JPH06157878A - Copolyestr composition - Google Patents
Copolyestr compositionInfo
- Publication number
- JPH06157878A JPH06157878A JP31524892A JP31524892A JPH06157878A JP H06157878 A JPH06157878 A JP H06157878A JP 31524892 A JP31524892 A JP 31524892A JP 31524892 A JP31524892 A JP 31524892A JP H06157878 A JPH06157878 A JP H06157878A
- Authority
- JP
- Japan
- Prior art keywords
- units
- copolymer
- composition
- present
- boron nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は３−ヒドロキシブチレー
ト単位（以下３ＨＢ単位と記す）と４−ヒドロキシブチ
レート単位（以下４ＨＢ単位と記す）からなるポリエス
テル共重合体組成物に関する。詳しくは成形性の改善さ
れた生分解性ポリエステル共重合体組成物に関する。TECHNICAL FIELD The present invention relates to a polyester copolymer composition comprising 3-hydroxybutyrate units (hereinafter referred to as 3HB units) and 4-hydroxybutyrate units (hereinafter referred to as 4HB units). Specifically, it relates to a biodegradable polyester copolymer composition having improved moldability.
【０００２】[0002]
【従来の技術】ポリ−３−ヒドロキシブチレート（以下
ＰＨＢと記す）は、エネルギー貯蔵物質として数多くの
微生物の菌体内に蓄積され、優れた生物分解性と生体適
合性を示す熱可塑性高分子であることから、環境を保全
するクリーンプラスチックとして注目され、手術糸や骨
折固定用材等の医用材料および医薬や農薬を徐々に放出
する徐放性システム等の多方面への応用が長年にわたり
期待されてきた。特に近年、合成プラスチックが環境汚
染や資源循環の観点から深刻な社会問題となるに到り、
ＰＨＢおよびその共重合体は石油に依存しないバイオポ
リマーとして注目されている。2. Description of the Related Art Poly-3-hydroxybutyrate (hereinafter referred to as PHB) is a thermoplastic polymer that accumulates in the cells of many microorganisms as an energy storage substance and exhibits excellent biodegradability and biocompatibility. Therefore, it has attracted attention as a clean plastic that preserves the environment, and it has been expected for many years to be applied to various fields such as medical materials such as surgical threads and materials for fixing bone fractures, and sustained-release systems that gradually release drugs and pesticides. It was Particularly in recent years, synthetic plastics have become a serious social problem from the viewpoint of environmental pollution and resource recycling,
PHB and its copolymers are attracting attention as petroleum-independent biopolymers.
【０００３】しかしながら、ＰＨＢは耐衝撃性に劣ると
いう物性上の問題があった。近時、３ＨＢ単位および３
−ヒドロキシバリレート単位（以下３ＨＶ単位と記す）
を含有する共重合体およびその製造法について、研究開
発がなされ、たとえば特開昭５７−１５０３９３号、特
開昭５９−２２０１９２号に記載されている。またこれ
らの共重合体の結晶化速度を増加させるためにリン酸化
合物を配合させる方法も提案されており、窒化ホウ素も
用いられている（特開平３−２４１５１）。しかしなが
ら、３ＨＶ単位含有率の高い共重合体は耐熱性に劣って
いた。すなわち、共重合体の３ＨＶ単位が０〜３３モル
％まで増大するとこの増大に伴って融解温度（Ｔｍ）が
１８５℃から８５℃まで急激に低下することが知られて
いた（Ｔ．Ｌ．Ｂｌｕｈｍ ｅｔ ａｌ Ｍａｃｒｏｍ
ｏｌｅｃｕｌｅｓ，１９，２８７１（１９８６））。However, PHB has a problem in physical properties that it is inferior in impact resistance. Recently, 3HB units and 3
-Hydroxyvalerate unit (hereinafter referred to as 3HV unit)
Research and development have been carried out on copolymers containing ## STR1 ## and methods for producing the same, and are described, for example, in JP-A-57-150393 and JP-A-59-220192. Further, a method of incorporating a phosphoric acid compound in order to increase the crystallization rate of these copolymers has also been proposed, and boron nitride is also used (Japanese Patent Laid-Open No. 3-24151). However, the copolymer having a high 3HV unit content was inferior in heat resistance. That is, it was known that when the 3HV unit of the copolymer was increased to 0 to 33 mol%, the melting temperature (Tm) was drastically decreased from 185 ° C. to 85 ° C. with the increase (TL Bluhm. et al Macrom
olecules, 19, 2871 (1986)).
