JPH0770276A - Heat-resistant resin - Google Patents
Heat-resistant resinInfo
- Publication number
- JPH0770276A JPH0770276A JP5221656A JP22165693A JPH0770276A JP H0770276 A JPH0770276 A JP H0770276A JP 5221656 A JP5221656 A JP 5221656A JP 22165693 A JP22165693 A JP 22165693A JP H0770276 A JPH0770276 A JP H0770276A
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- acid
- molecular weight
- reaction
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Polyurethanes Or Polyureas (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、得られる成形物の機械
的特性が著しく改良されたポリアミド、ポリイミドある
いはポリアミドイミドに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide, a polyimide or a polyamide-imide in which the resulting molded product has remarkably improved mechanical properties.
【０００２】[0002]
【従来の技術】ジイソシアネートと多価カルボン酸およ
び／または酸無水物をＮ−メチル−２−ピロリドン、ジ
メチルアセトアミドなどの有機極性溶媒中、１００〜２
００℃で数時間加熱縮合して、ポリアミド、ポリイミド
あるいはポリアミドイミドを得る方法は従来より行われ
てきた。2. Description of the Related Art Diisocyanate and polycarboxylic acid and / or acid anhydride are mixed with 100 to 2 in an organic polar solvent such as N-methyl-2-pyrrolidone or dimethylacetamide.
A method of obtaining a polyamide, a polyimide, or a polyamide-imide by heat-condensing at 00 ° C. for several hours has been conventionally performed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、このよ
うに溶媒中でジイソシアネートを加熱すると、該イソシ
アネートは溶媒分子と副反応を起こす。このような副反
応は、得られるポリマーの高分子量化の達成を妨げるば
かりでなく、成形物の機械的性質に悪影響を及ぼすポリ
マーの分岐・架橋反応をも促進する。However, when the diisocyanate is heated in the solvent in this manner, the isocyanate causes a side reaction with the solvent molecule. Such side reactions not only hinder the achievement of high molecular weight of the obtained polymer, but also promote the branching / crosslinking reaction of the polymer which adversely affects the mechanical properties of the molded product.
【０００４】一般に上記方法では、重合温度が高いほど
得られるポリマーの分子量はある程度高分子量化するこ
とができるが、同時にジイソシアネートの副反応および
ポリマーの分岐・架橋反応も進行するため、該ポリマー
の多分散度は広くなる。このためそのようなポリマーか
ら得られる成形物の機械的性質は、数平均分子量から予
想される程高いものではなくなる。Generally, in the above method, the higher the polymerization temperature is, the higher the molecular weight of the obtained polymer can be made, but at the same time, the side reaction of diisocyanate and the branching / crosslinking reaction of the polymer also proceed. The degree of dispersion is wide. As a result, the mechanical properties of moldings obtained from such polymers are not as high as expected from the number average molecular weight.
【０００５】すなわち本発明の目的は、多分散性を小さ
くしたまま、すなわちジイソシアネートと溶媒との副反
応やポリマーの分岐・架橋反応をおさえながら高分子量
化することにより、成形物の機械的性質が著しく改良さ
れたポリアミド、ポリイミドあるいはポリアミドイミド
を提供することにある。That is, the object of the present invention is to improve the mechanical properties of a molded article by keeping the polydispersity small, that is, by increasing the molecular weight while suppressing the side reaction between diisocyanate and a solvent and the branching / crosslinking reaction of the polymer. It is to provide a markedly improved polyamide, polyimide or polyamide-imide.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究した結果、本発明に至った。
すなわち本発明は、ジイソシアネートと多価カルボン酸
および／または多価カルボン酸から誘導される酸無水物
を縮合させて得られる、数平均分子量が少なくとも５
０，０００、多分散性が約１．５〜４．０の高分子量ポ
リアミド、ポリイミドあるいはポリアミドイミドに関す
る。なかでも、イソシアネートとしてｏ−トリジンジイ
ソシアネートを使用したものは、特に優れた機械的特性
をもつ。[Means for Solving the Problems] The present inventors have accomplished the present invention as a result of intensive studies for achieving the above-mentioned object.
