JPH05214184A - Polypropylene-based resin composition improved in processability - Google Patents
Polypropylene-based resin composition improved in processabilityInfo
- Publication number
- JPH05214184A JPH05214184A JP2255592A JP2255592A JPH05214184A JP H05214184 A JPH05214184 A JP H05214184A JP 2255592 A JP2255592 A JP 2255592A JP 2255592 A JP2255592 A JP 2255592A JP H05214184 A JPH05214184 A JP H05214184A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- polytetrafluoroethylene
- processability
- polypropylene resin
- weight
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリプロピレン樹脂に
ポリテトラフルオロエチレンを含有させることにより剛
性度を向上させると同時に、加工性を改良し、外観の優
れた良好な成形品を得ることを特徴とする熱可塑性組成
物に関するものである。さらに詳しくは射出成形におけ
る製品外観の向上、ブロー成形におけるパリソンのドロ
ーダウン防止、真空成形性の改良および発泡成形におけ
るセルの調整等の加工性の改良されたポリプロピレン樹
脂組成物に関するものである。BACKGROUND OF THE INVENTION The present invention is characterized in that a polypropylene resin containing polytetrafluoroethylene improves rigidity and, at the same time, improves processability and obtains a good molded product having an excellent appearance. The present invention relates to a thermoplastic composition. More specifically, the present invention relates to a polypropylene resin composition having improved product appearance in injection molding, prevention of drawdown of parison in blow molding, improved vacuum moldability, and improved processability such as cell adjustment in foam molding.
【０００２】[0002]
【従来の技術】ポリプロピレン樹脂は、非常に適用範囲
の広い樹脂で、射出成形、フィルム成形用として広く使
用されている。しかしＡＢＳ樹脂等に較べ剛性が劣って
おり、そのために用途が制約される事が多い。ポリプロ
ピレン樹脂の剛性改良に関しては既にいくつかの試みが
なされているがその殆どはアスベスト、タルク、ケイソ
ウ土、ガラス繊維等の無機質充填剤含有による改質であ
る。これら無機質充填剤を含有した場合にも確かに剛性
は大巾に向上するが一方それら無機質充填剤は吸湿性が
著しいため、成形前長時間乾燥を行っても、外観を悪化
させ、銀条が発生する等種々問題がある。2. Description of the Related Art Polypropylene resin has a very wide range of application and is widely used for injection molding and film molding. However, its rigidity is inferior to that of ABS resin and the like, which often limits its use. Some attempts have already been made to improve the rigidity of polypropylene resins, but most of them have been modified by the inclusion of inorganic fillers such as asbestos, talc, diatomaceous earth and glass fibers. Even when these inorganic fillers are contained, the rigidity is greatly improved, but since these inorganic fillers have remarkable hygroscopicity, even if they are dried for a long time before molding, the appearance is deteriorated and silver strips are formed. There are various problems such as occurrence.
【０００３】又ポリプロピレン樹脂は、結晶性ポリマー
で溶融点付近で急激に粘度が下がるため、無機質充填剤
を混入したものでも溶融加工時、溶融樹脂のダイスから
のドローダウンが大きく、特に押出成形時のサイジング
が非常に難しく、かつ金属との離形性が問題となってい
る。Polypropylene resin is a crystalline polymer, and its viscosity rapidly decreases in the vicinity of the melting point. Therefore, even when an inorganic filler is mixed, the melt resin has a large drawdown from the die during melt processing, especially during extrusion molding. Sizing is very difficult, and the releasability from metal is a problem.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、かかる現状
に鑑み、鋭意検討した結果、ポリプロピレン樹脂に特定
の分子量を有するポリテトラフルオロエチレンの特定量
を配合することにより、耐衝撃性、耐熱性の特性を低下
させることなく、剛性度を著しく向上させると同時に、
ドローダウン、ヒケ等を改良し、かつ、寸法性、表面状
態の優れた良好な成形品が得られることを見い出し本発
明を完成した。DISCLOSURE OF THE INVENTION The present invention has been intensively studied in view of the above situation, and as a result, by blending polypropylene resin with a specific amount of polytetrafluoroethylene having a specific molecular weight, impact resistance and heat resistance are improved. The rigidity is remarkably improved without deteriorating the characteristics of
The present invention has been completed by finding that a good molded product having improved drawdown, sink mark and the like and excellent dimensional properties and surface condition can be obtained.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、ポ
リプロピレン樹脂（Ａ）１００重量部に対して分子量５
０万〜２０００万のポリテトラフルオロエチレン（Ｂ）
を０．０１〜２０重量部含有させたことを特徴とする加
工性の改良されたポリプロピレン樹脂組成物を提供する
ものである。[Means for Solving the Problems] That is, the present invention has a molecular weight of 5 per 100 parts by weight of a polypropylene resin (A).
