plasticized. It can be used as a solvent having higher solubility in the agent and polyvinyl chloride resin.

また、この可塑剤除去工程で第二溶媒に同伴させて除去した可塑剤は、別工程で精製して、ポリ塩化ビニルコンパウンドを再生する際に再び添加するようにしてもよく、これにより再生前に有していた特性と近い特性を有する再生ポリ塩化ビニルコンパウンドを得ることができる。しかも、再生ポリ塩化ビニルコンパウンドに対する新たな可塑剤を添加する必要性を低減させ得る。
この第二溶媒と可塑剤の分離精製方法としては溶媒抽出法、蒸留法等が挙げられる。 In addition, the plasticizer removed in the plasticizer removal step accompanying the second solvent may be purified in a separate step and added again when the polyvinyl chloride compound is regenerated. It is possible to obtain a reclaimed polyvinyl chloride compound having characteristics close to those of the present invention. Moreover, the need to add a new plasticizer to the recycled polyvinyl chloride compound can be reduced.
Examples of the method for separating and purifying the second solvent and the plasticizer include a solvent extraction method and a distillation method.

次いで、可塑剤が除去されたポリ塩化ビニルコンパウンド溶液に、前記溶解工程で用いられた混合系有機溶媒よりも塩化ビニルレジンの溶解性が高く且つ鉛安定剤を溶解可能な酸性水溶液との相分離状態が形成可能な第三溶媒を添加する溶媒添加工程をさらに実施する。
このように、可塑剤が除去されたポリ塩化ビニルコンパウンド溶液に、塩化ビニルレジンの溶解性が高く且つ鉛安定剤を溶解可能な酸性水溶液との相分離状態が形成可能な第三溶媒を添加することで可塑剤が除去されてポリ塩化ビニルコンパウンド溶液に対する溶解性の低下した塩化ビニルレジンの溶解性を再び高めることができ、鉛安定剤除去工程時にポリ塩化ビニルレジンが析出することを抑制させ得る。
この第三溶媒としては、例えば、メチルエチルケトン、シクロヘキサノン、アセトン、テトラヒドロフランなどが挙げられる。なかでも、メチルエチルケトン、シクロヘキサノンおよびテトラヒドロフランのいずれかが用いられる場合には、鉛安定剤除去工程時に安定したポリ塩化ビニルコンパウンド溶液と酸性水溶液との安定した相分離状態を形成させることができる。このような点において特に第三溶媒としては、メチルエチルケトンが用いられることが好ましい。 Next, the polyvinyl chloride compound solution from which the plasticizer has been removed has a phase separation state with an acidic aqueous solution that has higher solubility of vinyl chloride resin than the mixed organic solvent used in the dissolution step and can dissolve the lead stabilizer. A solvent addition step of adding a third solvent capable of forming is further performed.
Thus, adding a third solvent capable of forming a phase-separated state with an acidic aqueous solution having a high solubility of vinyl chloride resin and capable of dissolving a lead stabilizer to the polyvinyl chloride compound solution from which the plasticizer has been removed. Thus, the plasticizer is removed and the solubility of the vinyl chloride resin whose solubility in the polyvinyl chloride compound solution is lowered can be increased again, and the precipitation of the polyvinyl chloride resin during the lead stabilizer removal step can be suppressed.
Examples of the third solvent include methyl ethyl ketone, cyclohexanone, acetone, and tetrahydrofuran. In particular, when any of methyl ethyl ketone, cyclohexanone and tetrahydrofuran is used, a stable phase separation state between the stable polyvinyl chloride compound solution and the acidic aqueous solution can be formed during the lead stabilizer removal step. In this respect, methyl ethyl ketone is preferably used as the third solvent.