That is, the present invention has a number average molecular weight of at least 5 obtained by condensing a diisocyanate with a polycarboxylic acid and / or an acid anhydride derived from the polycarboxylic acid.
10,000, a polydispersity of about 1.5 to 4.0 and a high molecular weight polyamide, polyimide or polyamideimide. Among them, those using o-tolidine diisocyanate as the isocyanate have particularly excellent mechanical properties.
【０００７】本発明のポリマーの製造において用いられ
るモノマーとして、以下のものが挙げられるが、これら
に限定されるわけではない。すなわち、酸成分として
は、多価カルボン酸および／または多価カルボン酸の酸
無水物が用いられる。多価カルボン酸として、たとえば
テレフタル酸、イソフタル酸、４，４’−ビフェニルジ
カルボン酸、ピロメリット酸、３，３’，４，４’−ベ
ンゾフェノンテトラカルボン酸、３，３’，４，４’−
ビフェニルスルホンテトラカルボン酸、３，３’，４，
４’−ビフェニルテトラカルボン酸、アジピン酸、セバ
シン酸、マレイン酸、フマール酸、ダイマー酸、スチル
ベンジカルボン酸など、脂肪族ジカルボン酸、芳香族ジ
カルボン酸、その他の多価カルボン酸が挙げられる。こ
れらの多価カルボン酸は、単独であるいは混合物として
用いられる。Monomers used in the preparation of the polymers of the present invention include, but are not limited to, the following: That is, as the acid component, a polyvalent carboxylic acid and / or an acid anhydride of the polyvalent carboxylic acid is used. Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, 4,4′-biphenyldicarboxylic acid, pyromellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4,4 ′. −
Biphenyl sulfone tetracarboxylic acid, 3,3 ', 4
4′-biphenyltetracarboxylic acid, adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbenedicarboxylic acid, and other aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and other polyvalent carboxylic acids. These polyvalent carboxylic acids may be used alone or as a mixture.
【０００８】多価カルボン酸の酸無水物として、たとえ
ば、無水トリメリット酸、ベンゾフェノンテトラカルボ
ン酸無水物、ジフェニルスルホンテトラカルボン酸無水
物、ビフェニルテトラカルボン酸無水物、ピロメリット
酸無水物などが挙げられる。これらの酸無水物は、単独
であるいは混合物として用いられる。Examples of polycarboxylic acid anhydrides include trimellitic anhydride, benzophenonetetracarboxylic acid anhydride, diphenylsulfonetetracarboxylic acid anhydride, biphenyltetracarboxylic acid anhydride, and pyromellitic acid anhydride. To be These acid anhydrides may be used alone or as a mixture.
【０００９】イソシアネート成分としては、たとえばｏ
−トリジンジイソシアネート、ｐ−フェニレンジイソシ
アネート、ｍ−フェニレンジイソシアネート、２，４−
トリレンジイソシアネート、２，６−トリレンジイソシ
アネート、４，４’−ジフェニルメタンジイソシアネー
ト、３，３’−ジメチルジフェニル−４，４’−ジイソ
シアネート、３，３’−ジエチルジフェニル−４，４’
−ジイソシアネート、イソホロンジイソシアネート、ヘ
キサメチレンジイソシアネート、４，４’−ジシクロヘ
キシルメタンジイソシアネート、ｍ−キシレンジイソシ
アネート、ｐ−キシレンジイソシアネート、ナフタレン
ジイソシアネートなどが挙げられ、特にｏ−トリジンジ
イソシアネートが好ましい。これらのイソシアネートは
単独であるいは混合物として用いられる。As the isocyanate component, for example, o
-Tolidine diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 2,4-
Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4,4 '
-Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene diisocyanate, etc. are particularly preferred, and o-tolidine diisocyanate is particularly preferred. These isocyanates may be used alone or as a mixture.
【００１０】ジイソシアネート成分と酸成分の配合比
は、モル比で酸成分／イソシアネート成分＝１１０／１
００〜１００／１１０、好ましくは１００／１００であ
る。The mixing ratio of the diisocyanate component and the acid component is a molar ratio of acid component / isocyanate component = 110/1.