0 to 20 million polytetrafluoroethylene (B)
The present invention provides a polypropylene resin composition having an improved processability, which comprises 0.01 to 20 parts by weight.
【０００６】本発明において使用されるポリプロピレン
樹脂（Ａ）は、一般にポリプロピレンとして市販されて
いるものであり、プロピレンホモポリマーのみならずエ
チレン−プロピレンコポリマー及び若干の低密度又は高
密度ポリエチレンをブレンドしたポリプロピレンを含む
ものである。The polypropylene resin (A) used in the present invention is generally commercially available as polypropylene, and is a polypropylene obtained by blending not only propylene homopolymer but also ethylene-propylene copolymer and some low or high density polyethylene. Is included.
【０００７】本発明において使用されるポリテトラフル
オロエチレン（Ｂ）としては、分子量が５０万以上、２
０００万以下のものである。ポリテトラフルオロエチレ
ンの分子量が５０万未満の場合には、ポリプロピレンの
剛性度及び加工時の弾性が向上せず、加工性改良の効果
が得られない。また分子量が２０００万を超える場合に
は、成形が難しくなり加工性の改良が出来なくなる。The polytetrafluoroethylene (B) used in the present invention has a molecular weight of 500,000 or more, 2
It is less than 10 million. When the molecular weight of polytetrafluoroethylene is less than 500,000, the rigidity of polypropylene and the elasticity during processing are not improved, and the effect of improving the workability cannot be obtained. On the other hand, when the molecular weight exceeds 20 million, molding becomes difficult and the workability cannot be improved.
【０００８】なお、本発明において使用されるポリテト
ラフルオロエチレンの分子量は、ＡＳＴＭ Ｄ ４５９
１で下記式によって算出されたものである。The molecular weight of polytetrafluoroethylene used in the present invention is ASTM D 459.
It is calculated by the following formula in 1.
【０００９】ＬｏｇＭｗ＝２７．５３４５−１２．１４
０５Ｄ （式中、Ｍｗは重量平均分子量、Ｄは標準比重を示
す。）ポリテトラフルオロエチレンは、溶解度指数が
６．２とポリマーの中で最も低く、他のポリマーとは相
溶性がないにもかかわらず、上記分子量範囲のポリテト
ラフルオロエチレンをポリプロピレン樹脂に配合するこ
とにより、ポリプロピレン樹脂の加工性を著しく改良で
きる。LogMw = 27.5345-12.14
05D (In the formula, Mw is a weight average molecular weight and D is a standard specific gravity.) Polytetrafluoroethylene has a solubility index of 6.2, which is the lowest among the polymers, and is incompatible with other polymers. Nevertheless, the processability of the polypropylene resin can be significantly improved by blending the polytetrafluoroethylene having the above molecular weight range with the polypropylene resin.
【００１０】本発明において、ポリテトラフルオロエチ
レンの配合量としては、ポリプロピレン樹脂１００重量
部に対して０．０１〜２０重量部、好ましくは０．１〜
５．０重量部の範囲であり、特に好ましくは０．１〜
１．０重量部の範囲である。０．０１重量部未満では加
工性の改良が困難となり、２０重量部を超えると成形
性、成形品外観が低下する。In the present invention, the compounding amount of polytetrafluoroethylene is 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight based on 100 parts by weight of polypropylene resin.
