JPS6239634A - Production of polyp-phenylene terephthalamide based film - Google Patents
Production of polyp-phenylene terephthalamide based filmInfo
- Publication number
- JPS6239634A JPS6239634A JP17828385A JP17828385A JPS6239634A JP S6239634 A JPS6239634 A JP S6239634A JP 17828385 A JP17828385 A JP 17828385A JP 17828385 A JP17828385 A JP 17828385A JP S6239634 A JPS6239634 A JP S6239634A
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- film
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Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、ポリパラフェニレンテレフタラミド(以下、
PPTAと称する)からなるフィルムの製造法に関し、
さらに詳しくは透明でかつ優れた面配向性により、フィ
ルムの長尺方向(以下、MD力方向略す)および幅方向
(TD力方向共に優れた機械特性を示すPPTAフィル
ムおよびそれを簡便な手段により得る製造法に関するも
のである。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to polyparaphenylene terephthalamide (hereinafter referred to as
Regarding the manufacturing method of a film consisting of PPTA),
More specifically, a PPTA film that is transparent and exhibits excellent mechanical properties in both the length direction (hereinafter referred to as the MD force direction) and the width direction (TD force direction) due to its excellent plane orientation, and can be obtained by a simple means. It concerns the manufacturing method.
(従来の技術)
PPTAに代表される直線配位性の芳香族ポリアミドは
、特に優れた結晶性や高い融点を有し、また剛直な分子
構造のゆえに、耐熱性で高い機械的強度を有しており、
近年、特に注目されている高分子素材である。またその
光学異方性を示す濃厚溶液から紡糸された繊維は高い強
度およびモジュラスを示すことが報告され、すでに工業
的に実施されるに到っているが、フィルムへの応用例の
提案は少なく、実用化例も未だ知られていない。(Prior art) A linearly coordinated aromatic polyamide represented by PPTA has particularly excellent crystallinity and a high melting point, and due to its rigid molecular structure, it has heat resistance and high mechanical strength. and
It is a polymer material that has received particular attention in recent years. It has also been reported that fibers spun from concentrated solutions exhibiting optical anisotropy exhibit high strength and modulus, and have already been put into practical use industrially, but there are few proposals for application to films. However, there are still no known examples of practical use.
PPTAの有する問題点としては、その有用な高分子量
のポリマーは有機溶媒に難溶であり、濃硫酸等の無機の
強酸が溶媒として用いられねばならないということが挙
げられ、これを回避するために、例えば特公昭56−4
5421号公報では、直線配位性芳香族ポリアミドの芳
香核にハロゲン基を導入した単位と、PPTA以外の芳
香核に置換基をもたない芳香族ポリアミドを共重合する
ことにより有機溶媒に可溶とし、それからフィルムを得
ようとする試みがなされている。しかし、これは七ツマ
−が高価なため、コストが高くなる上に、折角の直線配
位性芳香族ポリアミドの耐熱性や結晶性を損なう欠点が
ある。Problems with PPTA include that its useful high molecular weight polymer is poorly soluble in organic solvents, and strong inorganic acids such as concentrated sulfuric acid must be used as a solvent. , for example, Special Public Interest Publication No. 56-4
No. 5421 discloses a unit that is soluble in organic solvents by copolymerizing a unit in which a halogen group is introduced into the aromatic nucleus of a linearly coordinating aromatic polyamide and an aromatic polyamide other than PPTA that does not have a substituent in the aromatic nucleus. Attempts have been made to obtain films from it. However, this method has the disadvantage that the cost is high because the 7-mer is expensive, and that it impairs the heat resistance and crystallinity of the linearly coordinated aromatic polyamide.
一方、特公昭59−14567号公報には光学異方性を
有する芳香族ポリアミド溶液をスリットから短い空気層
を介して凝固浴中に押出す方法が開示されているが、こ
の方法ではMD方向の機械的強度のみ強く、それと直交
するTD力方向機械的強度は極端に弱く、裂けやすいも
のしか得られなかった。On the other hand, Japanese Patent Publication No. 59-14567 discloses a method of extruding an aromatic polyamide solution having optical anisotropy from a slit through a short air layer into a coagulation bath. Only the mechanical strength was strong, but the mechanical strength in the TD force direction perpendicular to the mechanical strength was extremely weak, and only a product that was easy to tear was obtained.
このように単に芳香族ポリアミドの光学異方性ドープを
押出し、そのまま凝固させただけでは、吐出方向に過度
に配向するために、フィブリル化′しやす<TD力方向
弱いものとなってしまうため、これを改良しようとする
フィルム製造方法が種々検討された。If the optically anisotropic dope of aromatic polyamide is simply extruded and solidified as it is, it will be excessively oriented in the extrusion direction, making it easy to fibrillate and weak in the TD force direction. Various film manufacturing methods have been studied to try to improve this problem.
例えば特公昭57−35088号公報には、光学異方性
を有する芳香族ポリアミド溶液を、リングダイから押出
し、インフレーション法を用いてドープの状態で2軸方
向に同時流延させた後、湿式凝固させることにより等方
性のフィルムが得られるとしている。しかし、この方法
では均一な厚みのフィルムを得るのは難しく、機械的強
度も低い゛という欠点がある。For example, Japanese Patent Publication No. 57-35088 discloses that an aromatic polyamide solution having optical anisotropy is extruded from a ring die, simultaneously cast in a doped state in two axes using an inflation method, and then wet coagulated. It is said that an isotropic film can be obtained by doing this. However, this method has the disadvantage that it is difficult to obtain a film with uniform thickness and its mechanical strength is low.
また特公昭59−5407号公報、特開昭54−132
674号公報では、直線配位性芳香族ポリアミドの光学
異方性または光学等方性のドープを、グイ中で押出し方
向と直角の方向に機械的に剪断力を与えることにより、
押出し時に押出し方向とその直角方向の2軸方向に配向
させる提案をしているが、ダイの構造が複雑で、工業的
実施上の難点がある。Also, Japanese Patent Publication No. 59-5407, Japanese Patent Publication No. 54-132
No. 674 discloses that by mechanically applying a shearing force to an optically anisotropic or optically isotropic dope of a linear aromatic polyamide in a goo in a direction perpendicular to the extrusion direction,
Although it has been proposed to orient the material in two axes, ie, in the extrusion direction and in a direction perpendicular to the extrusion direction during extrusion, the structure of the die is complicated and there are difficulties in industrial implementation.