次いで、前記溶媒添加工程で溶媒が添加されたポリ塩化ビニルコンパウンド溶液に鉛安定剤を溶解可能な酸性水溶液を混合し、前記鉛安定剤をこの酸性水溶液に溶解させて前記ポリ塩化ビニルコンパウンド溶液と前記酸性水溶液とを相分離させた後に、この酸性水溶液に溶解させた鉛安定剤を酸性水溶液に同伴させて除去する鉛安定剤除去工程を実施する。
このとき、ポリ塩化ビニルコンパウンド溶液中に含まれる鉛の塩が形成されて酸性水溶液に移行されて水に溶解される。酸性水溶液としては、鉛安定剤を溶解させ得るものであれば特に限定されず、例えば、塩酸、硫酸、硝酸、リン酸などが挙げられる。中でも、塩酸が好ましい。 Next, an acidic aqueous solution capable of dissolving a lead stabilizer is mixed into the polyvinyl chloride compound solution to which a solvent is added in the solvent addition step, and the lead stabilizer is dissolved in the acidic aqueous solution to obtain the polyvinyl chloride compound solution. After the phase separation of the acidic aqueous solution, a lead stabilizer removing step is performed in which the lead stabilizer dissolved in the acidic aqueous solution is removed by accompanying the acidic aqueous solution.
At this time, a lead salt contained in the polyvinyl chloride compound solution is formed, transferred to an acidic aqueous solution, and dissolved in water. The acidic aqueous solution is not particularly limited as long as it can dissolve the lead stabilizer, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Of these, hydrochloric acid is preferred.

なお、実施形態において除去可能な鉛安定剤としては、例えば、ステアリン酸鉛、酸化鉛、酢酸鉛、三塩基性硫酸鉛などが挙げられる。   In addition, examples of the lead stabilizer that can be removed in the embodiment include lead stearate, lead oxide, lead acetate, and tribasic lead sulfate.

なお、上記工程により得られたポリ塩化ビニルコンパウンド溶液から従来の方法によりポリ塩化ビニルコンパウンドを回収（再生）することができる。この方法としては、例えば、ポリ塩化ビニルコンパウンド溶液に撹拌下で、ポリ塩化ビニルコンパウンドの溶解度の低い溶媒（貧溶媒ともいう）の加熱蒸気を添加することにより、ポリ塩化ビニルコンパウンド溶液の溶媒を蒸発させつつ前記貧溶媒を凝集させてポリ塩化ビニルコンパウンドを析出させてろ過し、例えば、グラニューラ状の再生ポリ塩化ビニルコンパウンドを得る方法や、単に貧溶媒を添加し、ポリ塩化ビニルコンパウンドを析出させ、さらに析出したポリ塩化ビニルコンパウンドを加熱することにより残存する水系有機溶媒や貧溶媒を除去し、再生ポリ塩化ビニルコンパウンドを得る方法が挙げられる。
また、前記貧溶媒としては脂肪族炭化水素やメタノール、エタノール等の低級アルコールもしくは水を利用するのが好ましい。
また、得られた再生ポリ塩化ビニルコンパウンドは必要に応じて、ペレット化しても良い。このときさらに、鉛安定剤に代わる安定剤や、前記可塑剤除去工程で除去された可塑剤を前述のごとく精製して添加することもできる。 The polyvinyl chloride compound can be recovered (regenerated) by a conventional method from the polyvinyl chloride compound solution obtained in the above step. As this method, for example, the solvent of the polyvinyl chloride compound solution is evaporated by adding heated steam of a solvent having low solubility of the polyvinyl chloride compound (also referred to as a poor solvent) to the polyvinyl chloride compound solution while stirring. The poor solvent is agglomerated to precipitate a polyvinyl chloride compound and filtered, for example, a method for obtaining a granular recycled polyvinyl chloride compound, or simply adding a poor solvent to precipitate the polyvinyl chloride compound. Furthermore, there is a method of removing the remaining aqueous organic solvent or poor solvent by heating the precipitated polyvinyl chloride compound to obtain a regenerated polyvinyl chloride compound.
The poor solvent is preferably an aliphatic hydrocarbon, a lower alcohol such as methanol or ethanol, or water.
Moreover, you may pelletize the obtained reproduction | regeneration polyvinyl chloride compound as needed. At this time, a stabilizer in place of the lead stabilizer and the plasticizer removed in the plasticizer removing step can be purified and added as described above.

本実施形態においては、エステル化合物を含む可塑剤、鉛安定剤が配合された廃ポリ塩化ビニルコンパウンドから鉛安定剤を除去して再生させる再生方法を上記のような場合を例に説明したが本発明においては、ポリ塩化ビニルコンパウンドからの鉛安定剤除去方法ならびに再生ポリ塩化ビニルコンパウンドの製造方法を上記のように場合に限定するものではない。   In the present embodiment, the regeneration method for removing and stabilizing the lead stabilizer from the waste polyvinyl chloride compound containing the plasticizer and lead stabilizer containing the ester compound has been described as an example in the above case. In the invention, the method for removing the lead stabilizer from the polyvinyl chloride compound and the method for producing the recycled polyvinyl chloride compound are not limited to the above cases.