It is from 00 to 100/110, preferably 100/100.
【００１１】本発明のポリマーを製造する方法に特に制
限はないが、下記する方法によれば容易に本発明で規定
するポリマーを得ることができる。すなわち、あらかじ
め有機溶媒中に、酸成分として上記の多価カルボン酸お
よび／または多価カルボン酸無水物とイソシアネート成
分として上記のジイソシアネートを比較的高濃度に溶解
させ、これを比較的低温度で縮合させ（第１段反応）、
次にこのようにして得られた反応混合物を第１段反応の
モノマー濃度以下の濃度に希釈し、これを第１段反応の
反応温度以上の温度でさらに重縮合する（第２段反
応）。Although the method for producing the polymer of the present invention is not particularly limited, the polymer specified in the present invention can be easily obtained by the following method. That is, the above-mentioned polyvalent carboxylic acid and / or polyvalent carboxylic acid anhydride as an acid component and the above diisocyanate as an isocyanate component are dissolved in a relatively high concentration in an organic solvent in advance, and this is condensed at a relatively low temperature. Let (first stage reaction),
Next, the reaction mixture thus obtained is diluted to a concentration not higher than the monomer concentration of the first-step reaction, and this is further polycondensed at a temperature not lower than the reaction temperature of the first-step reaction (second-step reaction).
【００１２】第１段反応の温度は、１５０℃以下、好ま
しくは１００℃以下、さらに好ましくは６０〜１００℃
である。またモノマー濃度は、２０重量％以上、好まし
くは３０〜５５重量％である。第１段反応終了時のポリ
マーの分子量（数平均分子量）は２，０００〜２０，０
００、とりわけ５，０００〜１５，０００が、多分散性
は、１．３〜３．０、とりわけ１．５〜２．３が好まし
い。The temperature of the first stage reaction is 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 60 to 100 ° C.
Is. The monomer concentration is 20% by weight or more, preferably 30 to 55% by weight. The molecular weight (number average molecular weight) of the polymer at the end of the first stage reaction is 2,000 to 20,0.
00, especially 5,000 to 15,000, and polydispersity of 1.3 to 3.0, especially 1.5 to 2.3 are preferred.
【００１３】第２段反応は、第１段反応の反応温度以上
の反応温度で行なう。また得られた反応混合物を溶媒で
希釈し、その濃度を第１段反応のモノマー濃度以下の濃
度にして反応を行なう。特に、反応温度を第１段反応の
反応温度以上でかつ１００〜２００℃に、かつ反応混合
物濃度を第１段反応のモノマー濃度以下でかつ１５〜３
５重量％に調整するのが好ましい。The second-step reaction is carried out at a reaction temperature higher than the reaction temperature of the first-step reaction. Further, the obtained reaction mixture is diluted with a solvent so that the concentration thereof is equal to or lower than the monomer concentration of the first stage reaction, and the reaction is performed. In particular, the reaction temperature is not less than the reaction temperature of the first stage reaction and is 100 to 200 ° C., and the reaction mixture concentration is not more than the monomer concentration of the first stage reaction and 15 to 3
It is preferably adjusted to 5% by weight.
【００１４】本発明のポリマー製造において使用する有
機溶媒は、主として、ジメチルホルムアミド、ジメチル
アセトアミド、Ｎ−メチル−２−ピロリドン、ジメチル
スルフォキシド、スルホラン、γ−ブチロラクトンであ
るが、シクロヘキサノン、イソホロンなどのケトン類、
ジオキサン、テトラヒドロフランなどのエーテル類、ト
ルエン、キシレンなどの炭化水素類、プロピオニトリ
ル、アセトニトリルなどのニトリル系、ニトロメタン、
ニトロエタンなどのニトロ系溶媒なども使用しうる。こ
れらは単独あるいは混合溶媒として用いる。The organic solvent used in the production of the polymer of the present invention is mainly dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, and cyclohexanone, isophorone and the like. Ketones,
Ethers such as dioxane and tetrahydrofuran, hydrocarbons such as toluene and xylene, nitriles such as propionitrile and acetonitrile, nitromethane,
A nitro solvent such as nitroethane may also be used. These are used alone or as a mixed solvent.