さらにJ、Appj!、Pofym、Sc i、voA
、27、No、8、P、 2965〜2985(19
82)には、PPTAの光学異方性ドープをリングダイ
より油塗布した円錐状のマンドレル上に押出すことによ
り、2軸配向したフィルムが得られることが提案されて
いるが、このフィルムは、等方的な機械強度が低く、ド
ラフトをかけた場合、MD方向の機械的強度は高いが、
TD力方向それは著しく低いものであった。Furthermore, J, Appj! ,Pofym,Sc i,voA
, 27, No. 8, P, 2965-2985 (19
82) proposes that a biaxially oriented film can be obtained by extruding an optically anisotropic dope of PPTA from a ring die onto an oil-coated conical mandrel; The isotropic mechanical strength is low, and when drafted, the mechanical strength in the MD direction is high, but
The TD force direction was significantly lower.
特公昭57−17886号公報には、直線配位性芳香族
ポリアミドの光学異方性ドープを凝固直前に、光学等方
性となるまで加熱した後、凝固させることによって、透
明で機械的物性が等方的であるフィルムを得ることが記
載されている。この方法は、従来の光学異方性ドープの
活用により高性能を得んとする大刀の概念に逆らった独
創的なものであり、これにより光学異方性ドープの極端
な1軸配向性の緩和と同時に、光学異方性ドープの液晶
ドメイン構造がドープを押出した後も残り、そのまま凝
固して不透明なフィルムとなってしまうことを回避する
ことに成功している。しかし、この方法も前述のごとく
、PPTAは濃硫酸他の無機強酸を溶媒とせざるを得な
いため、光学異方性ドープを光学等方性となる温度にま
で加熱する際にポリマーの分解を伴わざるを得す、高い
強度のフィルムを得る上で問題があり、また単に加熱し
て光学等方性ドープとしてから押出すのみでは、押出し
時の流動配向は光学異方性ドープの場合よりは緩和され
るものの、非常な高粘度となり、そもそも押出すこと自
体が困難となる。Japanese Patent Publication No. 57-17886 discloses that an optically anisotropic dope of a linearly coordinated aromatic polyamide is heated until it becomes optically isotropic immediately before solidification, and then solidified to produce a transparent material with mechanical properties. It is described to obtain films that are isotropic. This method is an original method that goes against the conventional concept of achieving high performance by utilizing optically anisotropic doping, and it allows for the relaxation of the extreme uniaxial orientation of optically anisotropic doping. At the same time, it has been successfully avoided that the liquid crystal domain structure of the optically anisotropic dope remains even after the dope is extruded and solidifies as it is, resulting in an opaque film. However, as mentioned above, this method has no choice but to use concentrated sulfuric acid or other inorganic strong acids as a solvent, so the polymer decomposition occurs when the optically anisotropic dope is heated to a temperature at which it becomes optically isotropic. However, there is a problem in obtaining a high-strength film, and simply heating to form an optically isotropic dope and then extruding it will cause the flow orientation during extrusion to be more relaxed than in the case of an optically anisotropic dope. However, the viscosity is extremely high, making extrusion itself difficult.
(発明が解決しようとする問題点)
以上のように、光学異方性ドープはポリマーが液晶とし
て集合したドメイン構造を有するため、ドープをフィル
ム状とした際にもそのドメイン構造が残り、得られたフ
ィルムは不透明となる。これを避けようとして光学等方
性ドープを用いようとすれば、有用な高分子量のPPT
A系ポリマーでは極めて高粘度となり、約5重量%以下
のポリマー濃度でないと製膜不能となり、この濃度の光
学等方性ドープから製膜したフィルムは、凝固に際して
ボイドを生成しやすく、また機械的物性も全く不十分な
ものとなる。(Problems to be Solved by the Invention) As described above, since the optically anisotropic dope has a domain structure in which polymers are aggregated as liquid crystals, the domain structure remains even when the dope is made into a film, making it difficult to obtain a film. The film becomes opaque. If you try to use an optically isotropic dope to avoid this, you can use a useful high molecular weight PPT.
A-based polymers have extremely high viscosity and cannot be formed into films unless the polymer concentration is approximately 5% by weight or less. Films formed from optically isotropic dopes at this concentration tend to form voids during coagulation and are mechanically difficult to form. The physical properties are also completely inadequate.
本発明の目的は、すでに工業的に繊維が生産されている
PPTAまたはPPTA系ポリマーを用いて、上記のご
とき透明性に優れ、かつ短時間で透明性のフィルムを得
ることができ、さらにフィルムのMD力方向みならず、
TD力方向も十分配向し、縦横両方向共に高い強度およ
びモジュラスを有するフィルムの工業的な製法を提供す
ることにある。The purpose of the present invention is to use PPTA or PPTA-based polymers whose fibers have already been produced industrially to obtain a transparent film with excellent transparency as described above in a short time, and to further improve the film quality. Not only in the MD force direction,
The object of the present invention is to provide an industrial method for producing a film that is sufficiently oriented in the TD force direction and has high strength and modulus in both the longitudinal and lateral directions.
(問題点を解決するための手段)
先に述べた特公昭57−17886号公報の概念は、フ
ィルムの機械的物性を高める上では好ましい高いポリマ
ー濃度のドープを用いながら、PPTAにより自然に形
成される液晶現象に伴うドープの低粘度化を応用して、
ポリマーの熔解や移送、成形を容易とし、最後の凝固さ
せる直前の短時間のみ、ドープを加熱することにより光
学等方性化して、透明フィルムを得るというものである
。(Means for Solving the Problems) The concept of Japanese Patent Publication No. 17886/1986 described above uses a dope with a high polymer concentration, which is preferable for improving the mechanical properties of the film, while naturally forming a polymer with PPTA. By applying the lower viscosity of the dope associated with the liquid crystal phenomenon,
This method facilitates the melting, transport, and molding of the polymer, and makes the dope optically isotropic by heating it for a short period of time just before final solidification to obtain a transparent film.
本発明者らは、この発想の応用とその欠点の克服につき
鋭急検討した結果、偶然発見した現象とその機構の解明
により、次のごとき新規なフィルムとその製造法が、前
記問題点を解決することを見出し、本発明を完成するに
到った。The inventors of the present invention made a rapid study to apply this idea and overcome its shortcomings, and as a result of the accidental discovery of the phenomenon and elucidation of its mechanism, the following new film and its manufacturing method were developed to solve the above problems. They have discovered that this is the case, and have completed the present invention.