以下、実施例により本発明をより詳細に説明するが、本発明はこれらの実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

（実施例１）
質量で２８％のジオクチルフタレート（以下「ＤＯＰ」ともいう）と１％の鉛安定剤（ステアリン酸鉛と三塩基性硫酸鉛の混合物）を含むポリ塩化ビニルコンパウンド製の電線被覆材１０ｇをトルエン８０ｇとメチルエチルケトン（以下「ＭＥＫ」ともいう）２０ｇの混合系有機溶媒１００ｇに溶解させる溶解工程を実施してポリ塩化ビニルコンパウンド溶液を作製した。
次いで、５０ｇのジメチルスルホキシド（以下「ＤＭＳＯ」ともいう）を添加し撹拌したものを分液ロートに移して静置し、ポリ塩化ビニルコンパウンド溶液とＤＭＳＯとを相分離させてＤＭＳＯ相のみを分離除去する可塑剤除去工程を実施した。
さらにポリ塩化ビニルコンパウンド溶液にＭＥＫ５０ｇを添加して溶媒添加工程を実施した後に、質量で１０％濃度の塩酸水溶液３０ｇを添加して撹拌した。そして、分液ロートにて静置して相分離させたものから塩酸水溶液相のみを分離除去する鉛安定剤除去工程を実施した。
次に、残ったポリ塩化ビニルコンパウンド溶液にスチームを吹き込みトルエンとＭＥＫとを蒸発させて除去しながら吹き込んだスチームの凝縮水中にポリ塩化ビニルコンパウンド成分を析出沈澱させて再生ポリ塩化ビニルコンパウンドを製造した。
このとき、可塑剤除去工程後のポリ塩化ビニルコンパウンド溶液に含まれるＤＯＰの濃度をガスクロマトグラフ（島津製作所社製、型式：ＧＣ−２０１４）で分析測定した。結果を表１に示す。
また、再生ポリ塩化ビニルコンパウンド中の鉛濃度を酸分解法により測定した。酸分解法とは、詳しくは、再生ポリ塩化ビニルコンパウンド中に硫酸と過酸化水素水を加え、マイクロ波により有機物を完全に分解した分解残渣中の鉛を高周波誘導結合プラズマ放電（ＩＣＰ）分析装置で分析した。結果を表１に示す。 Example 1
10 g of a wire covering material made of a polyvinyl chloride compound containing 28% by mass of dioctyl phthalate (hereinafter also referred to as “DOP”) and 1% of a lead stabilizer (a mixture of lead stearate and tribasic lead sulfate) is added to 80 g of toluene. A polyvinyl chloride compound solution was prepared by carrying out a dissolution process in which 100 g of a mixed organic solvent of 20 g of methyl ethyl ketone (hereinafter also referred to as “MEK”) was dissolved.
Next, 50 g of dimethyl sulfoxide (hereinafter also referred to as “DMSO”) was added and stirred, and transferred to a separatory funnel and allowed to stand, and the polyvinyl chloride compound solution and DMSO were phase-separated to separate and remove only the DMSO phase. A plasticizer removing step was performed.
Further, 50 g of MEK was added to the polyvinyl chloride compound solution to carry out the solvent addition step, and then 30 g of a 10% strength hydrochloric acid aqueous solution was added and stirred. And the lead stabilizer removal process which isolate | separates and removes only the hydrochloric acid aqueous solution phase from what was left still by the separating funnel and was made to phase-separate was implemented.
Next, steam was blown into the remaining polyvinyl chloride compound solution to evaporate and remove toluene and MEK, and the polyvinyl chloride compound component was precipitated and precipitated in the condensed water of the blown steam to produce a regenerated polyvinyl chloride compound. .
At this time, the concentration of DOP contained in the polyvinyl chloride compound solution after the plasticizer removing step was analyzed and measured by a gas chromatograph (manufactured by Shimadzu Corporation, model: GC-2014). The results are shown in Table 1.
Further, the lead concentration in the recycled polyvinyl chloride compound was measured by an acid decomposition method. Specifically, the acid decomposition method is a high-frequency inductively coupled plasma discharge (ICP) analyzer for lead in decomposition residues in which sulfuric acid and hydrogen peroxide are added to recycled polyvinyl chloride compound and organic substances are completely decomposed by microwaves. Analyzed with The results are shown in Table 1.