It is in the range of 5.0 parts by weight, and particularly preferably 0.1 to
It is in the range of 1.0 part by weight. If it is less than 0.01 part by weight, it becomes difficult to improve the workability, and if it exceeds 20 parts by weight, the moldability and the appearance of the molded product deteriorate.
【００１１】ポリプロピレンにポリテトラフルオロエチ
レンを分散させるには、任意の方法が採用される。例え
ばポリテトラフルオロエチレンの分散液をポリプロピレ
ン粉粒体に撹拌下噴霧する方法、ポリテトラフルオロエ
チレンの分散液をポリプロピレン溶液に撹拌下添加し、
ニーダーの如き装置で溶媒を揮発させる方法、ベント付
き押出機でポリプロピレンをペレット化する際に、ポリ
テトラフルオロエチレンの分散液を定量供給し、ベント
部より揮発成分を除去する方法、ポリテトラフルオロエ
チレンの粉体とポリプロピレン樹脂粉粒体を、スーパー
ミキサーの如き強力な撹拌下混合する方法、ポリテトラ
フルオロエチレンの粉体をポリプロピレン溶液に添加混
合した後溶媒を揮発させる方法等をあげることができ
る。なお、ポリテトラフルオロエチレンを分散液として
使用する場合、０．５〜６０％程度にするのが好まし
い。Any method can be used to disperse polytetrafluoroethylene in polypropylene. For example, a method of spraying a dispersion of polytetrafluoroethylene to polypropylene powder particles with stirring, adding a dispersion of polytetrafluoroethylene to a polypropylene solution with stirring,
A method of volatilizing a solvent with a device such as a kneader, a method of removing a volatile component from a vent part by quantitatively supplying a dispersion liquid of polytetrafluoroethylene when polypropylene is pelletized by an extruder with a vent, polytetrafluoroethylene Examples of the method include a method of mixing the powder and the polypropylene resin powder and the like under a strong stirring such as with a super mixer, a method of adding and mixing the powder of polytetrafluoroethylene to the polypropylene solution and then volatilizing the solvent. When polytetrafluoroethylene is used as the dispersion liquid, it is preferably about 0.5 to 60%.
【００１２】このようにして得られるポリテトラフルオ
ロエチレンを含有するポリプロピレン樹脂粉粒体は、そ
のままペレットにした後ブロー成形に供することができ
る。また、一旦シート又はフィルムにした後、真空成形
に供することができる。The polypropylene resin powder containing polytetrafluoroethylene thus obtained can be directly pelletized and then subjected to blow molding. Further, it can be subjected to vacuum forming after being once made into a sheet or film.
【００１３】なお、本発明のポリプロピレン樹脂組成物
には、必要に応じて光および熱安定剤、可塑剤、滑剤、
耐衝撃強化剤、着色剤、発泡剤等の各種添加剤や無機充
填剤を配合することができる。The polypropylene resin composition of the present invention may contain, if necessary, a light and heat stabilizer, a plasticizer, a lubricant,
Various additives such as impact resistance enhancers, colorants, foaming agents and inorganic fillers can be added.
【００１４】[0014]
【発明の効果】本発明は、ポリプロピレン樹脂に特定分
子量のポリテトラフルオロエチレンを添加することによ
り、剛性及び加工時の弾性が向上し、従来製造し難かっ
たブロー成形物、特に大型のブロー成形物が容易に得ら
れ、かつ真空成形における深絞り性等が顕著に改良さ
れ、その用途拡大に有用である。INDUSTRIAL APPLICABILITY The present invention improves the rigidity and elasticity at the time of processing by adding polytetrafluoroethylene having a specific molecular weight to a polypropylene resin, and is a blow molded product which has been difficult to produce in the past, and particularly a large blow molded product. Is easily obtained, and the deep drawability in vacuum forming is remarkably improved, which is useful for expanding its applications.
【００１５】以下、実施例により本発明を具体的に説明
する。以下の記載において「部」とあるものは、すべて
「重量部」を意味する。The present invention will be specifically described below with reference to examples. In the following description, "part" means "part by weight".
【００１６】なお、各実施例、比較例での諸物性の測定
方法は、次の方法による。The methods of measuring various physical properties in the respective examples and comparative examples are as follows.