すなわち本発明は、対数粘度ηinhが2.5以上であ
るポリパラフェニレンテレフタルアミド系ポリマーと、
98ffif1%以上の濃度の硫酸、クロル硫酸および
フルオル硫酸からなる群より選択された少なくとも1種
の溶媒とを含んでなる、常温付近以上の温度で光学異方
性を有するドープを、光学異方性を保ったまま支持面上
にフィルム状となし、該ドープを45℃以上にて、飽和
水蒸気、過飽和水蒸気または霧状の水を含有する気体中
で吸湿させて光学異方性ドープを光学等方性ドープに実
質的に転化させた後、凝固させ、次いで洗浄することを
特徴とするポリバラフェニレンテレフタルアミド系フィ
ルムの製造方法に関するものである。That is, the present invention provides a polyparaphenylene terephthalamide-based polymer having a logarithmic viscosity ηinh of 2.5 or more,
Optically anisotropic dope containing at least one solvent selected from the group consisting of sulfuric acid, chlorosulfuric acid, and fluorosulfuric acid at a concentration of 98ffif1% or more and having optical anisotropy at a temperature around room temperature or higher. The optically anisotropic dope is optically isotropic by forming it into a film on a supporting surface while maintaining the same temperature, and absorbing moisture in a gas containing saturated steam, supersaturated steam, or mist water at 45°C or higher. The present invention relates to a method for producing a polyvalent phenylene terephthalamide film, which comprises substantially converting the film into a polyvalent dope, coagulating it, and then washing it.
本発明のフィルムは、実質的に
+C叶Qo −c OHN (◇−NH六で表わされる
PPTA系からなっている。ここで、「実質的に」なる
意味は、本発明の構成要件および作用効果を阻害しない
範囲の少量で、PPTA以外のポリマー〔例えば、ポリ
−(m−フェニレンテレフタルアミド)、ポリ=(p−
フェニレンイソフタルアミド)、ポリ−(m−フェニレ
ンイソフタルアミド)、ポリ−(メチレンテレフタルア
ミド)、脂肪族ポリアミド、脂肪族ポリアミド、ポリエ
ステル、ポリイミド、ポリウレタン、ポリ尿素等〕がブ
レンドされたり、PPTAに他のくり返し単位(例えば
、核置換されたp−フェニレン単位、核置換されたまた
は未置換のビフェニレン単位、0−フェニレン単位、m
−フェニレン単位、(ポリ)メチレン単位、ピリジレン
単位やエステル、ウレタン、尿素、エーテル、チオエー
テルなどの結合単位等)が共重合されたりしていてもよ
いことを意味する。The film of the present invention is substantially composed of a PPTA system represented by +C-Qo-cOHN (◇-NH6. Here, the meaning of "substantially" refers to the constituent features and effects of the present invention. Polymers other than PPTA [e.g., poly(m-phenylene terephthalamide), poly=(p-
phenylene isophthalamide), poly(m-phenylene isophthalamide), poly(methylene terephthalamide), aliphatic polyamide, aliphatic polyamide, polyester, polyimide, polyurethane, polyurea, etc.], or other materials are blended with PPTA. Repeating units (e.g. nuclear substituted p-phenylene units, nuclear substituted or unsubstituted biphenylene units, 0-phenylene units, m
- phenylene units, (poly)methylene units, pyridylene units, bonding units such as esters, urethanes, ureas, ethers, thioethers, etc.) may be copolymerized.
本発明のボ・リマーの重合度は、あまりに低いと本発明
の目的とする機械的性質の良好なフィルムが得られなく
なるため、通常2.5以上、好ましくは3.5以上の対
数粘度η1nh(硫酸100mj!にポリマー0.2g
を溶解して30℃で測定した値)を与える重合度のもの
が選ばれる。If the degree of polymerization of the polymer of the present invention is too low, it will not be possible to obtain a film with good mechanical properties, which is the object of the present invention, so the logarithmic viscosity η1nh ( 100mj of sulfuric acid! 0.2g of polymer
A polymer with a degree of polymerization that gives a value measured at 30°C when dissolved is selected.
本発明のPPTA系フィルムの成型に用いるドープを調
製するのに適した溶媒としては、98重量%以上の濃度
の硫酸、クロル硫酸、フルオル硫酸またはそれらの混合
物が挙げられる。硫酸は100%以上のもの、すなわち
発煙硫酸、トリハロゲン化酢酸などを、本発明の効果を
損なわない範囲で混合して用いてもよい。Suitable solvents for preparing the dope for forming the PPTA-based film of the present invention include sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, or mixtures thereof at a concentration of 98% by weight or more. Sulfuric acid of 100% or more, ie, fuming sulfuric acid, trihalogenated acetic acid, etc., may be mixed and used within a range that does not impair the effects of the present invention.
本発明に用いられるドープ中のポリマー濃度は、常温付
近(約20〜30℃)またはそれ以上の温度で光学異方
性を示す濃度以上のものが好ましく用いられ、具体的に
は約10重量%以上、好ましくは約12M量%以上で用
いられる。常温またはそれ以上の温度で光学異方性を示
さないポリマー濃度では、成型されたPPTA系フィル
ムが好ましい機械的性質を持たなくなることが多い、ド
ープのポリマー濃度の上限は特に限定されるものではな
いが、通常は25重量%以下、特に高いηinhのPP
TA系ポリマーに対しては20重量%以下が好ましく用
いられる。The concentration of the polymer in the dope used in the present invention is preferably at least a concentration that exhibits optical anisotropy at temperatures around room temperature (approximately 20 to 30°C) or higher, and specifically, approximately 10% by weight. It is preferably used in an amount of about 12 M% or more. At polymer concentrations that do not exhibit optical anisotropy at room temperature or higher temperatures, the formed PPTA film often does not have favorable mechanical properties.There is no particular upper limit to the polymer concentration of the dope. However, it is usually less than 25% by weight, especially PP with high ηinh.
For TA-based polymers, 20% by weight or less is preferably used.