（実施例２）
可塑剤除去工程に用いたヘキサンジメチルスルホキシドの添加量を１０ｇとしたこと以外は、実施例１と同様な方法により再生ポリ塩化ビニルコンパウンドを製造した。
可塑剤除去工程後のポリ塩化ビニルコンパウンド溶液に含まれるＤＯＰの濃度測定ならびに再生ポリ塩化ビニルコンパウンド中の鉛濃度の測定結果を表１に示す。 (Example 2)
A recycled polyvinyl chloride compound was produced in the same manner as in Example 1 except that the amount of hexanedimethylsulfoxide used in the plasticizer removing step was 10 g.
Table 1 shows the measurement results of the concentration of DOP contained in the polyvinyl chloride compound solution after the plasticizer removing step and the measurement of the lead concentration in the recycled polyvinyl chloride compound.

（実施例３）
溶解工程において、トルエンに代えてキシレンを用い、ＭＥＫに代えてテトラヒドロフラン（以下「ＴＨＦ」ともいう）を用い、キシレンを４０ｇとＴＨＦを１０ｇを混合して、混合系有機溶媒の量を５０ｇとしたこと以外は、実施例１と同様な方法により再生ポリ塩化ビニルコンパウンドを製造した。
可塑剤除去工程後のポリ塩化ビニルコンパウンド溶液に含まれるＤＯＰの濃度測定ならびに再生ポリ塩化ビニルコンパウンド中の鉛濃度の測定結果を表１に示す。 (Example 3)
In the dissolving step, xylene was used instead of toluene, tetrahydrofuran (hereinafter also referred to as “THF”) was used instead of MEK, 40 g of xylene and 10 g of THF were mixed, and the amount of the mixed organic solvent was 50 g. A recycled polyvinyl chloride compound was produced in the same manner as in Example 1 except that.
Table 1 shows the measurement results of the concentration of DOP contained in the polyvinyl chloride compound solution after the plasticizer removing step and the measurement of the lead concentration in the recycled polyvinyl chloride compound.

（実施例４）
溶解工程において、可塑剤除去工程に用いたジメチルスルホキシドの量を１０ｇとしたこと以外は、実施例１と同様な方法により再生ポリ塩化ビニルコンパウンドを製造した。
可塑剤除去工程後のポリ塩化ビニルコンパウンド溶液に含まれるＤＯＰの濃度測定ならびに再生ポリ塩化ビニルコンパウンド中の鉛濃度の測定結果を表１に示す。 Example 4
In the dissolving step, a regenerated polyvinyl chloride compound was produced in the same manner as in Example 1 except that the amount of dimethyl sulfoxide used in the plasticizer removing step was 10 g.
Table 1 shows the measurement results of the concentration of DOP contained in the polyvinyl chloride compound solution after the plasticizer removing step and the measurement of the lead concentration in the recycled polyvinyl chloride compound.

（実施例５）
鉛安定剤除去工程において、塩酸に代えて１０％濃度の硫酸水溶液を用いた以外は実施例１と同様な方法により再生ポリ塩化ビニルコンパウンドを製造した。
可塑剤除去工程後のポリ塩化ビニルコンパウンド溶液に含まれるＤＯＰの濃度測定ならびに再生ポリ塩化ビニルコンパウンド中の鉛濃度の測定結果を表１に示す。 (Example 5)
A recycled polyvinyl chloride compound was produced in the same manner as in Example 1 except that, in the lead stabilizer removal step, a 10% strength aqueous sulfuric acid solution was used instead of hydrochloric acid.
Table 1 shows the measurement results of the concentration of DOP contained in the polyvinyl chloride compound solution after the plasticizer removing step and the measurement of the lead concentration in the recycled polyvinyl chloride compound.

