JPS62263228A - Polyimide tubular body - Google Patents
Polyimide tubular bodyInfo
- Publication number
- JPS62263228A JPS62263228A JP10624286A JP10624286A JPS62263228A JP S62263228 A JPS62263228 A JP S62263228A JP 10624286 A JP10624286 A JP 10624286A JP 10624286 A JP10624286 A JP 10624286A JP S62263228 A JPS62263228 A JP S62263228A
- Authority
- JP
- Japan
- Prior art keywords
- tubular body
- mol
- polyimide resin
- aromatic
- tetracarboxylic acid
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 54
- 239000004642 Polyimide Substances 0.000 title claims abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 20
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims abstract description 17
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000009719 polyimide resin Substances 0.000 claims description 47
- 150000002170 ethers Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 150000004986 phenylenediamines Chemical class 0.000 claims description 5
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 23
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 abstract description 6
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 abstract description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003495 polar organic solvent Substances 0.000 abstract description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract 2
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 abstract 1
- 238000010106 rotational casting Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 239000000057 synthetic resin Substances 0.000 description 7
- 238000001175 rotational moulding Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- RCZJVHXVCSKDKB-UHFFFAOYSA-N tert-butyl 2-[[1-(2-amino-1,3-thiazol-4-yl)-2-(1,3-benzothiazol-2-ylsulfanyl)-2-oxoethylidene]amino]oxy-2-methylpropanoate Chemical compound N=1C2=CC=CC=C2SC=1SC(=O)C(=NOC(C)(C)C(=O)OC(C)(C)C)C1=CSC(N)=N1 RCZJVHXVCSKDKB-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KBLZUSCEBGBILB-UHFFFAOYSA-N 2,2-dimethylthiolane 1,1-dioxide Chemical compound CC1(C)CCCS1(=O)=O KBLZUSCEBGBILB-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- FJEOADHMTTVGTA-UHFFFAOYSA-N CC1=C(C)P(C)(C)C(C)=C1C Chemical compound CC1=C(C)P(C)(C)C(C)=C1C FJEOADHMTTVGTA-UHFFFAOYSA-N 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241001441724 Tetraodontidae Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】 ［発明の技術分野］ 本発明は、ポリイミド樹脂管状体に関するものである。[Detailed description of the invention] [Technical field of invention] The present invention relates to a polyimide resin tubular body.
さらに詳しくは本発明は特に電気機器。More specifically, the present invention particularly relates to electrical equipment.
電子機器、電子複写機などの各種の精密機器において回
転運動の伝達などの目的で用いるに適したエンドレスベ
ルトなどの管状体に関するものである。The present invention relates to a tubular body such as an endless belt suitable for use in transmitting rotational motion in various precision instruments such as electronic equipment and electronic copying machines.
［発明の背景］
電気機器、電子機器、電子複写機、あるいはその他の精
密機器などにおいて、回転運動の伝達などの目的でエン
ドレスベルトが多数用いられている。エンドレスベルト
としては、従来より弾性を有する合成ゴム、合成樹脂な
どからなるエンドレスベルトが一般的に用いられている
。しかしながら、近年における各種機器の発達により、
耐熱性や機械的特性において更に優れた特性を有するエ
ンドレスベルトの需要が高まっている。[Background of the Invention] Many endless belts are used for purposes such as transmitting rotational motion in electrical equipment, electronic equipment, electronic copying machines, and other precision equipment. As endless belts, endless belts made of elastic synthetic rubber, synthetic resin, etc. have been commonly used. However, due to the development of various devices in recent years,
There is a growing demand for endless belts with even better heat resistance and mechanical properties.
耐熱性や機械的特性の優れた樹脂としてはポリイミド樹
脂、ポリイミドアミド樹脂が知られている。そして、ポ
リイミド樹脂等の管状体を得たのち、必要に応じてこれ
を輪切りにして製造したエンドレスベルトも既に知られ
ている。このポリイミド樹脂製のエンドレスベルトは従
来の合成ゴムあるいは合成樹脂からなるエンドレスベル
トに比較して高い耐熱性を有し、また機械的特性も優れ
ているが、エンドレスベルトの信頼性、耐久性を更に高
めるために、引張強度、伸度、弾性率、耐引き裂き性な
どが更に改良されたエンドレスベルトが強く望まれてい
る。Polyimide resins and polyimide amide resins are known as resins with excellent heat resistance and mechanical properties. Endless belts are also known, which are produced by obtaining a tubular body of polyimide resin or the like and then cutting it into rings as needed. This endless belt made of polyimide resin has higher heat resistance than conventional endless belts made of synthetic rubber or synthetic resin, and also has excellent mechanical properties. In order to increase this, an endless belt with further improved tensile strength, elongation, elastic modulus, tear resistance, etc. is strongly desired.
［発明の構成］
本発明は、優れた機械的特性を示すポリイミド樹脂管状
体を提供することを主な目的とする。[Structure of the Invention] The main object of the present invention is to provide a polyimide resin tubular body exhibiting excellent mechanical properties.
本発明は特に、従来のポリイミド樹脂エンドレスベルト
よりも更に優れた機械的特性を有するポリイミド樹脂エ
ンドレスベルトなどのポリイミド樹脂管状体を提供する
ことを目的とする。A particular object of the present invention is to provide a polyimide resin tubular body, such as a polyimide resin endless belt, which has better mechanical properties than conventional polyimide resin endless belts.
