JPH0129382B2 - - Google Patents
Info
- Publication number
- JPH0129382B2 JPH0129382B2 JP8609284A JP8609284A JPH0129382B2 JP H0129382 B2 JPH0129382 B2 JP H0129382B2 JP 8609284 A JP8609284 A JP 8609284A JP 8609284 A JP8609284 A JP 8609284A JP H0129382 B2 JPH0129382 B2 JP H0129382B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- pai
- mol
- alkyl group
- diamine
- 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.)
- Expired
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- 229920002312 polyamide-imide Polymers 0.000 claims description 27
- 239000011347 resin Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 239000004962 Polyamide-imide Substances 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- 239000004416 thermosoftening plastic Substances 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910005965 SO 2 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- QGMGHALXLXKCBD-UHFFFAOYSA-N 4-amino-n-(2-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1N QGMGHALXLXKCBD-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
〔産業上の利用分野〕
本発明は特に300〜400℃の温度領域における良
好な熱安定性および流動性を兼備し、かつ射出成
形可能なジフエニルエーテル結合を必須成分とし
て含有する非晶性熱可塑性芳香族ポリアミドイミ
ド樹脂（以下、ポリアミドイミドをPAIと略称す
る）の熱変形温度および力学特性を改善すること
を目的とした樹脂組成物に関するものである。
〔従来の技術〕
米国デユポン社商標“ベスペルSP”およびア
ツプジヨン社商標“ポリイミド2080”で代表され
るポリイミド樹脂は、耐熱性、機械的強度、耐薬
品性、電気的特性が極めてすぐれているが、溶融
加工性がなく、溶融成形できないのに対し、ジア
ミン（またはジイソシアネート）残基が
（ただし、R1は炭素数１〜４のアルキル基、R2
は炭素数１〜４のアルキル基またはハロゲン原
子、Ｘは−SO2−基、
[Industrial Field of Application] The present invention particularly relates to an amorphous thermoplastic material having good thermal stability and fluidity in the temperature range of 300 to 400°C, and containing diphenyl ether bonds as an essential component, which can be injection molded. The present invention relates to a resin composition aimed at improving the heat distortion temperature and mechanical properties of a plastic aromatic polyamide-imide resin (hereinafter, polyamide-imide is abbreviated as PAI). [Prior art] Polyimide resins represented by the trademark "Vespel SP" by DuPont and the trademark "Polyimide 2080" by U.S. company U.S.A. have excellent heat resistance, mechanical strength, chemical resistance, and electrical properties. It has no melt processability and cannot be melt molded, whereas diamine (or diisocyanate) residues (However, R 1 is an alkyl group having 1 to 4 carbon atoms, R 2
is an alkyl group having 1 to 4 carbon atoms or a halogen atom, X is a -SO2- group,
【式】または[expression] or
そこで本発明者らは、上記の非晶性熱可塑性芳
香族PAI樹脂の熱変形温度および力学特性を向上
させることを目的として鋭意検討を行なつた結
果、特定の分子構造を有する第２の耐熱性PAI樹
脂を配合することが極めて効果的であることを見
出し、本発明に到達した。
〔問題点を解決するための手段および作用〕
すなわち、本発明は
(イ) ジアミン（またはジイソシアネート）残基が
次の構造および組成（ただし全体で100モル％）
で構成される非晶性熱可塑性芳香族PAI樹脂20
〜97重量％
および
(ロ) ジアミン（またはジイソシアネート）残基の
60モル％を越え100モル％以下が
Therefore, the present inventors conducted intensive studies with the aim of improving the heat distortion temperature and mechanical properties of the above-mentioned amorphous thermoplastic aromatic PAI resin. The present invention has been achieved based on the discovery that it is extremely effective to incorporate a synthetic PAI resin. [Means and effects for solving the problems] That is, the present invention provides (a) diamine (or diisocyanate) residues having the following structure and composition (however, 100 mol% in total)
Amorphous thermoplastic aromatic PAI resin composed of 20
~97% by weight and (b) diamine (or diisocyanate) residues.