【０００４】一方、３ＨＢ単位および４ＨＢ単位を含有
する共重合体およびその製造法についても、研究開発が
なされ、たとえば特開平１−４８８２１，１−２２２７
８８，１−３０４８９１，２−２７９９２に記載されて
いる。かかる共重合体は４ＨＢ単位の含有率が高い場合
に高い融点を有し、耐衝撃性が改良されることから工業
的な価値が高い。On the other hand, research and development have also been carried out on copolymers containing 3HB units and 4HB units and methods for producing the same, for example, Japanese Patent Laid-Open No. 48821, 1-22227.
88, 1-304891, 279292. Such a copolymer has a high melting point when the content of 4HB units is high, and the impact resistance is improved, so that it has a high industrial value.
【０００５】[0005]
【発明が解決しようとする課題】しかし上記３ＨＢ単位
および４ＨＢ単位を含有する共重合体の結晶化速度は、
その低い核形成密度のため非常に遅い。この低い結晶化
速度のため成形性に問題があった。例えば一般的な成形
方法である射出成形等に利用するためには、離型性の向
上、成形サイクル時間の短縮の目的のために結晶化速度
の増大が望まれている。However, the crystallization rate of the above copolymer containing 3HB units and 4HB units is
Very slow due to its low nucleation density. Due to this low crystallization rate, there was a problem in moldability. For example, in order to use it for injection molding, which is a general molding method, it is desired to increase the crystallization rate for the purpose of improving mold releasability and shortening molding cycle time.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、３ＨＢ単
位および４ＨＢ単位を含有する共重合体の結晶化速度の
増大方法について鋭意検討した結果、特定の３ＨＢ単位
および４ＨＢ単位を含有する共重合体に特定粒径の窒化
ホウ素を特定量添加することにより核形成速度が著しく
向上できることを見出し本発明に到達した。DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest studies on a method of increasing the crystallization rate of a copolymer containing 3HB units and 4HB units, and as a result, have found that copolymers containing specific 3HB units and 4HB units The inventors have found that the nucleation rate can be remarkably improved by adding a specific amount of boron nitride having a specific particle size to a polymer, and have reached the present invention.
【０００７】即ち本発明の要旨は、３−ヒドロキシブチ
レート単位９７〜８５モル％および４−ヒドロキシブチ
レート単位３〜１５モル％からなるポリエステル共重合
体９９．５〜９７ｗｔ％と、粒径５〜５０μｍの窒化ホ
ウ素粒子０．５〜３ｗｔ％とからなることを特徴とする
ポリエステル共重合体組成物に存する。以下、本発明を
詳細に説明する。That is, the gist of the present invention is 99.5 to 97 wt% of a polyester copolymer consisting of 97 to 85 mol% of 3-hydroxybutyrate units and 3 to 15 mol% of 4-hydroxybutyrate units, and a particle size of 5 ˜50 μm boron nitride particles 0.5 to 3 wt%. Hereinafter, the present invention will be described in detail.
【０００８】本発明において、使用されるポリエステル
共重合体に含有される３ＨＢ単位および４ＨＢ単位は各
々次式で表される。In the present invention, the 3HB unit and the 4HB unit contained in the polyester copolymer used are each represented by the following formula.