【００１７】（１）ＨＤＴ（熱変形温度℃） ＡＳＴＭ Ｄ ６４８に準じて測定した。１８．５ｋｇ
／ｃｍ2荷重。(1) HDT (heat distortion temperature ° C) Measured in accordance with ASTM D648. 18.5 kg
/ Cm 2 load.
【００１８】（２）ダイスウェル（％） 樹脂を押出機で押出した際に、バラス効果により膨らん
だ樹脂の膨らみ具合を下記の式により算出した。(2) Die swell (%) When the resin was extruded by an extruder, the degree of swelling of the resin swelled by the ballast effect was calculated by the following formula.
【００１９】ダイスウェル（％）＝［（（押出しサンプ
ルの径）−（ダイスのノズル径））／（ダイスのノズル
径）］×１００ ダイスウェル（％）の値が大きい程、溶融弾性にすぐ
れ、樹脂の加工性がよくなることを示す。Die swell (%) = [((extruded sample diameter)-(die nozzle diameter)) / (die nozzle diameter)] × 100 The larger the die swell (%) value, the better the melt elasticity. , Shows that the processability of the resin is improved.
【００２０】（３）ドローダウン（ｃｍ） 押出機のノズルからストランドを１５ｃｍ垂らしたとこ
ろで切断し、切断したサンプルの端を固定し、垂れ下が
りの状態で放置冷却し、サンプルの長さを測定する。(3) Drawdown (cm) The strand is hung down from the nozzle of the extruder for 15 cm and cut, the end of the cut sample is fixed, and the sample is left standing to cool in the hanging state, and the length of the sample is measured.
【００２１】サンプルの長さが短い程、ドローダウン防
止の効果にすぐれ、樹脂の加工性が良くなることを示
す。It is shown that the shorter the length of the sample, the better the effect of preventing drawdown and the better the processability of the resin.
【００２２】（４）曲げ剛性度（ｋｇ／ｃｍ2） ＡＳＴＭ Ｄ ７４７に準じて測定した。(4) Flexural rigidity (kg / cm 2 ) The flexural rigidity was measured according to ASTM D 747.
【００２３】（５）メルトストレングス（ｇ） メルトストレングスとは、フィラメント状の溶融ポリマ
ーを長さ方向に引張るときに生じる張力のことで降下式
フロテスターを使用し一定押出量の下（降下速度１０ｍ
ｍ／ｍｉｎ）に一定速度（１０ｍｍ／ｍｉｎ）で巻取り
張力を測定した。ノズルのＬ／Ｄは１０、測定温度は２
３０℃。(5) Melt Strength (g) Melt strength is the tension generated when the filamentous molten polymer is pulled in the lengthwise direction, using a falling type flotator at a constant extrusion rate (falling speed of 10 m).
m / min) and the winding tension was measured at a constant speed (10 mm / min). Nozzle L / D is 10, measured temperature is 2
30 ° C.
【００２４】（６）成形品の外観 射出成形品の外観を目視により判定した。(6) Appearance of molded product The appearance of the injection-molded product was visually determined.
【００２５】◎…すぐれる ○…良好 △…やや不
良 ×…不良 （７）発泡成形品の評価 発泡成形品における断面セル構造を目視より判定した。∘: Excellent ○: Good Δ: Slightly bad ×: Poor (7) Evaluation of foam-molded product The cross-sectional cell structure of the foam-molded product was visually determined.
【００２６】◎…微細で均一 ○…均一 △…やや
不均一 ×…不均一 実施例１〜１５、比較例５ ポリプロピレン樹脂（東燃石油化学（株）製品、Ｊ−２
０５）、エチレン−プロピレンゴム（住友化学工業
（株）製品、エスプレンＥ８０８）およびポリテトラフ
ルオロエチレン（旭硝子（株）製品、フルオンファイン
パウダー）を表１、表２に示す割合にてミキサーで混合
した後、二軸押出機（池貝鉄工（株）製、ＰＣＭ−３
０，Ｌ／Ｏ＝２８．５、スクリュー径＝３０ｍｍ）で、
シリンダー温度１９０〜２２０℃で押出しペレットに賦
形した。⊚: Fine and uniform ○: Uniform Δ: Slightly nonuniform ×: Nonuniform Examples 1 to 15 and Comparative Example 5 Polypropylene resin (product of Tonen Petrochemical Co., Ltd., J-2)
05), ethylene-propylene rubber (Sumitomo Chemical Co., Ltd. product, Esprene E808) and polytetrafluoroethylene (Asahi Glass Co., Ltd. product, Fluon Fine Powder) were mixed with a mixer at the ratios shown in Tables 1 and 2. After that, a twin-screw extruder (made by Ikegai Tekko KK, PCM-3
0, L / O = 28.5, screw diameter = 30 mm),
It was shaped into extruded pellets at a cylinder temperature of 190 to 220 ° C.