More than 60 mol% and less than 100 mol%
【式】または[expression] or
【式】の構造成分で構成
される耐熱性PAI樹脂80〜３重量％からなる
PAI樹脂組成物（ただし、R1は炭素数１〜４
のアルキル基、R2は炭素数１〜４のアルキル
基またはハロゲン原子、Ｘは−SO2−基、
Consists of 80-3% by weight of a heat-resistant PAI resin composed of the structural components of [Formula]
PAI resin composition (where R 1 is a carbon number of 1 to 4
an alkyl group, R 2 is an alkyl group having 1 to 4 carbon atoms or a halogen atom, X is a -SO 2 - group,
【式】または[expression] or
【式】ａは１〜25、ｂ
は０または１〜４、ｃは０または１〜２の整数
を示す）。を提供するものである。
本発明で用いられる第１成分としての非晶性熱
可塑性芳香族PAI樹脂は一般式
または
で表わされる高分子主鎖中にイミド結合およびア
ミド結合を必須成分として含有する芳香族重合体
類であり、式中、Ｚは３官能基のうちの２官能基
が隣接炭素に結合されている３官能性芳香族基、
Arは２価の芳香族残基を示す。また、Y1は合成
原料として用いるジアミン（またはジイソシアネ
ート）から誘導される残基を示し、次の構造およ
び組成（ただし全体で100％）で構成される。
（ただし、R1は炭素数１〜４のアルキル基、R2
は炭素数１〜４のアルキル基またはハロゲン原
子、Ｘは−SO2−基、[Formula] a represents an integer of 1 to 25, b represents 0 or 1 to 4, and c represents an integer of 0 or 1 to 2). It provides: The amorphous thermoplastic aromatic PAI resin used in the present invention as the first component has the general formula or These are aromatic polymers containing imide bonds and amide bonds as essential components in the main chain of the polymer represented by, where Z is two of the three functional groups bonded to adjacent carbons. trifunctional aromatic group,
Ar represents a divalent aromatic residue. In addition, Y 1 represents a residue derived from diamine (or diisocyanate) used as a synthetic raw material, and is composed of the following structure and composition (however, 100% in total). (However, R 1 is an alkyl group having 1 to 4 carbon atoms, R 2
is an alkyl group having 1 to 4 carbon atoms or a halogen atom, X is a -SO2- group,
【式】または[expression] or
【式】ａは１〜25、ｂは０または１〜４、
ｃは０または１〜２の整数を示す。）
この構造（）および（）の中でのイミド結
合の一部（たとえば30モル％未満）が、その閉環
前駆体としてのアミド酸結合[Formula] a represents an integer of 1 to 25, b represents 0 or 1 to 4, and c represents an integer of 0 or 1 to 2. ) A portion (e.g., less than 30 mol%) of the imide bonds in this structure () and () are amic acid bonds as their ring-closing precursors.