本発明は特に、引張強度、伸度１弾性率、耐引き裂き性
などの多くの機械的特性について、従来のポリイミド樹
脂エンドレスベルトよりも更に優れたポリイミド樹脂エ
ンドレスベルトなどのポリイミド樹脂管状体を提供する
ことを目的とする。In particular, the present invention provides a polyimide resin tubular body, such as a polyimide resin endless belt, which is more superior to conventional polyimide resin endless belts in terms of many mechanical properties such as tensile strength, elastic modulus at elongation, and tear resistance. The purpose is to
本発明は、全芳香族テトラカルボン酸成分に対して１５
〜８５モル％のビフェニルテトラカルボン酸類と８５〜
１５モル％のピロメリット酸類とからなる芳香族テトラ
カルボン酸成分と、全芳香族ジアミノ成分に対して３０
〜１００モル％のフェニレンジアミン類と７０−０モル
％のジアミノジフェニルエーテル類とからなる芳香族ジ
アミン成分から得られた芳香族ポリイミドからなること
を特徴とするポリイミド樹脂管状体にある。In the present invention, the total aromatic tetracarboxylic acid component has 15
~85 mol% of biphenyltetracarboxylic acids and 85~
30% for the aromatic tetracarboxylic acid component consisting of 15 mol% of pyromellitic acids and the wholly aromatic diamino component.
A polyimide resin tubular body comprising an aromatic polyimide obtained from an aromatic diamine component consisting of ~100 mol% of phenylene diamines and 70-0 mol% of diaminodiphenyl ethers.
以下１本発明のポリイミド樹脂管状体を製造する方法に
ついて、代表的な実施の態様を示して詳しく説明する。Hereinafter, a method for producing a polyimide resin tubular body according to the present invention will be described in detail by showing typical embodiments.
本発明のポリイミド樹脂管状体は、芳香族テトラカルボ
ン酸成分と芳香族ジアミン成分を極性有機溶媒中で重合
反応させてポリイミド樹脂の前駆体であるポリアミック
酸を製造したのち、このポリアミック酸溶液を公知の樹
脂管状体製造用円筒の内側表面に回転成形などの方法を
利用して塗布し、同時に、あるいは次いで、加熱するこ
とにより溶媒除去とイミド化を行なうような方法により
有利に製造することができる。The polyimide resin tubular body of the present invention is produced by polymerizing an aromatic tetracarboxylic acid component and an aromatic diamine component in a polar organic solvent to produce polyamic acid, which is a precursor of a polyimide resin, and then converting this polyamic acid solution into a publicly known solution. It can be advantageously manufactured by a method in which the resin is coated on the inner surface of a cylinder for manufacturing a resin tubular body using a method such as rotational molding, and the solvent is removed and imidized by heating at the same time or subsequently. .
本発明のポリイミド樹脂管状体の製造のために使用され
る芳香族ポリアミック酸は、全芳香族テトラカルボン酸
成分に対して１５〜８５モル％のビフェニルテトラカル
ボン酸類と８５〜１５モル％のピロメリット酸類とから
なる芳香族テトラカルボン酸成分と、全芳香族ジアミン
成分に対して３０〜１００モル％のフェニレンジアミン
類と７０〜Ｏモル％のジアミノジフェニルエーテル類と
からなる芳香族ジアミン成分を、実質的に等モル使用し
、有機極性溶媒中にて重合して得られる芳香族ポリアミ
ック酸である。The aromatic polyamic acid used for producing the polyimide resin tubular body of the present invention contains 15 to 85 mol% of biphenyltetracarboxylic acids and 85 to 15 mol% of pyromellitic acid based on the total aromatic tetracarboxylic acid component. An aromatic tetracarboxylic acid component consisting of acids, and an aromatic diamine component consisting of 30 to 100 mol% of phenylene diamines and 70 to 0 mol% of diaminodiphenyl ethers based on the total aromatic diamine component. This is an aromatic polyamic acid obtained by polymerizing in an organic polar solvent.
前記ビフェニルテトラカルボン酸類としては。As the biphenyltetracarboxylic acids.
ビフェニルテトラカルボン酸、その二無水物、またはそ
の低級アルキルエステル、さらにそれらの混合物を桑げ
るこンがでキス−ビアーグー１し÷−貴カルポン酸類と
しては、２．３°、３，４°−ビフェニルテトラカルボ
ン酸類、３．３’、４．４−ビフェニルテトラカルボン
酸類を好適に挙げることができる。Biphenyltetracarboxylic acid, its dianhydride, or its lower alkyl ester, as well as mixtures thereof, are mixed with a mulberry tree. Preferred examples include -biphenyltetracarboxylic acids and 3.3',4.4-biphenyltetracarboxylic acids.
前記ピロメリット酸類としては、ピロメリット酸、その
二無水物、またはその低級アルキルエステル、さらにそ
れらの混合物を挙げることができる。Examples of the pyromellitic acids include pyromellitic acid, its dianhydride, its lower alkyl ester, and mixtures thereof.
なお、上記芳香族テトラカルボン酸成分には、全芳香族
テトラカルボン酸成分に対して７０モル％以下、好まし
くは５０モル％以下、さらに好ましくは３０モル％以下
、の量にて他の芳香族テトラカルボン酸類を使用しても
よい、そのような他の芳香族テトラカルボン酸類の例と
しては。The aromatic tetracarboxylic acid component may contain other aromatic compounds in an amount of 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less based on the total aromatic tetracarboxylic acid component. Tetracarboxylic acids may be used as examples of other such aromatic tetracarboxylic acids.
３．３’、４，４°−ベンゾフェノンテトラカルポン酸
、２゜２−ビス（３，４−ジカルボキシフェニル）プロ
パン、ビス（３，４−ジカルボキシフェニル）メタン、
ビス（３，４−ジカルボキシフェニル）エーテル、ビス
Ｃ３，４−ジカルボキシフェニル
びこれらのカルボン酸の無水物、低級アルキルエステル
などを挙げることができる。3.3',4,4°-benzophenonetetracarboxylic acid, 2°2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyphenyl)methane,
Examples include bis(3,4-dicarboxyphenyl) ether, bisC3,4-dicarboxyphenyl, anhydrides and lower alkyl esters of these carboxylic acids.