【０００９】[0009]
【化１】 ３ＨＢ成分 ； −ＯＣＨ（ＣＨ3 ）ＣＨ2 ＣＯ− ４ＨＢ成分 ； −ＯＣＨ2 ＣＨ2 ＣＨ2 ＣＯ−## STR1 ## 3HB component; -OCH (CH 3) CH 2 CO- 4HB component; -OCH 2 CH 2 CH 2 CO-
【００１０】本発明のポリエステル共重合体は、このよ
うな３ＨＢ単位９７〜８５モル％および４ＨＢ単位３〜
１５モル％からなる。３モル％以下では共重合体の伸び
が小さく、生分解性も低下する。また１５モル％以上で
はＴｃが低くまたピーク面積も小さくなり、核剤添加の
効果が小さくなるため好ましくない。The polyester copolymer of the present invention contains 97 to 85 mol% of such 3HB units and 3 to 4HB units.
It consists of 15 mol%. When it is 3 mol% or less, the elongation of the copolymer is small and the biodegradability is also lowered. Further, if it is 15 mol% or more, Tc is low and the peak area is also small, and the effect of the addition of the nucleating agent becomes small, which is not preferable.
【００１１】本発明のポリエステル共重合体の製造方法
については特に限定されないが、例えばアルカリゲネス
属を使用する例としては、特開平１−４８８２１、同１
−２２２７８８、同１−３０４８９１及び同２−２７９
９２に記載されている方法等があり、その他の微生物を
使用する方法や、合成による製造方法等も利用すること
ができる。共重合体の３ＨＢ単位および４ＨＢ単位の比
を制御する方法は特に限定されないが、上記公知文献に
記載の方法によっても行うことができ、例えば微生物を
使用する方法においては炭素源の選定により容易に行う
ことができる。一例としては１，４−ブタンジオール、
γ−ブチロラクトン等を炭素源に共存させること等が挙
げられる。また該共重合体の分子量は特に限定されるも
のではないが、機械的物性が良いものが好ましい。その
ため３０℃クロロホルム中で測定した〔η〕が０．４ｄ
ｌ／ｇ以上であることが望ましい。The method for producing the polyester copolymer of the present invention is not particularly limited. For example, as an example of using Alcaligenes, Japanese Patent Laid-Open Nos.
-222788, 1-304891 and 2-279.
92, etc., and methods using other microorganisms, synthetic production methods and the like can also be used. The method of controlling the ratio of 3HB units and 4HB units of the copolymer is not particularly limited, but it can be carried out by the methods described in the above-mentioned known documents. For example, in the method using a microorganism, it is easy to select a carbon source. It can be carried out. As an example, 1,4-butanediol,
The coexistence of γ-butyrolactone and the like with a carbon source can be mentioned. The molecular weight of the copolymer is not particularly limited, but those having good mechanical properties are preferable. Therefore, [η] measured in chloroform at 30 ° C is 0.4d.
It is preferably 1 / g or more.
【００１２】上記共重合体の融点んは４ＨＢ単位の含有
量によって変化するが１５０〜１７５℃の範囲内であ
る。本発明における窒化ホウ素粒子は特に限定されない
が、粒径が５〜５０μｍであることが必要である。粒径
が５μｍより小さい場合は結晶化速度の向上効果が不十
分であり、また５０μｍより大きい場合には、共重合体
内での粒子の均一な分散が困難なため好ましくない。
尚、ここでいう粒径とは、主としてＪＩＳ篩法により求
められる平均粒径を意味する。The melting point of the above copolymer varies depending on the content of 4HB units, but is in the range of 150 to 175 ° C. The boron nitride particles in the present invention are not particularly limited, but it is necessary that the particle size is 5 to 50 μm. If the particle size is smaller than 5 μm, the effect of improving the crystallization rate is insufficient, and if it is larger than 50 μm, it is difficult to uniformly disperse the particles in the copolymer, which is not preferable.
The particle size as used herein means the average particle size mainly determined by the JIS sieving method.