（比較例１）
可塑剤除去工程を行わなかったこと以外は実施例１と同様に再生ポリ塩化ビニルコンパウンドを製造した。なお、この比較例１では、ポリ塩化ビニルコンパウンド溶液に１０％濃度の塩酸水溶液３０ｇを添加して撹拌したところ、ポリ塩化ビニルコンパウンドの一部が析出し、しかも、相分離状態が形成されなかったため、酸性水溶液を除去することなくスチームを吹き込みトルエンとＭＥＫとを蒸発させて除去しながら吹き込んだスチームの凝集水中にポリ塩化ビニルコンパウンド成分を析出沈殿させ、この凝集水とともに酸性水溶液を除去することにより再生ポリ塩化ビニルコンパウンドを製造した。
再生ポリ塩化ビニルコンパウンド中の鉛濃度の測定結果を表１に示す。 (Comparative Example 1)
A recycled polyvinyl chloride compound was produced in the same manner as in Example 1 except that the plasticizer removing step was not performed. In Comparative Example 1, when 30 g of 10% strength hydrochloric acid aqueous solution was added to the polyvinyl chloride compound solution and stirred, a part of the polyvinyl chloride compound was precipitated, and the phase separation state was not formed. By blowing steam without removing the acidic aqueous solution and evaporating and removing toluene and MEK, the polyvinyl chloride compound component is precipitated and precipitated in the agglomerated water of the blown steam, and the acidic aqueous solution is removed together with the agglomerated water. A recycled polyvinyl chloride compound was produced.
Table 1 shows the measurement results of the lead concentration in the recycled polyvinyl chloride compound.

（熱安定性の比較）
実施例１〜５及び比較例１により得られた再生ポリ塩化ビニルコンパウンド１００ｇに熱安定剤（旭電化工業社「アデカスタブ ＡＣ−２７８」）２ｇと安定補助剤（旭電化工業社「アデカサイザー Ｏ−１３０Ｐ」）２ｇを添加し、１６０℃で混練した。
このとき、比較例１の再生ポリ塩化ビニルコンパウンドは、混練の途中でＤＯＰの分解生成物であるフタル酸やオクタノールの発生が確認された。実施例１〜５の再生ポリ塩化ビニルコンパウンドの混練においては発生されなかった。
さらに混練した後、冷却し、熱安定性評価試料とした。この熱安定性評価試料を下記に示すＤＨＣ法により評価した。
（ＤＨＣ法：２００℃に加熱された直径２４ｍｍ、高さ１５０ｍｍのガラス管容器中に熱安定性評価試料０．５ｇを入れて、熱安定性評価試料を２００℃に加熱しつつ、ガラス管容器内を７Ｌ／時間の流量の窒素ガスでパージし、このガラス管容器から排出されるパージガスを純水中でバブリングさせて、熱安定性評価試料をガラス管容器中に入れてからこの純水の導電度が５０μＳ／ｃｍに到達するまでの時間を測定した。
なお、この純水は、６０ｍＬの量を直径４５ｍｍ、高さ９１ｍｍのプラスチック管容器に収容させて用いた。）
結果を表１に示す。 (Comparison of thermal stability)
100 g of the regenerated polyvinyl chloride compound obtained in Examples 1 to 5 and Comparative Example 1, 2 g of a heat stabilizer (Asahi Denka Kogyo "Adekastab AC-278") and a stabilizer (Asahi Denka Kogyo "Adekasizer O-") 130P ") 2g was added and kneaded at 160 ° C.
At this time, the recycled polyvinyl chloride compound of Comparative Example 1 was confirmed to generate phthalic acid and octanol, which are decomposition products of DOP, during kneading. It was not generated in the kneading of the recycled polyvinyl chloride compounds of Examples 1-5.
Furthermore, after kneading, it was cooled and used as a thermal stability evaluation sample. This thermal stability evaluation sample was evaluated by the following DHC method.
(DHC method: Putting 0.5 g of a thermal stability evaluation sample into a glass tube container having a diameter of 24 mm and a height of 150 mm heated to 200 ° C., and heating the heat stability evaluation sample to 200 ° C. The inside is purged with nitrogen gas at a flow rate of 7 L / hour, the purge gas discharged from the glass tube container is bubbled in pure water, and the thermal stability evaluation sample is placed in the glass tube container, and then the pure water is added. The time until the conductivity reached 50 μS / cm was measured.
The pure water was used in an amount of 60 mL accommodated in a plastic tube container having a diameter of 45 mm and a height of 91 mm. )
The results are shown in Table 1.