本発明のドープには普通の添加剤、例えば、増量剤、除
光火剤、紫外線安定化剤、熱安定化剤、抗酸化剤、顔料
、溶解助剤などを混入してもよい。The dope of the present invention may contain conventional additives, such as fillers, light removers, UV stabilizers, heat stabilizers, antioxidants, pigments, solubilizing agents, and the like.
ドープが光学異方性か光学等方性であるかは、公知の方
法、例えば特公昭50−8474号公報記載の方法で調
べることができるが、その臨界点は、溶媒の種類、温度
、ポリマー濃度、ポリマーの重合度、非溶媒の含有量等
に依存するので、これらの関係を予め調べることによっ
て、光学異方性ドープをつくることができる。Whether the dope is optically anisotropic or optically isotropic can be determined by a known method, such as the method described in Japanese Patent Publication No. 50-8474, but the critical point depends on the type of solvent, temperature, polymer Since it depends on the concentration, degree of polymerization of the polymer, content of non-solvent, etc., it is possible to create an optically anisotropic dope by examining these relationships in advance.
本発明の機械的性質に優れた透明フィルムを得る方法は
、特定の方法によりドープを支持面上にフィルム状にし
た後、凝固に先立ってドープを光学異方性から光学等方
性に転化するものである。The method of obtaining a transparent film with excellent mechanical properties according to the present invention involves forming a dope into a film on a support surface using a specific method, and then converting the dope from optically anisotropic to optically isotropic prior to solidification. It is something.
具体的には支持面上にフィルム状にした光学異方性ドー
プを凝固に先立ち、45℃以上にて飽和水蒸気、過飽和
水蒸気または霧状の水を含有する気体中で吸湿させる。Specifically, an optically anisotropic dope formed into a film on a support surface is allowed to absorb moisture in a gas containing saturated steam, supersaturated steam, or mist water at 45° C. or higher prior to solidification.
気体としては、経済的には、空気が最も好ましい。本発
明でいう霧状の水とは、100°C以上の水蒸気を空気
中に放出してできる凝集水のうち空気中に浮遊する程度
の水の粒状物、または市販されている加湿機で発せられ
る微細な水の粒状物等を示し、空気中に浮遊しないよう
な大きな粒子は除かれる。なぜなら、水の大きな粒子が
支持面上のドープと接触すると、部分的な凝固が始まっ
て好ましくないからである。温度は通常45℃以上が用
いられる。45℃未満の温度で吸湿させると部分的に凝
固するため、ポリマーが析出したり、フィルムの平面性
が失われるので好ましくない。またその上限はポリマー
の分解性を考慮した場合、一般的にあまり高くないこと
が望ましく、フィルム状のドープの温度が200°Cを
超えない程度に選ばれることが望ましい。ドープを吸湿
させる温度のより好ましい範囲は60−150°Cであ
る。From an economical point of view, air is the most preferable gas. Atomized water as used in the present invention refers to particles of water that float in the air among the condensed water that is produced by releasing water vapor at 100°C or higher into the air, or water that is generated by a commercially available humidifier. It shows fine water particles that are suspended in water, and excludes large particles that do not float in the air. This is because if large particles of water come into contact with the dope on the support surface, partial coagulation will begin, which is undesirable. A temperature of 45° C. or higher is usually used. Absorbing moisture at a temperature below 45° C. is not preferable because it will partially solidify, leading to polymer precipitation and loss of flatness of the film. In addition, when considering the decomposability of the polymer, it is generally desirable that the upper limit is not too high, and it is desirable that the temperature of the film-like dope is selected so as not to exceed 200°C. A more preferable temperature range for making the dope absorb moisture is 60-150°C.
このように、高温で多量の水分を含む気体によってドー
プを吸湿させることにより、PPTA系ポリマーの光学
異方性ドープを数秒以下の短時間で光学等方性化できる
ことが本発明の大きな特徴である。これにより、ドープ
の厚みが厚い場合、ドープ中のポリマー濃度が高い場合
、ポリマー重合度の大きい場合においても、工業上容易
に、かつフィルムの物性を損なうことなく、光学等方性
、のフィルムを製膜することができる。As described above, a major feature of the present invention is that an optically anisotropic dope of a PPTA-based polymer can be made optically isotropic in a short time of several seconds or less by absorbing moisture in the dope with a gas containing a large amount of water at high temperature. . As a result, even when the thickness of the dope is thick, the polymer concentration in the dope is high, and the degree of polymerization is high, optically isotropic films can be easily produced industrially and without impairing the physical properties of the film. Can be formed into a film.
この吸湿により光学等方性化する機構は必ずしも明らか
ではないが、おそらく吸湿することによるポリマー濃度
と溶媒濃度の低下により、PPTA系ポリマー溶媒系の
液晶域がかなり縮小するためであろうと思われる。The mechanism by which optical isotropy occurs due to moisture absorption is not necessarily clear, but it is probably because the liquid crystal region of the PPTA polymer solvent system is considerably reduced due to a decrease in polymer concentration and solvent concentration due to moisture absorption.
この光学等方性化する際に、吸湿を伴わず加熱のみで行
なおうとすると、高温かつ長時間の加熱が必要となり、
得られるフィルムもポリマーの一部分解を伴う結果、物
性の劣ったものとなりやすい。If we attempt to achieve this optical isotropy by heating alone without moisture absorption, heating at high temperatures and for a long time will be required.
The resulting film also tends to have poor physical properties due to partial decomposition of the polymer.
本発明において、ドープの凝固液として使用できるのは
、例えば水約70M量%以下の希硫酸、約20重量%以
下の水酸化ナトリウム水溶液およびアンモニア水、約5
0重量%以下の塩化ナトリウム水溶液および塩化カルシ
ウム水溶液などである。凝固浴の温度は特に制限される
ものではなく、通常約−5〜50℃の範囲で行なわれる
。In the present invention, examples of the dope coagulating liquid that can be used include water, dilute sulfuric acid containing about 70 M% or less, sodium hydroxide aqueous solution containing about 20% by weight or less, and aqueous ammonia, about 5% by weight or less.
These include 0% by weight or less sodium chloride aqueous solution and calcium chloride aqueous solution. The temperature of the coagulation bath is not particularly limited and is usually in the range of about -5 to 50°C.