【００１３】また、添加量は組成物全体の０．５〜３ｗ
ｔ％である。この範囲より少ない場合には結晶化速度の
向上効果が不十分であり、多すぎる場合は機械的物性
（引っ張り強度等）が低下し、好ましくない。本発明に
おける窒化ホウ素粒子の製造方法は特に限定されない
が、例えば尿素、ジシアンジアミド、塩化アンモニウム
等をほう酸に添加し、アンモニア中で高温で還元窒化す
る方法等が挙げられる。これらを公知の分級方法等によ
り、目的の粒径範囲の窒化ホウ素粒子を得ることができ
る。The amount of addition is 0.5 to 3 w of the whole composition.
t%. If it is less than this range, the effect of improving the crystallization rate is insufficient, and if it is too large, the mechanical properties (tensile strength, etc.) decrease, which is not preferable. The method for producing the boron nitride particles in the present invention is not particularly limited, and examples thereof include a method of adding urea, dicyandiamide, ammonium chloride or the like to boric acid, and reducing and nitriding in ammonia at a high temperature. Boron nitride particles having a desired particle size range can be obtained by a known classification method or the like.
【００１４】また本発明で使用する共重合体組成物の製
造方法は窒化ホウ素粒子を均一に分散させる方法であれ
ばよく、特に限定されないが、例えば混練機等を利用す
る混合方法、共重合体を溶媒を用いて溶液としてから窒
化ホウ素粒子を混合し、その後溶媒を除去する方法等が
挙げられる。溶媒としては、例えばハロゲン化炭化水
素、ジメチルホルムアミド等本発明の共重合体を溶解す
るものが使用可能である。The method for producing the copolymer composition used in the present invention is not particularly limited as long as it is a method for uniformly dispersing the boron nitride particles, but for example, a mixing method using a kneader or the like, a copolymer And the like, and then the boron nitride particles are mixed, and then the solvent is removed. As the solvent, for example, a solvent that dissolves the copolymer of the present invention such as a halogenated hydrocarbon or dimethylformamide can be used.
【００１５】更に本発明で使用する共重合体組成物には
混練機等を利用することで、所望に応じて充填剤、安定
剤、着色剤等の通常の高分子添加剤を添加することがで
きる。また、本発明の共重合体組成物の特性を失わない
範囲で他のポリアミド、ポリエステル等の重合体を配合
することもできる。本発明の共重合体組成物を利用した
成形方法は汎用の方法が可能であり、例えば射出成形、
押し出し成形、圧縮成形等が挙げられる。また、該成形
品は通常の成形品と同様の帯電防止、酸化防止や染色等
の表面処理等の後処理を行うことも可能である。Further, by using a kneader or the like, the copolymer composition used in the present invention can be added with usual polymer additives such as a filler, a stabilizer and a colorant as desired. it can. Further, other polymers such as polyamide and polyester may be blended within a range that does not lose the characteristics of the copolymer composition of the present invention. The molding method using the copolymer composition of the present invention can be a general-purpose method, for example, injection molding,
Examples include extrusion molding and compression molding. Further, the molded product can be subjected to post-treatments such as antistatic treatment, antioxidation treatment and surface treatment such as dyeing similar to the usual molded product.
【００１６】[0016]
【実施例】以下に本発明を実施例により更に具体的に説
明するが、本発明はその要旨を越えない限りこれら実施
例に限定されるものではない。 実施例１〜５および比較例１〜５ 表１に示すように、４ＨＢ成分含有共重合体のクロロホ
ルム溶液（共重合体濃度が１ｗｔ％）に各粒径の窒化ホ
ウ素粒子（商品名：ショウビーエヌＵＨＰ、昭和電工
製）を加え均一に分散させた。次に該溶液からクロロホ
ルムを室温で揮発させて各サンプルを得た。該サンプル
をＤＳＣ ＴＡ２０００（ＤＳＣ装置、ＤｕＰｏｎｔ社
製）で昇降温速度１６℃／分で測定した。その結果を表
−１に示す。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Examples 1 to 5 and Comparative Examples 1 to 5 As shown in Table 1, a 4HB component-containing copolymer in a chloroform solution (copolymer concentration: 1 wt%) was added to each particle of boron nitride particles (trade name: Shobee). N UHP, Showa Denko) was added and uniformly dispersed. Next, chloroform was volatilized from the solution at room temperature to obtain each sample. The sample was measured with a DSC TA2000 (DSC device, manufactured by DuPont) at a temperature rising / falling rate of 16 ° C./min. The results are shown in Table-1.
