JP4908698B2 - DYE-CONTAINING POLYAMIDE ACID SOLUTION AND POLYIMIDE-TYPE TONE FILM, AND METHOD FOR PRODUCING POLYIMIDE-TYPE TONE FILM - Google Patents

DYE-CONTAINING POLYAMIDE ACID SOLUTION AND POLYIMIDE-TYPE TONE FILM, AND METHOD FOR PRODUCING POLYIMIDE-TYPE TONE FILM Download PDF

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JP4908698B2
JP4908698B2 JP2001270557A JP2001270557A JP4908698B2 JP 4908698 B2 JP4908698 B2 JP 4908698B2 JP 2001270557 A JP2001270557 A JP 2001270557A JP 2001270557 A JP2001270557 A JP 2001270557A JP 4908698 B2 JP4908698 B2 JP 4908698B2
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polyimide
dye
group
polyamic acid
solvent
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JP2003073472A (en
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渉 山下
勝治 渡辺
貴久 小口
甲也 小島
英樹 生田
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Description

【0001】
【発明の属する技術分野】
本発明は、特定の有機系色素を含有したポリアミド酸溶液、およびそれらから得られるポリイミド系色調フィルム、さらには色素含有ポリアミド酸溶液、ポリイミド系色調フィルムの製造方法に関する。
【0002】
【従来の技術】
従来より、ポリイミドは、その優れた耐熱性に加え、機械特性、電気特性等の点において優れているため、成形材料、複合材料、電気・電子材料としてさまざまな分野で幅広く用いられている。
【0003】
例えば、代表的なポリイミドとして、式(A)や式(B)
のポリイミドが知られている。これらのポリイミドフィルムは、耐熱性や機械特性で優れているため、電子材料分野では幅広く用いられているが、黄〜赤褐色に呈色しており、色素を混ぜるなどの修飾を施して色調をコントロールしたフィルムを得ることは非常に困難である。
【化7】