【００１５】また、本発明においては、反応をイソシア
ネートと活性水素化合物の反応に対する触媒、たとえ
ば、３級アミン類、アルカリ金属化合物、アルカリ土類
金属化合物、コバルト、チタニウム、スズ、亜鉛などの
金属、反金属化合物などの存在下に行ってもよい。Further, in the present invention, the reaction is a catalyst for the reaction between isocyanate and an active hydrogen compound, for example, tertiary amines, alkali metal compounds, alkaline earth metal compounds, metals such as cobalt, titanium, tin and zinc, It may be carried out in the presence of an antimetal compound or the like.
【００１６】このようにして得られる本発明のポリマー
は、ＧＰＣで測定した数平均分子量（Ｍｎ）が少なくと
も５０，０００、好ましくは６０，０００〜１００，０
００であり、多分散性（Ｍｗ／Ｍｎ）は１．５〜４．
０、好ましくは、２．０〜３．０である。数平均分子量
が５０，０００以上でかつ多分散性が上記範囲内であれ
ば、従来では得られなかった引張り強度、引張り伸度な
ど機械的特性の優れた成形物が得られる。The polymer of the present invention thus obtained has a number average molecular weight (Mn) measured by GPC of at least 50,000, preferably 60,000 to 100,000.
And the polydispersity (Mw / Mn) is 1.5 to 4.
It is 0, preferably 2.0 to 3.0. When the number average molecular weight is 50,000 or more and the polydispersity is within the above range, a molded product excellent in mechanical properties such as tensile strength and tensile elongation, which has hitherto not been obtained, can be obtained.
【００１７】本発明のポリマーは、一般にＮ−メチル−
２−ピロリドンなどの有機溶媒に可溶であり、得られた
反応混合物をそのまま繊維やフィルムなどに溶液成形す
ることにより、優れた機械的特性を有する成形物を得る
ことができる。これは、本発明のポリマーの数平均分子
量および多分散性が上記した範囲内であるという特徴を
有しているためである。The polymers of the present invention are generally N-methyl-
A molded product that is soluble in an organic solvent such as 2-pyrrolidone and that has an excellent mechanical property can be obtained by directly solution-casting the obtained reaction mixture into a fiber or a film. This is because the polymer of the present invention has a feature that the number average molecular weight and the polydispersity are within the ranges described above.
【００１８】[0018]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれら実施例に限定されるものではな
い。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１９】各実施例で製造したポリマーあるいはフィ
ルムの物性は以下にように測定した。 １．対数粘度（ｄｌ／ｇ） Ｎ−メチル−２−ピロリドン１００ｍｌ中にポリマー
０．５ｇを溶解した希薄溶液について、温度２５℃で相
対粘度を測定し、以下の式より算出した。 対数粘度＝ｌｎηｒｅｌ／Ｃ （式中、ηｒｅｌは相対粘度を、Ｃはポリマー溶液の濃
度を示す。） ２．分子量（Ｍｎ：数平均分子量、Ｍｗ：重量平均分子
量） ＧＰＣ法により以下の方法で測定した。 ｉ）カラム：ｓｈｏｄｅｘ〔昭和電工（株）〕ＡＤ８０
０Ｐ、ＡＤ８０５／Ｓ、ＡＤ８０４／Ｓ、ＡＤ８０３／
Ｓ、ＡＤ８０２／Ｓを直列に接続した。 ｉｉ）移動相：臭化リチウムを０．１重量％溶解したＮ
−メチル−２−ピロリドン ｉｉｉ）標準物質：以下の分子量（Ｍｎ）のポリスチレ
ンを用いた。 １． ６，７７０，０００ ２． ２，８７０，０００ ３． １，２６０，０００ ４． ３５５，０００ ５． １０２，０００ ６． ４３，９００ ７． ９，５００ ８． ５，４００ ９． ２，８００ ｉｖ）装置：自動サンプラー〔島津（株）製、ＳＣＬ６
Ａ〕 ポンプ〔島津（株）製、ＬＣ６Ａ〕 データ換算システム〔島津（株）製、ＣＲ−４Ａ〕 屈打計〔昭和電工（株）製、ＳＥ−５１〕 ３．引張強度（ｋｇ／ｍｍ2 ）、引張伸度（％）および