【００１７】[0017]
【表１】 表−１ ──────────────────────────────────── 組 成 窒化ホウ素 窒化ホウ素 Ｔｃ ピーク面積 [4HB含有率］ 粒 径* 添加量 （モル％） （μｍ） （ｗｔ％） （℃） （Ｊ／ｇ） ──────────────────────────────────── 実施例 １ ９．２ ７〜１０ ２．０ ８３ ４３ ２ ９．２ ３５〜４５ ２．０ ８０ ４４ ３ ９．２ ７〜１０ １．０ ７９ ５５ ４ ５．４ ７〜１０ ２．０ ９４ ６３ ５ １３．５ ７〜１０ ２．０ ８４ ５１ 比較例 １ ９．２ ── ０ ── ０ ２ ９．２ １〜２ ２．０ ５３ ４１ ３ ９．２ ７〜１０ ０．２ ５３ ４７ ４ １５．９ ７〜１０ ２．０ ５１ ２７ ５ １９．７ ７〜１０ ２．０ ４９ １９ ──────────────────────────────────── ＊ 粒径：正規分布のピークトップ（全粒子の５０％）
に対応する粒径。 ・１〜２μｍ ＝光透過法を用いて測定。 ・７〜１０μｍ ＝レーザー法を用いて測定。 ・３５〜４５μｍ＝ＪＩＳ篩法を用いて測定。[Table 1] Table-1 ──────────────────────────────────── Composition Boron Nitride Boron Nitride Tc Peak area [4HB content] Grain size * Addition amount (mol%) (μm) (wt%) (℃) (J / g) ──────────────────── ───────────────── EXAMPLE 1 9.2 7-10 2.0 83 43 2 9.2 35-45 2.0 80 80 44 3 9.2 7-10 1.0 79 55 4 5.4 7 to 10 2.0 2.0 94 63 5 13.5 7 to 10 2.0 84 51 Comparative Example 1 9.2 ── 0 ── 0 2 9.2 1-2 2. 0 53 41 3 9.2 7-10 10 0.2 53 47 4 15.9 7-10 10 2.0 51 27 5 19.7 7-10 2.0 2.0 49 19 ──────────── ─────────── ───────────── * particle size: (50% of the total particles) peak top of the normal distribution
Corresponding to the particle size. -1-2 μm = measured using a light transmission method. * 7-10 micrometers = measured using the laser method. 35-45 μm = measured using the JIS sieving method.
【００１８】比較例６ 添加剤として、窒化ホウ素粒子の代わりに同等の粒径を
もつタルク、アルミナ、炭酸カルシウム、マグネシア、
チタニア粒子、アルミニウム粉を用いた以外は実施例１
と同様に操作し、ＤＳＣで測定したが、全ての場合にＤ
ＳＣでピークが検出できなかった。Comparative Example 6 As an additive, talc, alumina, calcium carbonate, magnesia, which has the same particle size, instead of boron nitride particles,
Example 1 except that titania particles and aluminum powder were used
The same operation as above was carried out, and the measurement was carried out by DSC.
No peak could be detected by SC.
【００１９】[0019]
【発明の効果】本発明の共重合体組成物は耐衝撃性、耐
熱性等の物性に優れたものであり、しかも生物分解性と
生体適合性を有しているため、医用高分子、環境問題対
策用高分子として、例えば手術糸、魚網、釣り糸等のよ
うに、広範囲の分野における応用が可能な組成物であ
る。The copolymer composition of the present invention is excellent in physical properties such as impact resistance and heat resistance, and has biodegradability and biocompatibility. It is a composition that can be applied in a wide range of fields such as surgical thread, fishnet, fishing line, etc. as a polymer for solving problems.
【００２０】該組成物の結晶化速度が著しく向上したた
め、一般的な成形方法が可能となり、種々の成形品を成
形でき、また成形サイクル時間の改善により、成形コス
トが削減できる。Since the crystallization rate of the composition is remarkably improved, a general molding method is possible, various moldings can be molded, and molding cost can be reduced by improving the molding cycle time.