凝固されたフィルムはそのままでは酸が含まれているた
め、加熱による機械的物性の低下の少ないフィルムを製
造するには酸分の洗浄、除去をできるだけ行なう必要が
ある。酸分の除去は、具体的には約500ppm以下ま
で行なうことが望ましい。洗浄液としては水が通常用い
られるが、必要に応じて温水で行なったり、アルカリ水
溶液で中和洗浄した後、水などで洗浄してもよい。洗浄
は、例えば洗浄液中でフィルムを走行させたり、洗浄液
を噴霧する等の方法により行なわれる。Since the coagulated film as it is contains acid, it is necessary to wash and remove the acid as much as possible in order to produce a film whose mechanical properties are less likely to deteriorate due to heating. Specifically, it is desirable to remove the acid content to about 500 ppm or less. Water is usually used as the cleaning liquid, but if necessary, hot water may be used, or washing may be performed by neutralizing with an alkaline aqueous solution and then washing with water. Cleaning is carried out, for example, by running the film in a cleaning liquid or by spraying the cleaning liquid.
洗浄されたフィルムは、次に乾燥されるが、ここで乾燥
とは、フィルムに付着している洗浄液などを取り除く操
作をいい、洗浄液などが取り除かれるならばいかなる方
法でもよく、常温で風乾、加熱された非活性気体、例え
ば空気、窒素、アルゴンなどでの雰囲気下の乾燥、加熱
ロール上での乾燥、テンターでの加熱雰囲気下の乾燥な
どいずれでもよい。また乾燥は、通常はフィルムにしわ
が寄るのを防ぐため、緊張下または定長下に、フィルム
の収縮を制限して行なうことが好ましい。The washed film is then dried. Drying here refers to the operation of removing the cleaning liquid etc. adhering to the film. Any method may be used as long as the cleaning liquid etc. can be removed, such as air drying at room temperature or heating. Any method may be used, such as drying in an atmosphere of an inert gas such as air, nitrogen, or argon, drying on a heated roll, or drying in a heated atmosphere with a tenter. Further, in order to prevent the film from wrinkling, drying is preferably carried out under tension or at a constant length to limit shrinkage of the film.
乾燥温度は、特に制置されるものではないが、常温以上
また、機械的強度を効果的にするためには、高温のほう
が好ましく、100℃以上、さらに好ましくは200℃
以上が用いられる。乾燥の最高温度は、特に限定される
ものではないが、乾燥エネルギーやポリマーの分解性を
考慮すれば、500℃以下が好ましい。The drying temperature is not particularly limited, but is preferably at least room temperature, and in order to effectively improve mechanical strength, it is preferably at a high temperature, 100°C or more, more preferably 200°C.
The above is used. The maximum temperature for drying is not particularly limited, but in consideration of drying energy and decomposability of the polymer, it is preferably 500° C. or lower.
本発明の方法によりフィルムを製造する上で、上記の工
程は、いずれも回分式でも連続的でもよく、また全工程
を通して連続してフィルムを走行させつつ製造すること
も好ましい実施態様の1つである。また任意の工程で油
剤、識別用の染料などをフィルムに付与してもさしつか
えない。In producing the film by the method of the present invention, the above steps may be carried out batchwise or continuously, and it is also a preferred embodiment to produce the film while running it continuously throughout the entire process. be. Further, an oil agent, an identification dye, etc. may be added to the film in any step.
(実施例)
以下に実施例および参考例(PPTAの製造例)を示す
が、これらの参考例および実施例は本発明を説明するも
のであって、本発明を限定するものではない。なお、実
施例中特に規定しない場合は重量部または重量%を示す
。対数粘度ηinhは98%硫酸]−00m (!にポ
リマー0.2gを熔解し、30°Cで常法で測定した。(Example) Examples and reference examples (manufacturing examples of PPTA) are shown below, but these reference examples and examples explain the present invention, and do not limit the present invention. In the examples, parts by weight or weight % are shown unless otherwise specified. The logarithmic viscosity ηinh was measured by a conventional method at 30° C. by melting 0.2 g of polymer in 98% sulfuric acid]-00 m (!).
ドープの粘度は、B型粘度計を用いlrpmの回転速度
でヘリ定したものである。フィルムの厚さは、直径2n
の測定面を持ったダイヤルゲージで測定した。強伸度お
よびモジュラスは、定速伸長型強伸度測定機により、フ
ィルム試料を100+nXIQ鶴の長方形に切り取り、
最初のつかみ長さ30m、引張速度30n/分で荷重−
伸長曲線を5回描き、これより算出したものである。The viscosity of the dope was determined using a B-type viscometer at a rotation speed of 1 rpm. The thickness of the film is 2n in diameter.
Measured using a dial gauge with a measuring surface. Strength and elongation and modulus were determined by cutting a film sample into a 100+nXIQ rectangle using a constant-speed extension type strength and elongation measuring machine.
Initial grip length 30m, pulling speed 30n/min, load -
The elongation curve was drawn five times and calculated from this.
光線透過率は次のように測定される。通常の光電光度計
(または分光光度針)の液体セルをセントする場所にフ
ィルムを張りつけ、600nmの波長の可視光線を選択
し、その透過率を測定する。Light transmittance is measured as follows. A film is pasted onto the liquid cell of an ordinary photoelectric photometer (or spectrophotometer needle), visible light with a wavelength of 600 nm is selected, and its transmittance is measured.
密度の値は四塩化炭素−トルエンを使用した密度勾配管
法により30°Cで測定されたものである。Density values were determined at 30°C by density gradient tube method using carbon tetrachloride-toluene.