【式】の状態でとどまつているものも含 まれる。ここでＺの例としては、Including those that remain in the state of [formula]. be caught. Here, as an example of Z,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】などの構造を具体
的に列挙することができる。Arは少なくとも一
つの炭素６員環を含む２価の芳香族基であり、た
とえば、Structures such as [Formula] can be specifically listed. Ar is a divalent aromatic group containing at least one carbon 6-membered ring, for example,
【式】【formula】
【式】【formula】
【式】（式中ＸはＯ、Ｓ、
CO、SO2、SO、炭素原子数１〜６個のアルキル
基を示す）などが挙げられる。上記式（）で示
されるPAI樹脂（）はジメチルホルムアミド、
ジメチルアセトアミド、Ｎ−メチルピロリドン、
クレゾールなどの極性有機溶媒中で[Formula] (wherein X represents O, S, CO, SO 2 , SO, or an alkyl group having 1 to 6 carbon atoms). The PAI resin () represented by the above formula () is dimethylformamide,
dimethylacetamide, N-methylpyrrolidone,
In polar organic solvents such as cresol
【式】【formula】
【式】【formula】
【式】などの組合せ
を反応させることにより合成される。
また、上記式（）で示されるPAI樹脂（）
は、PAI樹脂（）の原料のIt is synthesized by reacting combinations such as [Formula]. In addition, PAI resin () shown by the above formula ()
is the raw material of PAI resin ()
【式】ま たは[Formula] Ma Taha
【式】の一部をPart of [formula]
【式】 または【formula】 or
【式】で置換して反応させること により合成される。 Y1単位の具体例としてはたとえば It is synthesized by substituting with [Formula] and reacting. As a specific example of Y 1 unit, for example
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
などが挙げられる。
これらジアミン（またはジイソシアネート）残
基Ｙを構成する成分中、(ii)の構造体が80モル％を
越えるとPAIが次第に結晶性となつて溶融成形性
が著しく低下するので好ましくない。また(iii)の構
造体が60％を越えると、PAIの物性、特に強靭性
が目立つて低下するので実用上価値がない。
本発明で使用される第１成分PAI樹脂の典型例
として、次の３種を挙げることができる。
本発明で用いられる第２成分としての耐熱性
PAI樹脂は一般式
または
で表わされる高分子鎖中にイミド結合およびアミ
ド結合を必須成分として含有する芳香族重合体類
であり、Y2は合成原料として用いるジアミン
（またはジイソシアネート）から誘導される残基
を示し、その60モル％を越えた分（好ましくは70
モル％以上）が[Formula] etc. Among the components constituting these diamine (or diisocyanate) residues Y, if the structure (ii) exceeds 80 mol %, PAI gradually becomes crystalline and melt moldability is significantly reduced, which is not preferable. Furthermore, if the content of the structure (iii) exceeds 60%, the physical properties of PAI, particularly the toughness, will be noticeably reduced and thus have no practical value. Typical examples of the first component PAI resin used in the present invention include the following three types. Heat resistance as a second component used in the present invention
PAI resin has a general formula or These are aromatic polymers containing imide bonds and amide bonds as essential components in the polymer chain represented by Y 2 , where Y 2 represents a residue derived from diamine (or diisocyanate) used as a synthetic raw material, and the 60 Exceeding mol% (preferably 70
mole% or more)
【式】（R1は炭素数１
〜４のアルキル基、ｂは０または１〜４の整数を
示す）または[Formula] (R 1 is an alkyl group having 1 to 4 carbon atoms, b is 0 or an integer of 1 to 4) or
【式】で、残
りの40モル％以下（好ましくは30モル％以下）が
その他の芳香族二価残基で構成される。この構造
（）および（）の中でのイミド結合の一部
（たとえば30モル％以下）がその閉環前駆体とし
てのアミド酸結合In the formula, the remaining 40 mol% or less (preferably 30 mol% or less) is composed of other aromatic divalent residues. A part of the imide bonds (for example, 30 mol% or less) in this structure () and () are the amic acid bonds as their ring-closing precursors.