Claims (1)
５モル％および４−ヒドロキシブチレート単位３〜１５
モル％からなるポリエステル共重合体９９．５〜９７ｗ
ｔ％と、粒径５〜５０μｍの窒化ホウ素粒子０．５〜３
ｗｔ％とからなることを特徴とするポリエステル共重合
体組成物。1. 3-hydroxybutyrate units 97-8
5 mol% and 4-hydroxybutyrate units 3 to 15
Polyester copolymer consisting of mol% 99.5 to 97w
t%, and boron nitride particles having a particle size of 5 to 50 μm, 0.5 to 3
% of the polyester copolymer composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31524892A JPH06157878A (en) | 1992-11-25 | 1992-11-25 | Copolyestr composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31524892A JPH06157878A (en) | 1992-11-25 | 1992-11-25 | Copolyestr composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06157878A true JPH06157878A (en) | 1994-06-07 |
Family
ID=18063155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31524892A Pending JPH06157878A (en) | 1992-11-25 | 1992-11-25 | Copolyestr composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06157878A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023161A3 (en) * | 1997-10-31 | 1999-08-19 | Monsanto Co | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation |
| WO1999048962A1 (en) * | 1998-03-20 | 1999-09-30 | The Dow Chemical Company | Polymer composite comprising a hydroxy-functionalized polyether or polyester and an inorganic filler and method for preparing the same |
| JP2005179386A (en) * | 2003-12-16 | 2005-07-07 | Tosoh Corp | Molten-granulated matter of 3-hydroxy butyrate-based polymer and manufacturing method therefor |
| JP2006111747A (en) * | 2004-10-15 | 2006-04-27 | Sony Corp | Composite composition and molded product using the composite composition |
| US10519473B2 (en) | 2014-03-28 | 2019-12-31 | Kaneka Corporation | Microorganism having multiple genes encoding PHA synthase and method for producing PHA using same |
| US10865429B2 (en) | 2015-09-28 | 2020-12-15 | Kaneka Corporation | Microorganism having PHA synthase-coding genes and method for producing PHA using same |
| KR102419077B1 (en) * | 2022-01-03 | 2022-07-07 | 신영철 | Automotive electronics plastic composition and automotive electronics plastic manufactured therefrom |
-
1992
- 1992-11-25 JP JP31524892A patent/JPH06157878A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999023161A3 (en) * | 1997-10-31 | 1999-08-19 | Monsanto Co | Polymer blends containing polyhydroxyalkanoates and compositions with good retention of elongation |
| WO1999048962A1 (en) * | 1998-03-20 | 1999-09-30 | The Dow Chemical Company | Polymer composite comprising a hydroxy-functionalized polyether or polyester and an inorganic filler and method for preparing the same |
| AU746116B2 (en) * | 1998-03-20 | 2002-04-18 | Dow Chemical Company, The | Polymer composite comprising a hydroxy-functionalized polyether or polyester and an inorganic filler and method for preparing the same |
| JP2005179386A (en) * | 2003-12-16 | 2005-07-07 | Tosoh Corp | Molten-granulated matter of 3-hydroxy butyrate-based polymer and manufacturing method therefor |
| JP4635433B2 (en) * | 2003-12-16 | 2011-02-23 | 東ソー株式会社 | Melt granulated product of poly-3-hydroxybutyrate polymer and method for producing the same |
| JP2006111747A (en) * | 2004-10-15 | 2006-04-27 | Sony Corp | Composite composition and molded product using the composite composition |
| US10519473B2 (en) | 2014-03-28 | 2019-12-31 | Kaneka Corporation | Microorganism having multiple genes encoding PHA synthase and method for producing PHA using same |
| US11225676B2 (en) | 2014-03-28 | 2022-01-18 | Kaneka Corporation | Microorganism having multiple genes encoding PHA synthase and method for producing PHA using same |
| US10865429B2 (en) | 2015-09-28 | 2020-12-15 | Kaneka Corporation | Microorganism having PHA synthase-coding genes and method for producing PHA using same |
| KR102419077B1 (en) * | 2022-01-03 | 2022-07-07 | 신영철 | Automotive electronics plastic composition and automotive electronics plastic manufactured therefrom |
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