【００２７】このペレットを用いてブロー成形および射
出成形してその性能を評価した。また、この賦形ペレッ
トの各々１００重量部に対してアゾジカルボンアミド
（発泡剤）１．０部配合して、射出成形を行い、発泡成
形品を作製し、そのセルの状態を評価した。これらの結
果を表１、表２に示す。The pellets were blow-molded and injection-molded to evaluate their performance. Further, 1.0 part of azodicarbonamide (foaming agent) was added to 100 parts by weight of each of the shaped pellets, injection molding was carried out to prepare a foamed molded product, and the state of the cell was evaluated. The results are shown in Tables 1 and 2.
【００２８】 ブロー成形 成形機：田原昭栄機工（株）製、ＴＳ−５０２３Ｌ 成形温度（シリンダー温度）：１９０〜２２０℃ 金型温度：１２℃ 射出成形 成形機：（株）日本製鋼所製、Ｎ−１４０ＢII 成形温度（シリンダー温度）：１９０〜２２０℃ 金型温度：６０℃ なお、表１、表２中のＰＰはポリプロピレン樹脂、ＥＰ
Ｍはエチレン−プロピレンゴムを示す。Blow Molding Molding Machine: Tahara Shoei Kiko Co., Ltd., TS-5023L Molding Temperature (Cylinder Temperature): 190-220 ° C Mold Temperature: 12 ° C Injection Molding Molding Machine: Nippon Steel Works, Ltd., N -140BII Molding temperature (cylinder temperature): 190-220 ° C Mold temperature: 60 ° C PP in Tables 1 and 2 is polypropylene resin, EP
M represents ethylene-propylene rubber.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年３月６日[Submission date] March 6, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Name of item to be corrected] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００２３】（５）メルトストレングス（ｇ） メルトストレングスとは、フィラメント状の溶融ポリマ
ーを長さ方向に引張るときに生じる張力のことで降下式
フロテスターを使用し一定押出量の下（降下速度１０ｍ
ｍ／ｍｉｎ）に一定速度（１０ｍ／ｍｉｎ）で巻取り張
力を測定した。ノズルのＬ／Ｄは１０、測定温度は２３
０℃である。(5) Melt Strength (g) Melt strength is the tension generated when the filamentous molten polymer is pulled in the lengthwise direction, using a falling type flotator at a constant extrusion rate (falling speed of 10 m).
m / min) and the winding tension was measured at a constant speed (10 m / min). Nozzle L / D is 10, measured temperature is 23
It is 0 ° C.