【式】の状態にとどま
つているものも含まれる。また、（）、（）式
中のＺおよびArの内容および式（）、（）で
表わされるPAIの一般的合成法は、上記PAI樹脂
（）および（）の場合と同じである。
Y2の具体例としてはIt also includes those that remain in the state of [Formula]. Furthermore, the contents of Z and Ar in formulas () and () and the general synthesis method of PAI represented by formulas () and () are the same as in the case of the above-mentioned PAI resins () and (). A specific example of Y 2 is
【式】【formula】
【式】【formula】
【式】【formula】
以下、実施例をあげて本発明をさらに詳述す
る。
なお、本実施例に示す％、比および部の値は、
特にことわらない限りそれぞれ重量％、重量比お
よび重量部を示す。また、重合体の対数粘度は、
ポリマー濃度：0.5ｇ／dl、溶媒：Ｎ−メチル−
２−ピロリドン、温度：30℃の条件下に測定した
ものである。
実施例１〜４および比較例１〜３
まず、無水トリメリツト酸モノクロリド、４・
4′−スルホニルビス（パラフエニレンオキシ）ジ
アニリンおよび４・4′−ジアミノジフエニルエー
テル（102：50：50モル比）を室温条件下、Ｎ・
Ｎ−ジメチルアセトアミド（DMAC）溶媒中で
反応させて得られたポリアミド酸を回収し、180
〜230℃で加熱閉環させて次の構造を有するPAI
樹脂を合成した（これをPAI−A1と略称する）。
このPAI−A1の対数粘度は0.65であつた。
別途、無水トリメリツト酸モノクロリドおよび
メタフエニレンジアミン（102：100モル比）を室
温条件下、DMAC溶媒中で反応させて得られた
ポリアミド酸を回収し、180〜230℃で加熱閉環さ
せて次の構造を有するPAI樹脂を合成した（これ
をPAI−B1と略称する）。このPAI−B1の対数粘
度は0.35であつた。
次にPAI−A1を20％濃度でDMACに溶解した
溶液とPAI−B1を20％濃度でDMACに溶解した
溶液を第１表の組成で均一混合した後、大量の水
中に投入して混合組成物を沈殿させ、続いてロ
過／洗浄を３回繰返して沈殿物を回収した後、
150〜200℃で熱風処理して乾燥した混合組成物粉
末を得た。
次にこの混合組成物を圧縮成形（処理温度320
〜360℃、圧力50〜100Kg／cm2）にかけて厚さ３mm
の試験片を作成し、続いてこの試験片を220℃で
５時間、245℃で24時間、260℃で48時間の順で熱
処理した後、物性測定を行なつたところ次の第１
表のような結果が得られた。
この結果からわかるようにPAI−A1にPAI−
B1を10〜60％の量で配合すると比較例１のPAI
−A1そのものに比べて、熱変形温度（HDT）お
よび曲げ強度がともに効果的に改善される。また
比較例２および３にみられるようにPAI−B1が
80％を越えるところでは、HDTは高いものの曲
げ強度が大巾に低下して実用性がなくなる。
Hereinafter, the present invention will be further explained in detail by giving Examples. In addition, the values of %, ratio and parts shown in this example are as follows:
Unless otherwise specified, weight %, weight ratio, and weight parts are shown, respectively. Also, the logarithmic viscosity of the polymer is
Polymer concentration: 0.5g/dl, solvent: N-methyl-
2-Pyrrolidone, measured at a temperature of 30°C. Examples 1 to 4 and Comparative Examples 1 to 3 First, trimellitic anhydride monochloride, 4.
4′-sulfonylbis(paraphenyleneoxy)dianiline and 4,4′-diaminodiphenyl ether (102:50:50 molar ratio) were mixed with N.
The polyamic acid obtained by reaction in N-dimethylacetamide (DMAC) solvent was collected and 180
PAI with the following structure by ring-closing by heating at ~230℃
A resin was synthesized (abbreviated as PAI-A 1 ).