弾性率（ｋｇ／ｍｍ2 ）ＪＩＳ−Ｃ−２３１８に依る。The physical properties of the polymer or film produced in each example were measured as follows. 1. Logarithmic viscosity (dl / g) Relative viscosity was measured at a temperature of 25 ° C. for a dilute solution in which 0.5 g of the polymer was dissolved in 100 ml of N-methyl-2-pyrrolidone, and the relative viscosity was calculated from the following formula. Logarithmic viscosity = ln ηrel / C (wherein ηrel represents relative viscosity and C represents the concentration of the polymer solution). Molecular weight (Mn: number average molecular weight, Mw: weight average molecular weight) It was measured by the following method by the GPC method. i) Column: shodex [Showa Denko KK] AD80
0P, AD805 / S, AD804 / S, AD803 /
S and AD802 / S were connected in series. ii) Mobile phase: N in which 0.1% by weight of lithium bromide was dissolved
-Methyl-2-pyrrolidone iii) Standard: polystyrene with the following molecular weight (Mn) was used. 1. 6,770,000 2. 2,870,000 3. 1,260,000 4. 355,000 5. 102,000 6. 43,900 7. 9,500 8. 5,400 9. 2,800 iv) device: Automatic sampler [Shimadzu Corporation, SCL6
A] Pump [LC6A manufactured by Shimadzu Corporation] Data conversion system [CR-4A manufactured by Shimadzu Corporation] Deflection meter [SE-51 manufactured by Showa Denko KK] 3. Tensile strength (kg / mm 2 ), tensile elongation (%) and elastic modulus (kg / mm 2 ) according to JIS-C-2318.
【００２０】実施例１ 反応容器に下記の重合成分を仕込み、窒素雰囲気下、攪
拌しながら７０℃で約２時間、さらに１００℃で約３時
間反応させた（第１段反応）。重合成分 無水トリメリット酸 １９２ｇ ｏ−トリジンジイソシアネート ２１１ｇ ４，４’−ジフェニルメタンジイソシアネート ５０ｇ Ｎ−メチル−２−ピロリドン（蒸留されたもの） ３６５ｇ その後、Ｎ−メチル−２−ピロリドンを１リットル加
え、約２時間かけて２００℃まで昇温し、さらに２００
℃で約１時間攪拌して反応を停止した（第２段反応）。
得られたポリマー溶液を厚さ１００μｍの離型性ポリエ
ステルフィルム上に乾燥後の厚みが３０μｍとなるよう
に流延塗布し、１００℃で５分、１５０℃で３０分乾燥
した後、該離型性フィルムから剥離した。その後、溶媒
を完全に除去するため、減圧下、２００℃で約３時間加
熱した。このようにして得られたポリマーおよびポリマ
ーフィルムの各種物性を表１に示す。Example 1 The following polymerization components were charged in a reaction vessel, and reacted under nitrogen atmosphere with stirring at 70 ° C. for about 2 hours and further at 100 ° C. for about 3 hours (first stage reaction). Polymerization component trimellitic anhydride 192 g o-trizine diisocyanate 211 g 4,4′-diphenylmethane diisocyanate 50 g N-methyl-2-pyrrolidone (distilled) 365 g Then, 1 liter of N-methyl-2-pyrrolidone was added, and about 2 Temperature rises to 200 ℃ over time
The reaction was stopped by stirring at C for about 1 hour (second stage reaction).
The polymer solution thus obtained was cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying would be 30 μm, dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes, Peeled from the film. Then, in order to completely remove the solvent, the mixture was heated at 200 ° C. under reduced pressure for about 3 hours. Table 1 shows various physical properties of the thus obtained polymer and polymer film.