本発明において、フェニレンジアミン類としては、１．
４−ジアミノベンゼン（パラフェニレンジアミン） 、
１．３−ジアミノベンゼン、１．２−ジアミノベンゼ
ンなどを挙げることができる。In the present invention, the phenylenediamines include 1.
4-diaminobenzene (paraphenylenediamine),
Examples include 1,3-diaminobenzene and 1,2-diaminobenzene.
本発明におい・て芳香族ジアミン成分として、全芳香族
ジアミン成分に対して７０モル％以下、好ましくは５０
モル％以下、さらに好ましくは３０モル％以下、そして
好ましくは１モル％以上、さらに好ましくは５モル％以
上の量にて、ジアミノジフェニルエーテル類を併用する
こともできる。In the present invention, the aromatic diamine component is 70 mol% or less, preferably 50 mol% or less based on the total aromatic diamine component.
Diaminodiphenyl ethers can also be used in an amount of mol % or less, more preferably 30 mol % or less, and preferably 1 mol % or more, still more preferably 5 mol % or more.
そのようなジアミノジフェニルエーテル類としては、４
，４°−ジアミノジフェニルエーテル、３．４°−ジア
ミノジフェニルエーテル、３．３°−ジアミノジフェニ
ルエーテルを好適に挙げることができる。Such diaminodiphenyl ethers include 4
, 4°-diaminodiphenyl ether, 3.4°-diaminodiphenyl ether, and 3.3°-diaminodiphenyl ether.
なお、上記芳香族ジアミン成分には、全芳香族ジアミン
成分に対して７０モル％以下、好ましくは５０モル％以
下、さらに好ましくは３０モル％以下、の量にて他の芳
香族ジアミン類を使用してもよい、そのような他の芳香
族ジアミン成分としては、４．４°−ジアミノジフェニ
ルチオエーテルなどのジフェニルチオエーテル系ジアミ
ン、３，３°−ジアミノベンゾフェノン、４，４−ジア
ミノベンゾフェノンなどのベンゾフェノン系ジアミン、
３．３’−ジアミノジフェニルホスフィン、４，４°
−ジアミノジフェニルホスフィンなどのジフェニルポス
フィン系ジアミン、３．３°−ジアミノジフェニルメタ
ン、 ４．４’−ジアミノジフェニルメタンなどのジフ
ェニルメタン系ジアミンなどを挙げることができる。In addition, other aromatic diamines are used in the aromatic diamine component in an amount of 70 mol% or less, preferably 50 mol% or less, more preferably 30 mol% or less, based on the total aromatic diamine component. Examples of such other aromatic diamine components include diphenylthioether-based diamines such as 4.4°-diaminodiphenylthioether, benzophenone-based diamines such as 3,3°-diaminobenzophenone, and 4,4-diaminobenzophenone. diamine,
3.3'-diaminodiphenylphosphine, 4,4°
Examples include diphenylphosphine diamines such as -diaminodiphenylphosphine, diphenylmethane diamines such as 3.3°-diaminodiphenylmethane, and 4.4'-diaminodiphenylmethane.
前記重合反応に使用される有機極性溶媒としては、各モ
ノマー成分、および／または両モノマー成分が生成する
オリゴマー、または低分子のポリアミック酸を均一に溶
解する溶媒を用いる。そのような有機極性溶媒の例とし
ては、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチ
ルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ−メ
チルカプロラクタムなどのアミド系溶媒、ジメチルスル
ホキシド、ヘキサメチルフォスホルアミド、ジメチルス
ルホン、テトラメチレンスルホン、ジメチルテトラメチ
レンスルホン、ピリジン、エチレングリコールなどを挙
げることができる。これらの有機極性溶媒は、ベンゼン
、トルエン、ベンゾニトリル、キシレン、ソルベントナ
フサ、およびジオキサンのような他の有機溶媒と混合し
て使用することもできる。As the organic polar solvent used in the polymerization reaction, a solvent that uniformly dissolves each monomer component and/or an oligomer produced by both monomer components, or a low-molecular polyamic acid is used. Examples of such organic polar solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam, dimethylsulfoxide, and hexamethylphosphorol. Amide, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, pyridine, ethylene glycol and the like can be mentioned. These organic polar solvents can also be used in mixtures with other organic solvents such as benzene, toluene, benzonitrile, xylene, solvent naphtha, and dioxane.
重合反応を実施するに際して、有機極性溶媒中の全七ツ
マ−の濃度は５〜４０重量％、好ましくは６〜３５重量
、％、特に好ましくは１０〜３０重量％とされる。When carrying out the polymerization reaction, the concentration of all heptamers in the organic polar solvent is 5 to 40% by weight, preferably 6 to 35% by weight, particularly preferably 10 to 30% by weight.
上記の芳香族テトラカルボン酸成分と芳香族ジアミン成
分との重合反応は、たとえば、それぞれを実質的に等モ
ルにて混合し１反応温度１００”０以下、好ましくは８
０℃以下にて約０．２〜６．０時間の反応を行なわせる
ことにより実施する。The polymerization reaction of the above-mentioned aromatic tetracarboxylic acid component and aromatic diamine component can be carried out, for example, by mixing substantially equimolar amounts of each component at a reaction temperature of 100"0 or less, preferably 80" or less.
The reaction is carried out at 0° C. or below for about 0.2 to 6.0 hours.