参考例(PPTAの製造)
低温溶液重合法により、次のごと<PPTAを得た。特
公昭53−43986号公報に示された重合装置中でN
−メチルピロリドン1000部に無水塩化リチウム70
部を溶解し、次いでバラフェニレンジアミン48.6部
を熔解した。8℃に冷却した後、テレフタル酸ジクロラ
イド91.4部を粉末状で一度に加えた。数分後に重合
反応物はチーズ状に固化したので、特公昭53−439
86号公報記載の方法に従って重合装置より重合反応物
を排出し、直ちに2軸の密閉型ニーグーに移し、同ニー
グー中で重合反応物を微粉砕した。次に微粉砕物をヘキ
シエルミキサー中に移し、はぼ等量の水を加えさらに粉
砕した後、濾過し数回温水中で洗浄して、110℃の熱
風中で乾燥した。ηinhが6.5の淡黄色のPPTA
ポリマー95部を得た。なお、異なったηtnhのポリ
マーは、N−メチルピロリドンとモノマー(バラフェニ
レンジアミンおよびテレフタル酸ジクロライド)の比、
または/およびモノマー間の比等を変えることによって
容易に得ることができる。Reference Example (Manufacture of PPTA) The following PPTA was obtained by a low temperature solution polymerization method. In the polymerization apparatus shown in Japanese Patent Publication No. 53-43986, N
-70 parts of anhydrous lithium chloride in 1000 parts of methylpyrrolidone
Then, 48.6 parts of bulk phenylene diamine were dissolved. After cooling to 8°C, 91.4 parts of terephthalic acid dichloride was added at once in powder form. After a few minutes, the polymerization reaction product solidified into a cheese-like shape, so
The polymerization reaction product was discharged from the polymerization apparatus according to the method described in Japanese Patent Application No. 86, and immediately transferred to a two-screw closed Niegoo, and the polymerization reaction product was finely pulverized in the same Niigoo. Next, the finely pulverized product was transferred to a hexyl mixer, an approximately equal amount of water was added, and the mixture was further pulverized, filtered, washed several times in hot water, and dried in hot air at 110°C. Pale yellow PPTA with ηinh of 6.5
95 parts of polymer were obtained. In addition, polymers with different ηtnh have different ratios of N-methylpyrrolidone and monomers (phenylenediamine and terephthalic acid dichloride),
Or/and can be easily obtained by changing the ratio between monomers.
実施例1
ηinhが6.2のPPTAを60゛cでポリマー濃度
が14,0%になるように99.6%の硫酸に溶解した
。このドープは80℃で光学異方性を示し、粘度は33
00ポイズであった。このドープを120℃のガラス板
上に、0.1flの段差のついたアプリケータにより塗
布した。その塗布したドープ上に約3kg/cnlGの
圧の飽和水蒸気から得られた常圧の霧状の水を含む空気
を吹きつけたところ、第1表の等方性化時間に示した時
間で光学等方性になるのが確認された。その直後ドープ
をガラス板と共に20°Cの水に入れ、凝固させた後、
5%のカセイソーダ水溶液で中和処理を行ない、その後
さらに2昼夜水洗した。この湿フィルムを250℃で1
時間、定長乾燥した後の性質を第1表に示す。Example 1 PPTA having an ηinh of 6.2 was dissolved in 99.6% sulfuric acid at 60°C to a polymer concentration of 14.0%. This dope exhibits optical anisotropy at 80°C and has a viscosity of 33
It was 00 poise. This dope was applied onto a glass plate at 120° C. using an applicator with a 0.1 fl step. When air containing atomized water at normal pressure obtained from saturated steam at a pressure of about 3 kg/cnlG was blown onto the applied dope, the optical It was confirmed that it became isotropic. Immediately after that, the dope was placed in water at 20°C along with the glass plate and solidified.
It was neutralized with a 5% aqueous solution of caustic soda, and then washed with water for two days and nights. This wet film was heated at 250℃ for 1
Table 1 shows the properties after drying for a fixed length of time.
比較例1
実施例1の光学異方性ドープを同様にガラス板に塗布し
た後、ガラス板の温度を120℃に保ったまま空気中に
放置していたら、第1表の等方性化時間に示した時間後
に光学等方性になるのが確認された。そのときの気温は
28℃で相対湿度は58%だった。その後、実施例1と
同様に凝固、中和、水洗、乾燥処理を行なった。このフ
ィルムの性質を第1表に示す。Comparative Example 1 After applying the optically anisotropic dope of Example 1 to a glass plate in the same manner, if the glass plate was left in the air while keeping the temperature at 120°C, the isotropy time shown in Table 1 It was confirmed that the film became optically isotropic after the time indicated in . The temperature at that time was 28°C and the relative humidity was 58%. Thereafter, coagulation, neutralization, water washing, and drying treatments were performed in the same manner as in Example 1. The properties of this film are shown in Table 1.
比較例2
実施例Iの光学異方性ドープを、同様にガラス板に塗布
した後、すぐに120℃の乾燥窒素オーブン中に入れ、
90秒間保った。このドープは光学等方化していなかっ
たが、実施例1と同様に凝固、中和、水洗、乾燥処理を
行なった。このフィルムの性質を第1表に示す。Comparative Example 2 The optically anisotropic dope of Example I was similarly applied to a glass plate, and then immediately placed in a dry nitrogen oven at 120°C.
It was held for 90 seconds. Although this dope was not optically isotropic, it was coagulated, neutralized, washed with water, and dried in the same manner as in Example 1. The properties of this film are shown in Table 1.
実施例2
実施例1と同じドープを用いて50℃のガラス板上で実
施例1と同じように行なった。光学等方性になる時間と
得られたフィルムの性質を第1表に示す。Example 2 A test was conducted in the same manner as in Example 1 using the same dope as in Example 1 on a glass plate at 50°C. Table 1 shows the time required to achieve optical isotropy and the properties of the obtained film.
以下余白
比較例3
実施例1の光学異方性ドープを、同様に力゛ラス板に塗
布した後、ガラス板の温度を保ったまま空気中に保った
。第1表の等方性化時間に示した時間後に光学等方性に
なった。気温および相対湿度はそれぞれ32℃、76%
だった。得られたフィルムの性質を第1表に示した。Comparative Example 3 The optically anisotropic dope of Example 1 was similarly applied to a glass plate, and then the glass plate was kept in air while maintaining its temperature. Optical isotropy was achieved after the time shown in Table 1, Isotropy time. Temperature and relative humidity are 32℃ and 76%, respectively.
was. The properties of the obtained film are shown in Table 1.