【００２１】実施例２ 第１段反応の重合成分を以下のようにした以外は実施例
１と同様の方法でポリマーを得、さらにフィルムの製造
を行った。重合成分 無水トリメリット酸 １５４ｇ ３，３’，４，４’−ベンゾフェノンテトラカルボン酸無水物 ６５ｇ ｏ−トリジンジイソシアネート ２６４ｇ Ｎ−メチル−２−ピロリドン（蒸留されたもの） ３９５ｇ 得られたポリマーおよびフィルムの各種物性を表１に示
す。Example 2 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-stage reaction were changed as follows, and a film was further produced. Polymerization component trimellitic anhydride 154 g 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride 65 g o-tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 395 g of the obtained polymer and film Table 1 shows various physical properties.
【００２２】実施例３ 第１段反応の重合成分を以下のようにした以外は実施例
１と同様の方法でポリマーを得、さらにフィルムの製造
を行った。重合成分 無水トリメリット酸 １９２ｇ ２，４−トリレンジイソシアネート ３５ｇ ｏ−トリジンジイソシアネート ２６４ｇ Ｎ−メチル−２−ピロリドン（蒸留されたもの） ４５０ｇ 得られたポリマーおよびフィルムの各種物性を表１に示
す。Example 3 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-stage reaction were changed as follows, and a film was further produced. Polymerization component trimellitic anhydride 192 g 2,4-tolylene diisocyanate 35 g o-tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 450 g Table 1 shows various physical properties of the obtained polymer and film.
【００２３】実施例４ 第１段反応の重合成分を以下のようにした以外は実施例
１と同様の方法でポリマーを得、さらにフィルムの製造
を行った。重合成分 イソフタル酸 ８３ｇ テレフタル酸 ８３ｇ ｏ−トリジンジイソシアネート ２６４ｇ Ｎ−メチル−２−ピロリドン（蒸留されたもの） ４１８ｇ 得られたポリマーおよびフィルムの各種物性を表１に示
す。Example 4 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-stage reaction were changed as follows, and a film was produced. Polymerization component Isophthalic acid 83 g Terephthalic acid 83 g o-Tolidine diisocyanate 264 g N-methyl-2-pyrrolidone (distilled) 418 g Various physical properties of the obtained polymer and film are shown in Table 1.
【００２４】実施例５ 第１段反応の重合成分を以下のようにした以外は実施例
１と同様の方法でポリマーを得、さらにフィルムの製造
を行った。重合成分 イソフタル酸 １６６ｇ ｏ−トリジンジイソシアネート ２６４ｇ ２，４−トリレンジイソシアネート ３５ｇ Ｎ−メチル−２−ピロリドン（蒸留されたもの） ４６０ｇ 得られたポリマーおよびフィルムの各種物性を表１に示
す。Example 5 A polymer was obtained in the same manner as in Example 1 except that the polymerization components in the first-step reaction were changed as follows, and a film was produced. Polymerization component Isophthalic acid 166 g o-Tolidine diisocyanate 264 g 2,4-Tolylene diisocyanate 35 g N-methyl-2-pyrrolidone (distilled) 460 g Table 1 shows various physical properties of the obtained polymer and film.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【発明の効果】本発明のポリアミド、ポリイミドあるい
はポリアミドイミドは、多分散性を小さくしたままで高
分子量化されているので、特に機械的特性の著しく優れ
た成形品が得られる。EFFECT OF THE INVENTION Since the polyamide, polyimide or polyamide-imide of the present invention is made into a high molecular weight while keeping the polydispersity small, a molded article having particularly excellent mechanical properties can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西野 英雄 滋賀県大津市堅田二丁目１番１号 東洋紡 績株式会社総合研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Nishino 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.
Claims (2)
び／または多価カルボン酸から誘導される酸無水物を縮
合させて得られる、数平均分子量が少なくとも５０，０
００、多分散性が約１．５〜４．０の高分子量ポリアミ
ド、ポリイミドあるいはポリアミドイミド。1. A number average molecular weight of at least 50,0 obtained by condensing a diisocyanate with a polyvalent carboxylic acid and / or an acid anhydride derived from the polyvalent carboxylic acid.