上記のポリアミック酸溶液は、３０”Ｏで測定した回転
粘度が、約０．１〜５ｏポイズ、特に０．１−１０ポイ
ズ、さらに好ましくは０．１〜５ポイズ程度のものであ
ることが、このポリアミック酸溶液を取り扱う作業性お
よび膜厚の均一性、表面平滑性の面から好ましい、従っ
て、前記の重合反応は、生成するポリアミック酸が上記
のような粘度を示す程度にまで実施することが望ましい
。The above polyamic acid solution has a rotational viscosity of about 0.1 to 5 poise, particularly 0.1 to 10 poise, more preferably about 0.1 to 5 poise, as measured at 30"O. This is preferable from the viewpoint of workability in handling the polyamic acid solution, uniformity of film thickness, and surface smoothness. Therefore, the above-mentioned polymerization reaction can be carried out to the extent that the polyamic acid produced exhibits the above-mentioned viscosity. desirable.
次に、上記のようにして得られたポリアミック酸溶液を
そのまま、あるいは溶媒の変更、追加、部分除去などを
行なったのち、ポリイミド樹脂管状体製造の工程に供す
る。Next, the polyamic acid solution obtained as described above is used as it is or after the solvent has been changed, added, or partially removed, and then subjected to the process of producing a polyimide resin tubular body.
ポリイミド樹脂などの合成樹脂の薄肉の管状体を製造す
る方法は各種知られており、本発明のポリイミド樹脂の
管状体の製造に際しても、それらの方法を適宜利用する
ことができる。Various methods are known for producing thin tubular bodies made of synthetic resin such as polyimide resin, and these methods can be appropriately utilized in producing the tubular body made of polyimide resin of the present invention.
すなわち、薄肉の合成樹脂管状体の代表的な製造方法と
しては、いわゆる回転成形法を挙げることができるが、
本発明のポリイミド樹脂の管状体の製造に際しても、こ
の回転成形法を利用することができる。That is, a typical manufacturing method for a thin-walled synthetic resin tubular body is the so-called rotational molding method.
This rotational molding method can also be used in manufacturing the polyimide resin tubular body of the present invention.
回転成形法は、回転下の金属製のドラム（円筒状の５）
の内側の壁表面に合成樹脂溶液あるいは合ｒ＆樹脂前駆
体溶液を付与したのち、回転を高速にし、遠心力を利用
してドラム内壁表面に均一な樹脂液塗膜を形成し１次い
でこのドラムを加熱することにより、上記塗膜からの溶
媒の除去あるいは樹脂の固化などを行なって樹脂管状体
を得ることからなる方法である。なお、得られた樹脂管
状体は、ドラムから外したのち必要に応じて、円筒の芯
などに巻き付けた状ｊｇで更に加熱されることもある。The rotational molding method uses a rotating metal drum (cylindrical 5)
After applying a synthetic resin solution or a composite R&resin precursor solution to the inner wall surface of the drum, the drum is rotated at high speed and a uniform resin liquid coating is formed on the inner wall surface of the drum using centrifugal force. This method consists of removing the solvent from the coating film or solidifying the resin by heating to obtain a resin tubular body. In addition, after the obtained resin tubular body is removed from the drum, it may be further heated by wrapping it around a cylindrical core or the like, if necessary.
本発明のポリイミド樹脂管状体を製造するための管状体
の製造に際しては、まず回転下の金属製ドラムの内側の
壁表面にポリアミック酸溶液を付与したのち１回転を高
速にし、遠心力を利用してドラム内壁表面に均一な厚さ
が１０〜１１０００ＪＬ程度のポリアミック酸溶液塗膜
を形成し、次いでこのドラムを６０−１６０℃程度に加
熱することにより、上記塗膜からの溶媒の除去を行ない
自己支持性樹脂皮膜を得る９次に、この自己支持性樹脂
皮膜をドラムから取り外し、今度は円筒芯にかぶせて、
更に３００〜４５０℃程度に加熱することによりイミド
化を完了させて目的のポリイミド樹脂管状体を得る。そ
して、必要に応じてこの管状体を輪切りにすることによ
り細幅のエンドレスベルトとする。When manufacturing the tubular body for producing the polyimide resin tubular body of the present invention, first, a polyamic acid solution is applied to the inner wall surface of a rotating metal drum, and then one rotation is made high speed to utilize centrifugal force. A polyamic acid solution coating film with a uniform thickness of about 10 to 11,000 JL is formed on the inner wall surface of the drum, and then the solvent is removed from the coating film by heating this drum to about 60 to 160°C. Obtaining a Supportive Resin Film 9 Next, this self-supporting resin film is removed from the drum and placed over the cylindrical core.
By further heating to about 300 to 450°C, imidization is completed and the desired polyimide resin tubular body is obtained. Then, if necessary, this tubular body is cut into rings to obtain a narrow endless belt.
なお、合成樹脂の回転成形において・、成形用のドラム
の内側表面に離型剤を付与すること、あるいは合成樹脂
溶液に離型剤あるいは他の種の添加剤を添加しておくこ
とは一般的に行なわれることであり、本発明の管状体の
製造に際しても、そのような公知技術を併用することが
できる。また。In addition, in rotational molding of synthetic resins, it is common to apply a mold release agent to the inner surface of the molding drum, or to add mold release agents or other types of additives to the synthetic resin solution. Such known techniques can be used in combination when manufacturing the tubular body of the present invention. Also.
回転ドラムの内壁に樹脂塗膜の形成する際の補助具とし
てスクレーパを用いること（特開昭６０−１６６４２４
号公報に記載）、回転成形する前に回転ドラムの内壁に
樹脂層を形成すること（特公昭５７−１５４５４号公報
に記載）なども併用することができる。Using a scraper as an auxiliary tool when forming a resin coating on the inner wall of a rotating drum (Japanese Patent Laid-Open No. 60-166424)
(described in Japanese Patent Publication No. 57-15454), and forming a resin layer on the inner wall of the rotating drum before rotational molding (described in Japanese Patent Publication No. 15454/1983) can also be used.