(発明の効果)
本発明によれば、実施例に示したように市販のフィルム
には見られない高い強度と高いモジュラスで表わされる
良好な機械的性質を有し、しかもMD方向とTD力方向
掻めてノ\ランスのとれた物性を有する芳香族ポリアミ
ドフィルムを短時間で製造することができる。また本発
明の方法により得られるフィルムは、機械的特性のみな
らず、優れた電気絶縁性、耐熱性、耐油性、耐圧性、強
酸以外の耐薬品性、構造の緻密性を有する。このため、
高速回転する電気機器の絶縁材料や磁気テープ、フレキ
シブルプリント配線基板、電線被覆材、濾過膜等に好適
に使用することができ、さらにもう1つの特徴である透
明性に優れていることから、包装材料、製版材料、写真
フィルム等にも有用なものである。このように優れた性
質をもつPPTA系フィルムを、工業上極めて容易な方
法で、かつ特に2軸延伸機を用いる必要もなく、製造し
得ることは本発明の重要な効果の1つである。(Effects of the Invention) As shown in the examples, the present invention has good mechanical properties such as high strength and high modulus that are not found in commercially available films, and also has good mechanical properties in the MD direction and TD force direction. Aromatic polyamide films with well-balanced physical properties can be produced in a short time. Furthermore, the film obtained by the method of the present invention has not only mechanical properties but also excellent electrical insulation, heat resistance, oil resistance, pressure resistance, resistance to chemicals other than strong acids, and dense structure. For this reason,
It can be suitably used for insulating materials, magnetic tapes, flexible printed wiring boards, wire coating materials, filtration membranes, etc. for electrical equipment that rotates at high speed, and another feature of its excellent transparency makes it suitable for packaging. It is also useful for materials, plate-making materials, photographic films, etc. One of the important effects of the present invention is that a PPTA film having such excellent properties can be manufactured by an industrially extremely easy method and without the need to use a biaxial stretching machine.
代理人 弁理士 川 北 武 長
手続補正書
昭和60年 9月27日
特許庁長官 宇 賀 道 部 殿
1、事件の表示
昭和60年 特 許 廓 第178283号2、発明の
名称 ポリバラフェニレンテレフタルアミド系フィルム
の製造方法
3、補正をする者
事件との関係 特許出願人
住 所 大阪府大阪市北区堂島浜1丁目2番6号名 称
(003)旭化成工業株式会社代表者世古真臣
4、代理人〒103
住 所 東京都中央区日本橋茅場町−丁目11番8号(
紅萌ビルディング)電話03 (639”) 5592
番氏 名(7658)弁理士 川 北 武 長5
、補正命令の日付 自発
6、補正の対象 明細書の発明の詳細な説明の欄。Agent Patent Attorney Takeshi Kawakita Long Procedural Amendment September 27, 1985 Director General of the Patent Office Michibe Uga 1, Indication of Case 1985 Patent Office No. 178283 2, Name of Invention Polybara Phenylene Terephthalamide Process for manufacturing 3-based film, relationship with the amended case Patent applicant address 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Name (003) Asahi Kasei Industries Co., Ltd. Representative Masaomi Seko 4, Agent 103 Address: 11-8 Nihonbashi Kayabacho, Chuo-ku, Tokyo (
Benimoe Building) Telephone 03 (639”) 5592
Number Name (7658) Patent Attorney Takeshi Kawakita 5
, Date of amendment order Voluntary 6, Subject of amendment Detailed explanation of the invention in the specification.
7、補正の内容
(1)明細書箱6頁5行目の「高い強度」をr高い伸度
」に改める。7. Contents of the amendment (1) In the specification box, page 6, line 5, "high strength" is changed to "r high elongation."
(2)明細書第1頁下行目の「高い強度」を「高い強伸
度」に改める。(2) "High strength" on the bottom line of page 1 of the specification has been changed to "high strength and elongation."
(3)明細書第1頁下行目の「有するフィルム」を「有
する平面性にすぐれたフィルム」に改める。(3) In the lower line of page 1 of the specification, the phrase "having a film" has been changed to "having a film with excellent flatness."
(4)明細書第16頁5行目の「損なうことなく、光学
等方性」を「損なうことなく、透明性に非常にすぐれ、
強伸度ともに大きい等方性Jに改める。(4) "Optical isotropy without loss" on page 16, line 5 of the specification: "Excellent transparency without loss,"
Changed to isotropic J, which has greater strength and elongation.
(5)明細書第16頁2行目の「防ぐため、緊張」を「
防ぐため、或いはフィルムの平面性を出すため、緊張J
に改める。(5) Change “to prevent tension” from line 2 on page 16 of the specification to “
To prevent this, or to make the film flat, the tension is
Changed to
(6)明細書第16頁下から3行目と2行目の間に下記
を加える。(6) Add the following between the third and second lines from the bottom of page 16 of the specification.
「 ボイド数は次のように測定される。適当な大きさの
フィルム片を、透過光を用いた通常の光学顕微鏡により
、100倍から400倍の範囲の倍率で少なくとも異な
った5視野について観察し、その長径が30μ以上の大
きさのボイド数を数え、フィルム表面1mrr?当たり
に換算する。The number of voids is determined as follows: A piece of film of suitable size is observed under a conventional optical microscope using transmitted light in at least five different fields of view at magnifications ranging from 100x to 400x. , the number of voids with a major axis of 30μ or more is counted and calculated per 1 mrr of film surface.
結晶配向角の測定方法としては公知の方法が採用でき、
例えば次のような方法によって行なわれる。X線の入射
はフィルム表面に直角に入射する場合(以下、TV方向
と称する)と表面に並行に入射する場合(以下、SV力
方向称する)とに分けられる。本発明のフィルムはTV
方向からのX線による(200)面の反射である2θζ
23゜に大きな回折ピークを持ち、さらにs V方向か
らの入射による(010)面の反射である2θ−18°
の大きな回折ピークが赤道線上に現れる。所定の20の
角度に計数管を置き、フィルムを180”回転すること
により、回折強度曲線を得る。A known method can be used to measure the crystal orientation angle.
For example, the following method is used. The incidence of X-rays can be divided into two cases: a case where the X-ray is incident at right angles to the film surface (hereinafter referred to as the TV direction) and a case where the X-ray is incident parallel to the surface (hereinafter referred to as the SV force direction). The film of the present invention
2θζ, which is the reflection of the (200) plane by X-rays from the direction
It has a large diffraction peak at 23°, and is further reflected at 2θ-18° from the (010) plane due to incidence from the s V direction.
A large diffraction peak appears on the equator line. A diffraction intensity curve is obtained by placing the counter at a predetermined 20 angle and rotating the film 180''.