Figure 0004473225
Figure 0004473225

この表からも、エステル化合物を含む可塑剤、鉛安定剤およびポリ塩化ビニルレジンが含有されてなるポリ塩化ビニルコンパウンドを、前記鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な溶媒に溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程と、該溶解工程で作製された前記ポリ塩化ビニルコンパウンド溶液と鉛安定剤を溶解可能な酸性水溶液とを混合してポリ塩化ビニルコンパウンド溶液と酸性水溶液とを相分離させることによりポリ塩化ビニルコンパウンド溶液から鉛安定剤を除去する鉛安定剤除去工程とを実施した後に、該鉛安定剤除去工程で鉛安定剤が除去されたポリ塩化ビニルコンパウンド溶液からポリ塩化ビニルコンパウンドを再生させる再生ポリ塩化ビニルコンパウンド製造方法において、前記鉛安定剤除去工程前に前記可塑剤を除去する可塑剤除去工程をさらに実施するにより、熱安定性の低下を抑制しつつ十分低鉛化された再生ポリ塩化ビニルコンパウンドを提供させ得ることがわかる。   Also from this table, a solvent capable of forming a phase separation state between a plasticizer containing an ester compound, a lead stabilizer and a polyvinyl chloride compound containing a polyvinyl chloride resin and an acidic aqueous solution capable of dissolving the lead stabilizer. A polyvinyl chloride compound solution prepared by mixing a polyvinyl chloride compound solution prepared in the dissolution step and an acidic aqueous solution capable of dissolving a lead stabilizer. A lead stabilizer removal step of removing the lead stabilizer from the polyvinyl chloride compound solution by phase separation from the acidic aqueous solution, and then the polyvinyl chloride compound from which the lead stabilizer has been removed in the lead stabilizer removal step In a recycled polyvinyl chloride compound production method for regenerating polyvinyl chloride compound from a solution, It can be seen that by further carrying out the plasticizer removal step of removing the plasticizer before the lead stabilizer removal step, it is possible to provide a recycled polyvinyl chloride compound that is sufficiently lead-free while suppressing a decrease in thermal stability. .

本実施形態に係る再生ポリ塩化ビニルコンパウンド製造方法を説明するためのブロック図。The block diagram for demonstrating the reproduction | regeneration polyvinyl chloride compound manufacturing method which concerns on this embodiment.

Claims (6)