本発明のポリイミド樹脂管状体の厚みは、通常５〜５０
０ ｐｍの範囲にあり、好ましくは１０〜１００終ｍの
範囲にある。The thickness of the polyimide resin tubular body of the present invention is usually 5 to 50 mm.
It is in the range of 0 pm, preferably in the range of 10 to 100 pm.
［発明の効果］
本発明のポリイミド樹脂管状体は、その製造のだめの芳
香族カルボン酸成分として、それぞれ特定量のビフェニ
ルテトラカルボン酸類とピロメリット酸類とを併用して
得られたものであり、そのような芳香族ポリイミドフィ
ルムは、ポリイミドとしての優れた耐熱性を有する外、
優れた機械的物性、たとえば高い引張強度（室温で約２
２ｋｋ／ｍｒｎ’以上）、低い伸び率（室温で約４０％
以下）、適度なりフグ率（室温で約３００〜９００ｋｇ
／ｍｍ’）を有する。また熱的性質についても高い二次
転移温度（通常は約３００℃以上）、高い熱分解温度（
通常は約４００℃以上）を有するなど顕著に優れている
０本発明のポリイミド樹脂管状体が有するこれらの優れ
た性質は、従来より知られている種類のポリイミド樹脂
から得らえた管状体では達成することが困難である。[Effects of the Invention] The polyimide resin tubular body of the present invention is obtained by using a specific amount of biphenyltetracarboxylic acids and pyromellitic acids in combination as aromatic carboxylic acid components that are used for production. In addition to having excellent heat resistance as a polyimide, aromatic polyimide films such as
Excellent mechanical properties, such as high tensile strength (approx. 2
2kk/mrn'), low elongation rate (approximately 40% at room temperature)
below), moderate blowfish rate (approximately 300 to 900 kg at room temperature)
/mm'). In addition, regarding thermal properties, there is a high second-order transition temperature (usually about 300°C or higher) and a high thermal decomposition temperature (
These excellent properties of the polyimide resin tubular body of the present invention cannot be achieved with tubular bodies obtained from conventionally known types of polyimide resins. difficult to do.
従って１本発明のポリイミド樹脂管状体は、特に電気機
器、電子機器、電子複写機などの各種の精密機器におい
て回転運動の伝達などの目的で用いるに適したエンドレ
スベルトとして優れた特性を示ｆ−
また、本発明のポリイミド樹脂管状体は上記のように優
れた熱的性質と機械的性質を示すところから、各種のパ
イプなどとしても有用である。Therefore, the polyimide resin tubular body of the present invention exhibits excellent properties as an endless belt particularly suitable for use in various precision instruments such as electrical equipment, electronic equipment, and electronic copying machines for the purpose of transmitting rotational motion. Further, since the polyimide resin tubular body of the present invention exhibits excellent thermal properties and mechanical properties as described above, it is useful as various pipes.
次に本発明の実施例と比較例を挙げる。Next, examples of the present invention and comparative examples will be given.
［実施例１］
攪拌機を備えたセパラブルフラスコに、 Ｎ、Ｎ−ジメ
チルアセトアミド９３６ｇ、ｐ−７エニレンジアミンＣ
ＰＦＤ） ４５ 、１９１ ｇ、 ４，４°−ジアミノ
ジフェニルエーテル（４，４°−ＤＡＤＥ）３５．８６
２ｇを入れ、窒素中室温（約３０℃）で攪拌した。この
溶液に３，３°、４，４°−ビフェニルテトラカルボン
酸二無水物（ｓ−ＢＰＤＡ）８６ 。[Example 1] In a separable flask equipped with a stirrer, 936 g of N,N-dimethylacetamide and p-7 enylenediamine C were added.
PFD) 45, 191 g, 4,4°-diaminodiphenyl ether (4,4°-DADE) 35.86
2 g was added and stirred at room temperature (approximately 30°C) under nitrogen. 3,3°,4,4°-biphenyltetracarboxylic dianhydride (s-BPDA) 86 was added to this solution.
０７０ｇおよびピロメリット酸二無水物（ＰＭＤＡ）６
５．１２２ｇ、３．３’ 、４．４’−ビフェニルテト
ラカルボン酸類ＢＰＴＡ）１ ＋ ７５６ｇを添加し、
５０℃で６時間攪拌してポリアミック酸の溶液を得た。070g and pyromellitic dianhydride (PMDA) 6
5.122 g, 3.3', 4.4'-biphenyltetracarboxylic acids BPTA)1 + 756 g were added,
The mixture was stirred at 50° C. for 6 hours to obtain a polyamic acid solution.
このポリ７ミ７り酸溶液の固形分濃度は２０％であり、
回転粘度は９．３ボイズ（３０℃）であった、このポリ
アミック酸溶液の固形分濃度が１２％になるようにに、
Ｎ−ジメチルアセトアミドで希釈して成形用ドープ液と
した。この成形用ドープ液の回転粘度は１．４ポイズ（
３０℃）であった。The solid content concentration of this poly-7m-7-lic acid solution is 20%,
The rotational viscosity was 9.3 voids (30°C).The solid content concentration of this polyamic acid solution was 12%.
It was diluted with N-dimethylacetamide to obtain a molding dope. The rotational viscosity of this molding dope is 1.4 poise (
30°C).