Claims (1)
に対して分子量５０万〜２０００万のポリテトラフルオ
ロエチレン（Ｂ）を０．０１〜２０重量部含有すること
を特徴とする加工性の改良されたポリプロピレン樹脂組
成物。1. An improved processability characterized by containing 0.01 to 20 parts by weight of polytetrafluoroethylene (B) having a molecular weight of 500,000 to 20 million with respect to 100 parts by weight of a polypropylene resin (A). Polypropylene resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255592A JPH05214184A (en) | 1992-02-07 | 1992-02-07 | Polypropylene-based resin composition improved in processability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255592A JPH05214184A (en) | 1992-02-07 | 1992-02-07 | Polypropylene-based resin composition improved in processability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05214184A true JPH05214184A (en) | 1993-08-24 |
Family
ID=12086104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255592A Pending JPH05214184A (en) | 1992-02-07 | 1992-02-07 | Polypropylene-based resin composition improved in processability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05214184A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995033008A1 (en) * | 1994-05-31 | 1995-12-07 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Fluororesin-containing resin composition, process for producing the same, and thermo-forming sheet and foam made therefrom |
| WO1999010431A1 (en) * | 1997-08-22 | 1999-03-04 | Mitsubishi Rayon Co., Ltd. | Melt tension improver for polyolefin resins and process for producing the same |
| US6025441A (en) * | 1996-07-31 | 2000-02-15 | Mitsubishi Rayon Company Ltd. | Polytetrafluoroethylene-containing powder mixture, thermoplastic resin compositions including same and molded articles made therefrom |
| JP2008143951A (en) * | 2006-12-06 | 2008-06-26 | Inoac Corp | Low-gloss thermoplastic resin composition |
| WO2010116756A1 (en) | 2009-04-10 | 2010-10-14 | 三菱レイヨン株式会社 | Additive for thermoplastic resin and method for producing same, thermoplastic resin composition, and molded article |
| WO2012043754A1 (en) | 2010-09-30 | 2012-04-05 | ダイキン工業株式会社 | Dripping inhibitor and resin compound |
| US9006333B2 (en) | 2010-09-30 | 2015-04-14 | Daikin Industries, Ltd. | Method for manufacturing fine polytetrafluoroethylene powder |
| JP2015224266A (en) * | 2014-05-26 | 2015-12-14 | 三菱レイヨン株式会社 | Resin foam and method for producing the same |
| US9309335B2 (en) | 2010-09-30 | 2016-04-12 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
| JP2019023253A (en) * | 2017-07-24 | 2019-02-14 | 日本ポリプロ株式会社 | Sheet for thermoforming and thermoformed product |
-
1992
- 1992-02-07 JP JP2255592A patent/JPH05214184A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995033008A1 (en) * | 1994-05-31 | 1995-12-07 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Fluororesin-containing resin composition, process for producing the same, and thermo-forming sheet and foam made therefrom |
| US6025441A (en) * | 1996-07-31 | 2000-02-15 | Mitsubishi Rayon Company Ltd. | Polytetrafluoroethylene-containing powder mixture, thermoplastic resin compositions including same and molded articles made therefrom |
| WO1999010431A1 (en) * | 1997-08-22 | 1999-03-04 | Mitsubishi Rayon Co., Ltd. | Melt tension improver for polyolefin resins and process for producing the same |
| JP2008143951A (en) * | 2006-12-06 | 2008-06-26 | Inoac Corp | Low-gloss thermoplastic resin composition |
| US8765866B2 (en) | 2009-04-10 | 2014-07-01 | Mitsubishi Rayon Co., Ltd. | Additive for a thermoplastic resin, a process for producing the same, a thermoplastic resin composition, and a shaped article |
| WO2010116756A1 (en) | 2009-04-10 | 2010-10-14 | 三菱レイヨン株式会社 | Additive for thermoplastic resin and method for producing same, thermoplastic resin composition, and molded article |
| WO2012043754A1 (en) | 2010-09-30 | 2012-04-05 | ダイキン工業株式会社 | Dripping inhibitor and resin compound |
| US9006333B2 (en) | 2010-09-30 | 2015-04-14 | Daikin Industries, Ltd. | Method for manufacturing fine polytetrafluoroethylene powder |
| US9309335B2 (en) | 2010-09-30 | 2016-04-12 | Daikin Industries, Ltd. | Process for producing polytetrafluoroethylene fine powder |
| US9458316B2 (en) | 2010-09-30 | 2016-10-04 | Daikin Industries, Ltd. | Dripping inhibitor and resin compound |
| US9475935B2 (en) | 2010-09-30 | 2016-10-25 | Daikin Industries, Ltd. | Dripping inhibitor and resin compound |
| JP2015224266A (en) * | 2014-05-26 | 2015-12-14 | 三菱レイヨン株式会社 | Resin foam and method for producing the same |
| JP2019023253A (en) * | 2017-07-24 | 2019-02-14 | 日本ポリプロ株式会社 | Sheet for thermoforming and thermoformed product |
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