00, a high molecular weight polyamide, polyimide or polyamide-imide having a polydispersity of about 1.5 to 4.0.
ジイソシアネートを必須とする請求項１記載のポリアミ
ド、ポリイミドあるいはポリアミドイミド。2. The polyamide, polyimide or polyamide-imide according to claim 1, wherein o-tolidine diisocyanate is essential as the diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22165693A JP3531184B2 (en) | 1993-09-07 | 1993-09-07 | Heat resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22165693A JP3531184B2 (en) | 1993-09-07 | 1993-09-07 | Heat resistant resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0770276A true JPH0770276A (en) | 1995-03-14 |
| JP3531184B2 JP3531184B2 (en) | 2004-05-24 |
Family
ID=16770200
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22165693A Expired - Lifetime JP3531184B2 (en) | 1993-09-07 | 1993-09-07 | Heat resistant resin |
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| Country | Link |
|---|---|
| JP (1) | JP3531184B2 (en) |
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|---|---|---|---|---|
| JP2006281453A (en) * | 2005-03-31 | 2006-10-19 | Furukawa Electric Co Ltd:The | Material for electric and electronic component and its manufacturing method |
| JP2013527294A (en) * | 2010-05-27 | 2013-06-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Material, manufacturing method thereof, and component thereof |
| TWI558740B (en) * | 2015-12-07 | 2016-11-21 | 財團法人工業技術研究院 | Thermal conductive resin and thermal interface material comprising the same |
| JP2020019937A (en) * | 2018-07-19 | 2020-02-06 | 住友化学株式会社 | Polyamide-imide resin |
| WO2020137871A1 (en) * | 2018-12-26 | 2020-07-02 | 住友化学株式会社 | Polyimide resin and method for producing same |
| JP2020105497A (en) * | 2018-12-26 | 2020-07-09 | 住友化学株式会社 | Polyimide resin and manufacturing method thereof |
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1993
- 1993-09-07 JP JP22165693A patent/JP3531184B2/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006281453A (en) * | 2005-03-31 | 2006-10-19 | Furukawa Electric Co Ltd:The | Material for electric and electronic component and its manufacturing method |
| JP2013527294A (en) * | 2010-05-27 | 2013-06-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Material, manufacturing method thereof, and component thereof |
| TWI558740B (en) * | 2015-12-07 | 2016-11-21 | 財團法人工業技術研究院 | Thermal conductive resin and thermal interface material comprising the same |
| CN106832282A (en) * | 2015-12-07 | 2017-06-13 | 财团法人工业技术研究院 | Heat conductive resin and thermal interface material containing same |
| EP3178868A1 (en) * | 2015-12-07 | 2017-06-14 | Industrial Technology Research Institute | Thermally conductive resin and thermal interface material comprising the same |
| JP2017106011A (en) * | 2015-12-07 | 2017-06-15 | 財團法人工業技術研究院Ｉｎｄｕｓｔｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｒｅｓｅａｒｃｈ Ｉｎｓｔｉｔｕｔｅ | Thermally conductive resin and thermal interface material comprising the same |
| US10329468B2 (en) | 2015-12-07 | 2019-06-25 | Industrial Technology Research Institute | Thermally conductive resin and thermal interface material comprising the same |
| JP2020019937A (en) * | 2018-07-19 | 2020-02-06 | 住友化学株式会社 | Polyamide-imide resin |
| WO2020137871A1 (en) * | 2018-12-26 | 2020-07-02 | 住友化学株式会社 | Polyimide resin and method for producing same |
| JP2020105497A (en) * | 2018-12-26 | 2020-07-09 | 住友化学株式会社 | Polyimide resin and manufacturing method thereof |
| CN113227205A (en) * | 2018-12-26 | 2021-08-06 | 住友化学株式会社 | Polyimide resin and method for producing same |
| CN113227205B (en) * | 2018-12-26 | 2023-10-03 | 住友化学株式会社 | Polyimide resin and method for producing same |
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| Publication number | Publication date |
|---|---|
| JP3531184B2 (en) | 2004-05-24 |
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