別に、外径１３８ｍｍ、内径１３０ｍｍ、長さ３００ｍ
ｍの円筒金型（両端部が１２０ｍｍリングで液留めされ
たもの）を用意し、この円筒金型の内壁面に上記のドー
プ液６０ｇを注入した後、金型を２５℃で回転数５〜１
０ｒｐｍにて５分間回転させてドープ液を金型内壁面に
均等に付着させた。このようにしてドープ液塗膜を形成
したのち、金型の回転数を３８Ｏｒｐｍに上げるととも
に、温度を１３０℃に上げ、その温度で４００分間回転
行なって、ドープ液塗膜から溶媒の大部分を除去した。Separately, outer diameter 138mm, inner diameter 130mm, length 300m
Prepare a cylindrical mold (both ends of which are secured with 120 mm rings), inject 60 g of the above dope into the inner wall of the cylindrical mold, and then rotate the mold at 25°C and at a rotation speed of 5 to 1
The dope solution was evenly adhered to the inner wall surface of the mold by rotating at 0 rpm for 5 minutes. After forming the dope coating film in this way, the rotation speed of the mold was increased to 38 Orpm, the temperature was raised to 130°C, and the rotation was continued at that temperature for 400 minutes to remove most of the solvent from the dope coating film. Removed.
上記の方法により得られた自己支持性の乾燥膜を金型か
ら取り外し、これを一対の並列した回転可俺なローラの
周囲に掛は回し、ローラを回転させながら、１５０℃に
て３０分間、２００℃にて２０分間、２５０℃にて２０
分間、３８０℃にて１０分間の条件にて乾燥膜を加熱し
てイミド化を完了させ、ポリイミド樹脂管状体を得た。The self-supporting dry film obtained by the above method was removed from the mold, wrapped around a pair of parallel rotatable rollers, and heated at 150°C for 30 minutes while rotating the rollers. 20 minutes at 200℃, 20 minutes at 250℃
The dried film was heated at 380° C. for 10 minutes to complete imidization, and a polyimide resin tubular body was obtained.
［比較例１］
芳香族ジアミン成分として６２．８９１ｇのＰＰＤのみ
を用い、かつ芳香族テトラカルボン酸成分として１６９
．３９８ｇのｓ−Ｂ Ｐ Ｄ Ａと。[Comparative Example 1] Only 62.891 g of PPD was used as the aromatic diamine component, and 169 g of PPD was used as the aromatic tetracarboxylic acid component.
．． and 398g of s-B PDA.
２．１３０ｇのＢＰＴＡを用いた以外は実施例１と同様
にしてポリアミック酸の溶液を得た。A polyamic acid solution was obtained in the same manner as in Example 1 except that 2.130 g of BPTA was used.
得られたポリアミック酸溶液の固形分濃度は２０％であ
り、回転粘度は１３ボイズ（３０℃）であった、このポ
リアミック酸溶液の固形分濃度が１２％になるようにＮ
、Ｎ−ジメチルアセトアミドで希釈して成形用ドープ液
とした。この成形用ドープ液の回転粘度は１．６ポイズ
（３０℃）であった・
上記のドープ液を用いて実施例１と同様にしてポリイミ
ド樹脂管状体を得た。なお、この管状体の製造工程に操
作性は悪かった。The solid content concentration of the obtained polyamic acid solution was 20%, and the rotational viscosity was 13 voids (30°C). N was added so that the solid content concentration of this polyamic acid solution was 12%.
, and diluted with N-dimethylacetamide to obtain a molding dope. The rotational viscosity of this molding dope was 1.6 poise (30° C.). A polyimide resin tubular body was obtained in the same manner as in Example 1 using the above dope. Note that the process for manufacturing this tubular body had poor operability.
［比較例２］
芳香族ジアミン成分として９４．７６２ｇの４．４’−
Ｄ Ａ Ｄ Ｅのみを用い、かつ芳香族テトラカルボン
酸成分として１３７．８４６ｇのｓ−Ｂ Ｐ ＤＡと１
．７３３ｇのＢＰＴＡとを用いた以外は実施例１と同様
にしてポリアミック酸の溶液を得た。[Comparative Example 2] 94.762 g of 4.4'- as aromatic diamine component
Using only DAD E, and 137.846 g of s-B PDA as the aromatic tetracarboxylic acid component and 1
．． A solution of polyamic acid was obtained in the same manner as in Example 1 except that 733 g of BPTA was used.
得られたポリアミック酸溶液の固形分濃度は２０％であ
り、回転粘度は８．８ポイズ（３０℃）であった、この
ポリアミック酸溶液の固形分濃度が１２％になるように
Ｎ、Ｎ−ジメチルアセトアミドで希釈して成形用ドープ
液とした。この成形用ドープ液の回転粘度は１．３ボイ
ズ（３０℃）であった。The solid content concentration of the obtained polyamic acid solution was 20%, and the rotational viscosity was 8.8 poise (30°C). N, N- It was diluted with dimethylacetamide to obtain a molding dope. The rotational viscosity of this molding dope was 1.3 voids (30° C.).
上記のドープ液を用いて実施例１と同様にしてポリイミ
ド樹脂管状体を得た。A polyimide resin tubular body was obtained in the same manner as in Example 1 using the above dope solution.
［比較例３］
攪拌機を備えたセパラブルフラスコに、Ｎ、Ｎ−ジメチ
ルアセトアミド９３６ｇ、４，４°−ＤＡＤＥｌ １１
．９８９ｇとＰＭＤＡ１２２．ＯＬｌｇを入れ、５０℃
で６時間、次いで３０℃で３時間攪拌してポリアミック
酸溶液を得た。[Comparative Example 3] 936 g of N,N-dimethylacetamide and 4,4°-DADEl 11 were placed in a separable flask equipped with a stirrer.
．． 989g and PMDA122. Add OLlg and heat to 50℃
The mixture was stirred for 6 hours at 30° C. and then for 3 hours at 30° C. to obtain a polyamic acid solution.