The logarithmic viscosity of this PAI-A 1 was 0.65. Separately, the polyamic acid obtained by reacting trimellitic anhydride monochloride and metaphenylene diamine (102:100 molar ratio) in a DMAC solvent at room temperature was recovered, ring-closed by heating at 180 to 230°C, and then We synthesized a PAI resin with the structure (abbreviated as PAI-B 1 ). The logarithmic viscosity of this PAI-B 1 was 0.35. Next, a solution of PAI-A 1 dissolved in DMAC at a concentration of 20% and a solution of PAI-B 1 dissolved in DMAC at a concentration of 20% were mixed uniformly with the composition shown in Table 1, and then poured into a large amount of water. After precipitating the mixed composition and subsequently repeating filtration/washing three times to collect the precipitate,
A mixed composition powder was obtained by hot air treatment at 150 to 200°C and drying. Next, this mixed composition is compression molded (processing temperature 320
~360℃, pressure 50~100Kg/ cm2 ) to a thickness of 3mm
A test piece of
The results shown in the table were obtained. As can be seen from this result, PAI−A 1 and PAI−
When B 1 is blended in an amount of 10 to 60%, the PAI of Comparative Example 1
− Compared with A 1 itself, both heat distortion temperature (HDT) and bending strength are effectively improved. Also, as seen in Comparative Examples 2 and 3, PAI-B 1
If it exceeds 80%, although the HDT is high, the bending strength decreases significantly, making it impractical.
【表】
実施例５、６および比較例４、５
まず、無水トリメリツト酸モノクロリドおよび
４・4′−スルホニルビス（パラフエニレンオキ
シ）ジアニリン（102：100モル比）を室温条件下
Ｎメチル−２−ピロリドン（NMP）溶媒中で反
応させて得られたポリアミド酸を回収し、180〜
230℃で加熱閉環させて次の構造を有するPAI樹
脂を合成した（これをPAI−A2と略称する）。こ
のPAI−A2の対数粘度は0.50であつた。
別途、無水トリメリツト酸モノクロリド、イソ
フタロイルクロリドおよびメタフエニレンジアミ
ン（70：32：100モル比）を室温条件下、NMP
溶媒中で反応させて得られたポリアミド酸を回収
し、180〜230℃で加熱閉環させて次の構造を有す
るPAI樹脂を合成した（これをPAI−B2と略称す
る）。このPAI−B2の対数粘度は0.31であつた。
次にPAI−A2およびPAI−B2を第２表の組成
でドライブレンドした後、ブラベンダープラスト
グラフ押出機（処理温度320〜360℃）に供給して
均一配合ペレツトを得た。
次にこのペレツトを射出成形機（バレル温度
330〜350℃、金型温度180〜220℃、射出圧力1250
〜1500Kg／cm2）にかけて射出成形試験片を作成
し、物理的特性を測定したところ第２表のような
結果を得た。第２表からわかるように実施例５お
よび６の組成物はPAI−A2およびPAI−B2の単
独系に対応した比較例４および５に比べて曲げ強
度が顕著に改善された。[Table] Examples 5 and 6 and Comparative Examples 4 and 5 First, trimellitic anhydride monochloride and 4,4'-sulfonylbis(paraphenyleneoxy)dianiline (102:100 molar ratio) were mixed with N-methyl- The polyamic acid obtained by reaction in 2-pyrrolidone (NMP) solvent is collected and
A PAI resin having the following structure was synthesized by heating and ring-closing at 230°C (this is abbreviated as PAI-A 2 ). The logarithmic viscosity of this PAI-A 2 was 0.50. Separately, trimellitic anhydride monochloride, isophthaloyl chloride, and metaphenylenediamine (70:32:100 molar ratio) were mixed with NMP under room temperature conditions.
The polyamic acid obtained by the reaction in a solvent was collected and ring-closed by heating at 180 to 230°C to synthesize a PAI resin having the following structure (this will be abbreviated as PAI-B 2 ). The logarithmic viscosity of this PAI-B 2 was 0.31. Next, PAI-A 2 and PAI-B 2 were dry blended according to the composition shown in Table 2, and then fed to a Brabender plastograph extruder (processing temperature 320-360°C) to obtain uniformly blended pellets. Next, this pellet is put into an injection molding machine (barrel temperature
330~350℃, mold temperature 180~220℃, injection pressure 1250
-1500Kg/cm 2 ), injection molded test pieces were prepared and physical properties were measured, and the results shown in Table 2 were obtained. As can be seen from Table 2, the bending strength of the compositions of Examples 5 and 6 was significantly improved compared to Comparative Examples 4 and 5, which corresponded to single systems of PAI-A 2 and PAI-B 2 .