エステル化合物を含む可塑剤、鉛安定剤およびポリ塩化ビニルレジンが含有されてなるポリ塩化ビニルコンパウンドを、前記鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な溶媒に溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程と、該溶解工程で作製された前記ポリ塩化ビニルコンパウンド溶液と鉛安定剤を溶解可能な酸性水溶液とを混合してポリ塩化ビニルコンパウンド溶液と酸性水溶液とを相分離させることによりポリ塩化ビニルコンパウンド溶液から鉛安定剤を除去する鉛安定剤除去工程とを実施した後に、該鉛安定剤除去工程で鉛安定剤が除去されたポリ塩化ビニルコンパウンド溶液からポリ塩化ビニルコンパウンドを再生させる再生ポリ塩化ビニルコンパウンド製造方法であって、
前記鉛安定剤除去工程前に前記可塑剤を除去する可塑剤除去工程をさらに実施することを特徴とする再生ポリ塩化ビニルコンパウンド製造方法。 A polyvinyl chloride compound containing a plasticizer containing an ester compound, a lead stabilizer and a polyvinyl chloride resin is dissolved in a solvent capable of forming a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer. Mixing the polyvinyl chloride compound solution and the acidic aqueous solution by mixing the dissolution step of preparing the vinyl chloride compound solution, and the polyvinyl chloride compound solution prepared in the dissolution step and the acidic aqueous solution capable of dissolving the lead stabilizer. And a lead stabilizer removing step for removing the lead stabilizer from the polyvinyl chloride compound solution by separating the polyvinyl chloride from the polyvinyl chloride compound solution from which the lead stabilizer has been removed in the lead stabilizer removing step. A method for producing a regenerated polyvinyl chloride compound for regenerating a compound, comprising:
A method for producing a reclaimed polyvinyl chloride compound, further comprising a plasticizer removing step of removing the plasticizer before the lead stabilizer removing step. 前記溶解工程、前記可塑剤除去工程および前記鉛安定剤除去工程として、下記ａ〜ｃに示す工程を実施する請求項１に記載の再生ポリ塩化ビニルコンパウンド製造方法。
ａ．鉛安定剤を溶解可能な酸性水溶液との相分離状態が形成可能で且つ前記ポリ塩化ビニルコンパウンドを溶解可能な第一溶媒にポリ塩化ビニルコンパウンドを溶解させてポリ塩化ビニルコンパウンド溶液を作製する溶解工程。
ｂ．前記ポリ塩化ビニルコンパウンド溶液と相分離状態を形成可能で、しかも、前記第一溶媒よりも前記可塑剤の溶解性が高く、前記第一溶媒よりも前記塩化ビニルレジンの溶解性が低い第二溶媒と、前記ポリ塩化ビニルコンパウンド溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記二溶媒とを相分離させることにより前記ポリ塩化ビニルコンパウンド溶液から前記可塑剤を除去する可塑剤除去工程。
ｃ．前記可塑剤が除去された前記ポリ塩化ビニルコンパウンド溶液と、前記鉛安定剤を溶解可能な酸性水溶液とを混合して、ポリ塩化ビニルコンパウンド溶液と前記酸性水溶液とを相分離させることにより前記鉛安定剤を除去する鉛安定剤除去工程。 The recycled polyvinyl chloride compound manufacturing method according to claim 1, wherein the steps shown in the following ac are performed as the dissolving step, the plasticizer removing step, and the lead stabilizer removing step.
a. Dissolution step of producing a polyvinyl chloride compound solution by dissolving the polyvinyl chloride compound in a first solvent capable of forming a phase separation state with an acidic aqueous solution capable of dissolving the lead stabilizer and capable of dissolving the polyvinyl chloride compound. .
b. A second solvent capable of forming a phase-separated state with the polyvinyl chloride compound solution, and having a higher solubility of the plasticizer than the first solvent and a lower solubility of the vinyl chloride resin than the first solvent; A plasticizer removing step of removing the plasticizer from the polyvinyl chloride compound solution by mixing the polyvinyl chloride compound solution and phase separating the polyvinyl chloride compound solution and the two solvents.
c. By mixing the polyvinyl chloride compound solution from which the plasticizer has been removed and an acidic aqueous solution capable of dissolving the lead stabilizer, the polyvinyl chloride compound solution and the acidic aqueous solution are phase-separated to thereby stabilize the lead. Lead stabilizer removal process to remove the agent. 前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒よりも塩化ビニルレジンの溶解性が高く且つ鉛安定剤を溶解可能な酸性水溶液との相分離状態を形成可能な第三溶媒を、前記可塑剤除去工程後、前記鉛安定剤除去工程前のポリ塩化ビニルコンパウンド溶液に添加する溶媒添加工程をさらに実施する請求項１または２に記載の再生ポリ塩化ビニルコンパウンド製造方法。   A third solvent capable of forming a phase separation state with an acidic aqueous solution having a higher solubility of vinyl chloride resin than the solvent used for dissolving the polyvinyl chloride compound in the dissolving step and capable of dissolving the lead stabilizer; The method for producing a regenerated polyvinyl chloride compound according to claim 1 or 2, further comprising a solvent addition step of adding to the polyvinyl chloride compound solution before the lead stabilizer removal step after the removal step. 前記溶解工程でポリ塩化ビニルコンパウンドの溶解に用いられる溶媒には、水系有機溶媒と非水系有機溶媒とが混在する混合系有機溶媒が用いられる請求項１乃至３のいずれか１項に記載の再生ポリ塩化ビニルコンパウンド製造方法。   The regeneration according to any one of claims 1 to 3, wherein a mixed organic solvent in which an aqueous organic solvent and a non-aqueous organic solvent are mixed is used as the solvent used for dissolving the polyvinyl chloride compound in the dissolving step. Polyvinyl chloride compound manufacturing method. 前記混合系有機溶媒には、水系有機溶媒と非水系有機溶媒が質量比で（水系有機溶媒／非水系有機溶媒）＝５／９５〜５０／５０となる割合で混在している請求項４に記載の再生ポリ塩化ビニルコンパウンド製造方法。   The mixed organic solvent includes a mixture of an aqueous organic solvent and a non-aqueous organic solvent in a mass ratio of (aqueous organic solvent / non-aqueous organic solvent) = 5/95 to 50/50. The manufacturing method of the reproduction | regeneration polyvinyl chloride compound of description. 前記水系有機溶媒がメチルエチルケトンであり、且つ、前記非水系有機溶媒がトルエンである請求項４または５に記載の再生ポリ塩化ビニルコンパウンド製造方法。   The method for producing a reclaimed polyvinyl chloride compound according to claim 4 or 5, wherein the aqueous organic solvent is methyl ethyl ketone and the non-aqueous organic solvent is toluene.
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