得られたポリアミック酸溶液の固形分濃度は２０％であ
り、回転粘度は１８ポイズ（３０℃）であった、このポ
リアミック酸溶液の固形分温度が１２％になるようにＮ
、Ｎ−ジメチルアセトアミドで希釈して成形用ドープ
液とした。この成形用ドープ液の回転粘度は２．３ポイ
ズ（３０℃）であった。The solid content concentration of the obtained polyamic acid solution was 20%, and the rotational viscosity was 18 poise (30°C). N was added so that the solid content temperature of this polyamic acid solution was 12%.
, and diluted with N-dimethylacetamide to obtain a molding dope. The rotational viscosity of this molding dope was 2.3 poise (30°C).
上記のドープ液を用いて実施例１と同様にしてポリイミ
ド樹脂管状体を得た。なお、この管状体の製造工程の操
作性は悪かった。A polyimide resin tubular body was obtained in the same manner as in Example 1 using the above dope solution. Note that the operability of the manufacturing process for this tubular body was poor.
［ポリイミド樹脂管状体の評価］
実施例と比較例で得られたポリイミド樹脂管状体を幅１
０ｍｍに輪切りにして、ポリイミド樹脂エンドレスベル
トとした。[Evaluation of polyimide resin tubular bodies] The polyimide resin tubular bodies obtained in Examples and Comparative Examples were
It was cut into rounds of 0 mm to make polyimide resin endless belts.
上記のポリイミド樹脂エンドレスベルトについてモ均厚
さを測定し、次いで２５℃と２００℃における引張強度
、伸度、引張弾性率および端裂抵抗を測定した。なお、
端裂抵抗のａｌｌ定はＪＩＳ−Ｃ−２３１８に従って行
ない、また引張強度、伸度および引張弾性率はＡＳＴＭ
−Ｄ−８８２に従って測定した。測定結果を第１表に示
す。The uniform thickness of the above polyimide resin endless belt was measured, and then the tensile strength, elongation, tensile modulus, and end tear resistance at 25°C and 200°C were measured. In addition,
All end tear resistance was determined according to JIS-C-2318, and tensile strength, elongation, and tensile modulus were determined according to ASTM.
-D-882. The measurement results are shown in Table 1.
第１表
平均 引張 伸度 引張 端裂
厚さ 強度 弾性率 抵抗
（ｈ ｍ） （ｋｇ／ｍｒｒＩ′） （Ｘ）
（ｋｇ／ｍｒｎ’ ） （ｋｇ／２ｃｍ）実施例１
２５℃ ４０ ２５ ３５ ４５４ ２９２００℃
１７ ４０ ３２６ −比較例１
２５℃ ５０ ３５ ３２ ８００ ２０２００℃
３０ ４０ ５５０ −比較例２
２５℃ ４０ ２０ ６５ ３７６ ２５２００℃
１２ ７５ １８３ −比較例３
２５℃ ４０ １９ ７５ ３６０ ２３２００℃
１３ ８５ １９０ −上記の結果から
明らかなように、本発明のポリイミド樹脂管状体は引張
強度については公知のポリイミド樹脂管状体の引張強度
のほぼ中間的な値を示すが、その伸度は公知のボリイミ
下樹脂管状体の伸度のうち最も低い（すなわち伸びにく
い）ものとほぼ同等であり、また引張弾性率は公知のポ
リイミド樹脂管状体の引張弾性率のうち最も低い（すな
わち弾性が高い）ものに近い値を示している。そして、
特に端裂抵抗についは本発明のポリイミド樹脂管状体が
公知のポリイミド樹脂管状体のいずれに比較しても顕著
に高い（すなわち最も裂けにくい）ことが明らかである
。Table 1 Average Tensile Elongation Tensile End Crack Thickness Strength Modulus Resistance (hm) (kg/mrrI') (X)
(kg/mrn') (kg/2cm) Example 1 25°C 40 25 35 454 29200°C
17 40 326 - Comparative Example 1 25°C 50 35 32 800 20200°C
30 40 550 - Comparative Example 2 25°C 40 20 65 376 25200°C
12 75 183 - Comparative Example 3 25°C 40 19 75 360 23200°C
13 85 190 - As is clear from the above results, the polyimide resin tubular body of the present invention exhibits a tensile strength that is approximately intermediate to that of known polyimide resin tubular bodies, but its elongation is higher than that of known polyimide resin tubular bodies. It is almost the same as the lowest elongation (i.e., difficult to stretch) of the polyimide resin tubular body, and the tensile modulus is the lowest (i.e., high elasticity) of the tensile modulus of known polyimide resin tubular bodies. It shows a value close to . and,
In particular, it is clear that the polyimide resin tubular body of the present invention has significantly higher end tear resistance (that is, it is the least likely to tear) than any of the known polyimide resin tubular bodies.
Claims (1)
モル％のビフェニルテトラカルボン酸類と８５〜１５モ
ル％のピロメリット酸類とからなる芳香族テトラカルボ
ン酸成分と、全芳香族ジアミン成分に対して３０〜１０
０モル％のフェニレンジアミン類と７０〜０モル％のジ
アミノジフェニルエーテル類とからなる芳香族ジアミン
成分から得られた芳香族ポリイミドからなることを特徴
とするポリイミド樹脂管状体。 ２、芳香族ジアミン成分が、全芳香族ジアミン成分に対
して３０〜９５モル％のフェニレンジアミン類と７０〜
５モル％のジアミノジフェニルエーテル類とからなる芳
香族ジアミン成分からなることを特徴とする特許請求の
範囲第１項記載のポリイミド樹脂管状体。 ３、エンドレスベルトの形態にあることを特徴とする特
許請求の範囲第１項もしくは第２項記載のポリイミド樹
脂管状体。[Scope of Claims] 1. 15 to 85 with respect to the wholly aromatic tetracarboxylic acid component
An aromatic tetracarboxylic acid component consisting of 85 to 15 mol% of biphenyltetracarboxylic acids and 85 to 15 mol% of pyromellitic acids, and 30 to 10% of the total aromatic diamine component.