本発明の樹脂組成物は、
特に300〜400℃の温度領域における良好な熱安
定性および流動性を兼備し、かつ射出成形可能な
ジフエニルエーテル結合を必須成分として含有す
る非晶性熱可塑性芳香族ポリアミドイミド樹脂の
熱変形温度および力学特性が改善され、射出成形
または押出成形を行うことが可能であり、多くの
用途に活用することができる。
The resin composition of the present invention is an amorphous thermoplastic aromatic composition that has good thermal stability and fluidity, especially in the temperature range of 300 to 400°C, and contains injection moldable diphenyl ether bonds as an essential component. The heat distortion temperature and mechanical properties of group polyamide-imide resins are improved, and they can be injection molded or extruded, and can be utilized in many applications.
Claims (1)
基が次の構造および組成（ただし全体で100モ
ル％）で構成される非晶性熱可塑性芳香族ポリ
アミドイミド樹脂20〜97重量％ および (ロ) ジアミン（またはジイソシアネート）残基の
60モル％を越え100モル％以下が
【式】または 【式】の構造成分で構成 される耐熱性ポリアミドイミド樹脂80〜３重量
％からなるポリアミドイミド樹脂組成物（ただ
し、R1は炭素数１〜４のアルキル基、R2は炭
素数１〜４のアルキル基またはハロゲン原子、
Ｘは−SO2−基、【式】または 【式】ａは１〜25、ｂは０または１〜 ４、ｃは０または１〜２の整数を示す）。[Scope of Claims] 1 (a) 20 to 97% by weight of an amorphous thermoplastic aromatic polyamide-imide resin in which diamine (or diisocyanate) residues have the following structure and composition (however, the total is 100% by mole) and (b) diamine (or diisocyanate) residues.
A polyamide-imide resin composition consisting of 80 to 3% by weight of a heat-resistant polyamide-imide resin in which more than 60 mol% and 100 mol% of which is a structural component of [Formula] or [Formula] (However, R 1 is a carbon number of 1 ~4 alkyl group, R2 is an alkyl group having 1 to 4 carbon atoms or a halogen atom,
X is a -SO 2 - group, [Formula] or [Formula] a is 1 to 25, b is 0 or 1 to 4, and c is 0 or an integer of 1 to 2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8609284A JPS60231759A (en) | 1984-05-01 | 1984-05-01 | Polyamide-imide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8609284A JPS60231759A (en) | 1984-05-01 | 1984-05-01 | Polyamide-imide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60231759A JPS60231759A (en) | 1985-11-18 |
| JPH0129382B2 true JPH0129382B2 (en) | 1989-06-09 |
Family
ID=13877062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8609284A Granted JPS60231759A (en) | 1984-05-01 | 1984-05-01 | Polyamide-imide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60231759A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61203171A (en) * | 1985-03-06 | 1986-09-09 | Toray Ind Inc | Polyamide-imide resin composition |
| JPS62257828A (en) * | 1986-05-01 | 1987-11-10 | Toray Ind Inc | Sliding member of clip chain for oven |
| JP2653401B2 (en) * | 1987-02-20 | 1997-09-17 | 日立化成工業 株式会社 | Method for producing polyamidoimide silicone polymer |
| JP2833744B2 (en) * | 1987-06-11 | 1998-12-09 | 日立化成工業株式会社 | Polyetheramide imide resin paste |
| DE4119300A1 (en) * | 1991-06-12 | 1992-12-17 | Huels Chemische Werke Ag | POLYAMIDE MOLDS |
-
1984
- 1984-05-01 JP JP8609284A patent/JPS60231759A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60231759A (en) | 1985-11-18 |
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