なお、TVにおいては、最高強度を中心とし、前後90
°の間を回転させる。この曲線の最高強度の、最低強度
点間に引いたベースラインに対する半分の強度を示す点
に対応する、回折写真における円弧長を度で表した値(
すなわち、最高強度のベースラインに対する50%の点
に対する角度)を測定し、それを試料の結晶配向角とす
る。測定に際し、フィルムは必要により何枚か重ねて回
折強度を測ることができる。縞模様は、もし存在すれば
通常の光学顕微鏡によっても認めることができるが、偏
光顕微鏡を用いて、直交ニコルまたは直交ニコルに近い
状態で観察すると、より鮮明に、種々の色をもった縞と
して、観測される。j(7)明細書箱20頁の第1表を
下記のように改める。In addition, for TV, the maximum intensity is centered around 90
Rotate between °. The value of the arc length in degrees in the diffraction photograph corresponding to the point where the highest intensity of this curve is half the intensity of the baseline drawn between the lowest intensity points (
In other words, the angle relative to the 50% point of the baseline with the highest intensity is measured, and this is taken as the crystal orientation angle of the sample. During the measurement, the diffraction intensity can be measured by stacking several films if necessary. Striped patterns, if present, can be seen with a normal optical microscope, but when observed under a polarized light microscope at crossed Nicols or close to crossed Nicols, they become more clearly visible as stripes with various colors. , observed. j(7) Table 1 on page 20 of the specification box has been amended as follows.
以下余白Below margin
Claims (1)
ェニレンテレフタルアミド系ポリマーと、98重量%以
上の濃度の硫酸、クロル硫酸およびフルオル硫酸からな
る群より選択された少なくとも1種の溶媒とを含んでな
る、常温付近以上の温度で光学異方性を有するドープを
、光学異方性を保ったまま支持面上にフィルム状となし
、該ドープを45℃以上にて、飽和水蒸気、過飽和水蒸
気または霧状の水を含有する気体中で吸湿させて光学異
方性ドープを光学等方性ドープに実質的に転化させた後
、凝固させ、次いで洗浄することを特徴とするポリパラ
フェニレンテレフタルアミド系フィルムの製造方法。(1) A polyparaphenylene terephthalamide-based polymer having a logarithmic viscosity ηinh of 2.5 or more and at least one solvent selected from the group consisting of sulfuric acid, chlorosulfuric acid, and fluorosulfuric acid at a concentration of 98% by weight or more. A dope containing optical anisotropy at temperatures around room temperature or higher is formed into a film on a support surface while maintaining optical anisotropy, and the dope is heated to 45° C. or higher with saturated steam or supersaturated steam. Or polyparaphenylene terephthalamide, which is characterized in that the optically anisotropic dope is substantially converted into an optically isotropic dope by absorbing moisture in a gas containing atomized water, and then solidified and then washed. A method for producing a film based on the method.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17828385A JPS6239634A (en) | 1985-08-13 | 1985-08-13 | Production of polyp-phenylene terephthalamide based film |
EP19860104494 EP0198326B1 (en) | 1985-04-04 | 1986-04-02 | Poly-p-phenylene-terephthalamide film and process for producing the same |
DE8686104494T DE3680695D1 (en) | 1985-04-04 | 1986-04-02 | POLY-P-PHENYLENE TEREPHTHALAMIDE FILM AND METHOD FOR THE PRODUCTION THEREOF. |
US06/847,741 US4752643A (en) | 1985-04-04 | 1986-04-03 | Transparent poly-p-phenylene-terephthalamide film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17828385A JPS6239634A (en) | 1985-08-13 | 1985-08-13 | Production of polyp-phenylene terephthalamide based film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6239634A true JPS6239634A (en) | 1987-02-20 |
JPH0352775B2 JPH0352775B2 (en) | 1991-08-13 |
Family
ID=16045758
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17828385A Granted JPS6239634A (en) | 1985-04-04 | 1985-08-13 | Production of polyp-phenylene terephthalamide based film |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6239634A (en) |
Cited By (7)
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---|---|---|---|---|
US9644157B2 (en) | 2012-07-30 | 2017-05-09 | Headwaters Heavy Oil, Llc | Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
US9790440B2 (en) | 2011-09-23 | 2017-10-17 | Headwaters Technology Innovation Group, Inc. | Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker |
US10118146B2 (en) | 2004-04-28 | 2018-11-06 | Hydrocarbon Technology & Innovation, Llc | Systems and methods for hydroprocessing heavy oil |
US10822553B2 (en) | 2004-04-28 | 2020-11-03 | Hydrocarbon Technology & Innovation, Llc | Mixing systems for introducing a catalyst precursor into a heavy oil feedstock |
US11414607B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with increased production rate of converted products |
US11414608B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor used with opportunity feedstocks |
US11421164B2 (en) | 2016-06-08 | 2022-08-23 | Hydrocarbon Technology & Innovation, Llc | Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product |
-
1985
- 1985-08-13 JP JP17828385A patent/JPS6239634A/en active Granted
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10118146B2 (en) | 2004-04-28 | 2018-11-06 | Hydrocarbon Technology & Innovation, Llc | Systems and methods for hydroprocessing heavy oil |
US10822553B2 (en) | 2004-04-28 | 2020-11-03 | Hydrocarbon Technology & Innovation, Llc | Mixing systems for introducing a catalyst precursor into a heavy oil feedstock |
US10941353B2 (en) | 2004-04-28 | 2021-03-09 | Hydrocarbon Technology & Innovation, Llc | Methods and mixing systems for introducing catalyst precursor into heavy oil feedstock |
US9790440B2 (en) | 2011-09-23 | 2017-10-17 | Headwaters Technology Innovation Group, Inc. | Methods for increasing catalyst concentration in heavy oil and/or coal resid hydrocracker |
US9644157B2 (en) | 2012-07-30 | 2017-05-09 | Headwaters Heavy Oil, Llc | Methods and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
US9969946B2 (en) | 2012-07-30 | 2018-05-15 | Headwaters Heavy Oil, Llc | Apparatus and systems for upgrading heavy oil using catalytic hydrocracking and thermal coking |
US11414607B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor with increased production rate of converted products |
US11414608B2 (en) | 2015-09-22 | 2022-08-16 | Hydrocarbon Technology & Innovation, Llc | Upgraded ebullated bed reactor used with opportunity feedstocks |
US11421164B2 (en) | 2016-06-08 | 2022-08-23 | Hydrocarbon Technology & Innovation, Llc | Dual catalyst system for ebullated bed upgrading to produce improved quality vacuum residue product |
Also Published As
Publication number | Publication date |
---|---|
JPH0352775B2 (en) | 1991-08-13 |
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