A polyimide resin tubular body comprising an aromatic polyimide obtained from an aromatic diamine component consisting of 0 mol% of phenylene diamines and 70 to 0 mol% of diaminodiphenyl ethers. 2. The aromatic diamine component is 30 to 95 mol% of phenylene diamines and 70 to 95 mol% of the total aromatic diamine component.
The polyimide resin tubular body according to claim 1, characterized in that the polyimide resin tubular body comprises an aromatic diamine component consisting of 5 mol% of diaminodiphenyl ethers. 3. The polyimide resin tubular body according to claim 1 or 2, which is in the form of an endless belt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61106242A JPH0694509B2 (en) | 1986-05-08 | 1986-05-08 | Polyimide resin ring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61106242A JPH0694509B2 (en) | 1986-05-08 | 1986-05-08 | Polyimide resin ring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62263228A true JPS62263228A (en) | 1987-11-16 |
| JPH0694509B2 JPH0694509B2 (en) | 1994-11-24 |
Family
ID=14428646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61106242A Expired - Lifetime JPH0694509B2 (en) | 1986-05-08 | 1986-05-08 | Polyimide resin ring |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694509B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01139228A (en) * | 1987-11-26 | 1989-05-31 | Nitto Denko Corp | Manufacture of tube-shaped material |
| JP2005068227A (en) * | 2003-08-21 | 2005-03-17 | Suzuka Fuji Xerox Co Ltd | Polyimide film and transfer or fixing member for electrophotography using the polyimide film |
| JP2009120796A (en) * | 2007-10-22 | 2009-06-04 | Hitachi Chem Co Ltd | Heat-resistant polyimide resin, and seamless tubular body, coated film, coated plate and heat-resistant coating material, using the same |
| JP2009221397A (en) * | 2008-03-18 | 2009-10-01 | Ube Ind Ltd | Polyimide precursor solution composition, and polyimide film |
| JP2009221398A (en) * | 2008-03-18 | 2009-10-01 | Ube Ind Ltd | Polyamic acid solution composition, and polyimide film |
| JP2009269958A (en) * | 2008-05-01 | 2009-11-19 | Fuji Xerox Co Ltd | Polyamic acid composition and polyimide resin molding |
| CN114854011A (en) * | 2022-05-27 | 2022-08-05 | 中化学科学技术研究有限公司 | Polyamide acid solution, polyimide film and preparation method thereof |
| CN114920931A (en) * | 2022-05-27 | 2022-08-19 | 中化学科学技术研究有限公司 | Polyimide precursor composition, polyimide film, and method for producing same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118827A (en) * | 1980-02-25 | 1981-09-18 | Nitto Electric Ind Co Ltd | Manufacture of polyimide tube |
| JPS57181857A (en) * | 1981-05-06 | 1982-11-09 | Ube Industries | Polyimide laminated material and its manufacture |
| JPS58162635A (en) * | 1982-03-19 | 1983-09-27 | Nitto Electric Ind Co Ltd | Manufacture of polyimide tube |
| JPS6213436A (en) * | 1985-07-11 | 1987-01-22 | Nitto Electric Ind Co Ltd | Colorless transparent polyimide molding |
-
1986
- 1986-05-08 JP JP61106242A patent/JPH0694509B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118827A (en) * | 1980-02-25 | 1981-09-18 | Nitto Electric Ind Co Ltd | Manufacture of polyimide tube |
| JPS57181857A (en) * | 1981-05-06 | 1982-11-09 | Ube Industries | Polyimide laminated material and its manufacture |
| JPS58162635A (en) * | 1982-03-19 | 1983-09-27 | Nitto Electric Ind Co Ltd | Manufacture of polyimide tube |
| JPS6213436A (en) * | 1985-07-11 | 1987-01-22 | Nitto Electric Ind Co Ltd | Colorless transparent polyimide molding |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01139228A (en) * | 1987-11-26 | 1989-05-31 | Nitto Denko Corp | Manufacture of tube-shaped material |
| JP2005068227A (en) * | 2003-08-21 | 2005-03-17 | Suzuka Fuji Xerox Co Ltd | Polyimide film and transfer or fixing member for electrophotography using the polyimide film |
| JP2009120796A (en) * | 2007-10-22 | 2009-06-04 | Hitachi Chem Co Ltd | Heat-resistant polyimide resin, and seamless tubular body, coated film, coated plate and heat-resistant coating material, using the same |
| JP2009221397A (en) * | 2008-03-18 | 2009-10-01 | Ube Ind Ltd | Polyimide precursor solution composition, and polyimide film |
| JP2009221398A (en) * | 2008-03-18 | 2009-10-01 | Ube Ind Ltd | Polyamic acid solution composition, and polyimide film |
| JP2009269958A (en) * | 2008-05-01 | 2009-11-19 | Fuji Xerox Co Ltd | Polyamic acid composition and polyimide resin molding |
| CN114854011A (en) * | 2022-05-27 | 2022-08-05 | 中化学科学技术研究有限公司 | Polyamide acid solution, polyimide film and preparation method thereof |
| CN114920931A (en) * | 2022-05-27 | 2022-08-19 | 中化学科学技术研究有限公司 | Polyimide precursor composition, polyimide film, and method for producing same |
| CN114854011B (en) * | 2022-05-27 | 2023-08-18 | 中化学科学技术研究有限公司 | Polyamide acid solution, polyimide film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0694509B2 (en) | 1994-11-24 |
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