Figure 0004908698
【0004】
また、式(C)で示されるポリエーテルイミドは、前記式(A)、(B)のポリイミドと比べれば無色透明性は格段に向上するものの、それでもまだやや淡黄色であり、色調をコントロールしたフィルムとしての使用は困難である。また、このポリエーテルイミドはガラス転移温度が215℃程度であり、耐熱性樹脂としてもそれほど魅力あるものではない。
【0005】
更に、ポリイミドの主鎖骨格中にフルオロ基やトリフルオロメチル基の導入により無色透明性を向上させる試みがなされている。例えば、米国航空宇宙局(NASA)所属のA.K.St.Clairらが、Polymeric Materials Science and Engineering,vol.59,pp28(1988年)や欧州特許02999865で、山下らが米国特許5354839や同5410084でさまざまなポリイミドを開示している。これらのポリイミドについては無色透明性が高いことから色調をコントロールしたポリイミドフィルムを得ることは可能である。しかしながら、それらのポリイミドはフルオロ基やトリフルオロメチル基等の必須置換基導入のために、非常に高価な原材料を使用しなければならなく、実用化では大きな障壁となっている。
【0006】
一方、カラー液晶表示装置のカラーフィルターとして、顔料等を含有したポリイミドは既に知られている。例えば、特開昭58−46325号公報、特開昭60−184202号公報、特開昭60−184203号公報、特開昭61−254905号公報、特開平2−4201号公報、特開平7−11132号公報、特開平7−13012号公報、特開平7−198929号公報、特開平8−152617号公報、特開平9−20865号公報、特開平10−63193号公報等である。しかしながら、これらに含まれる顔料(カラーインデックスで言うC.I.Pigment)は基本的に溶媒に対して不溶であり、ポリイミド層中に分散した形で存在する。従って、その分散性が問題となってくる。また、これらの先行技術は液晶表示素子を構成する層の一部であり、単独のフィルムとして利用されるものではない。更に、これらの先行技術で用いられるポリイミド自身も、基本的には芳香族のポリイミドであり、ポリイミドフィルムとしての無色透明性はあまり良好ではない。
【0007】
従って、無色透明であるポリイミドを利用し、更に色素等を添加して色調をコントロールしたポリイミド系色調フィルムについては未だ実現されていない。
【0008】
【発明が解決しようとする課題】
本発明の目的は、耐熱性、機械特性、耐薬品性、電気特性等を有し、かつ無色透明性を有する特異なポリイミドに有機系色素を添加して、色調をコントロールしたポリイミド系の色調フィルムを提供することにある。また、その前駆体であるポリアミド酸に色素添加した色素含有ポリアミド酸を提供する事にある。
【0009】
【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検討を重ねた結果、特定の構造を有するポリアミド酸の溶液に有機系色素を添加して色素含有ポリアミド酸を構成し、かつフィルム化により色調を制御したポリイミド系色調フィルムを得ることが可能であることを見出し、本発明を完成した。
【0010】
すなわち、本発明は、以下を含む。
【0011】
[1]
一般式(1)
【化1】
Figure 0004908698
で表される繰り返し構造単位を有するポリアミド酸の溶液と、
前記溶液に溶解している有機系色素と、を含み、
前記溶液は、フェノール系溶媒、非プロトン性アミド系溶媒、エーテル系溶媒およびアミン系溶媒からなる群から選ばれており、前記有機系色素を可溶とする有機溶剤を含有する、
色素含有ポリアミド酸溶液(式中、Rは炭素数4〜27であり、かつ脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、環式脂肪族基または芳香族基が直接または架橋員により相互に連結された非縮合多環式脂肪族基または芳香族基からなる群より選ばれた4価の基を示す。)。
[2]
式(2)
【化2】
Figure 0004908698
で表される繰り返し構造単位を有するポリアミド酸の溶液と、前記有機系色素と、を含有してなる[1]に記載の色素含有ポリアミド酸溶液。
[3]
ポリマー100重量部に対して少なくとも1種以上の前記有機系色素を0.001〜10.0重量部含有してなる[1]または[2]に記載の色素含有ポリアミド酸溶液。
[4]
[1]に記載の色素含有ポリアミド酸溶液から得られるポリイミド系色調フィルムであって、
一般式(3)
【化3】
Figure 0004908698
で表される繰り返し構造単位を有する無色透明ポリイミドと、フェノール系溶媒、非プロトン性アミド系溶媒、エーテル系溶媒およびアミン系溶媒からなる群から選ばれる有機溶剤に可溶な有機系色素と、を含有してなるポリイミド系色調フィルム(式中、Rは炭素数4〜27であり、かつ脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、環式脂肪族基または芳香族基が直接または架橋員により相互に連結された非縮合多環式脂肪族基または芳香族基からなる群より選ばれた4価の基を示す。)。
[5]
式(4)
【化4】
Figure 0004908698
で表される繰り返し構造単位を有する無色透明ポリイミドと、前記有機系色素と、を含有してなる請求項4に記載のポリイミド系色調フィルム。
[6]
ポリマー100重量部に対して少なくとも1種以上の前記有機系色素を0.001〜10.0重量部含有してなる請求項4または5に記載のポリイミド系色調フィルム。
[7]
ポリアミド酸溶液を加熱処理することにより、脱溶媒及びイミド化する工程と、を含み、
前記ポリアミド酸溶液は、[1]から[3]のいずれか1項に記載の色素含有ポリアミド酸溶液である、ポリイミド系色調フィルムの製造方法。
【0023】
【発明の実施の形態】
本発明において、母体となるポリイミド、およびその前駆体であるポリアミド酸のくり返し単位構造は下記の通りであり、
【0024】
【化14】
Figure 0004908698
【0025】
【化15】
Figure 0004908698
【0026】
(式中Rは前記に同じ。)、好ましくはポリイミド、およびその前駆体であるポリアミド酸の構造が
【0027】
【化16】
Figure 0004908698
【0028】
【化17】
Figure 0004908698
【0029】
式(3)および(4)で表される繰り返し構造単位を有するポリイミドは、ポリイミドが本来有する優れた諸物性、すなわち、耐熱性、機械特性、電気特性等の物性を有し、かつ優れた無色透明性を有する樹脂である(特願平12−226324記載)。このポリイミドは、必須モノマーとして、ジアミノメチル−ビシクロ[2.2.1]ヘプタン(以下NBDA)とテトラカルボン酸二無水物より構成される。ここで、NBDAは単独の構造でも、あるいは構造異性体の混合物でも良い。包含される構造異性体としては、主として(2S,5S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン((2S,5S)−NBDA)、(2S,5R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン((2S,5R)−NBDA)、(2S,6R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン((2S,6R)−NBDA)、および(2S,6S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン((2S、6S)−NBDA)等であるが、その他の構造異性体が含有されても構わない。また、それらの組成比についてはいかなる組成であっても構わない。テトラカルボン酸二無水物については、一般的には高純度の二無水物を用いるが、開環物あるいはエステル化物等を用いても構わない。この時、テトラカルボン酸二無水物がピロメリット酸二無水物であるとき、式(2)で表されるポリアミド酸、および式(3)で表されるポリイミドが得られる。
【0030】
更に、本発明において使用されるポリイミドが本来有する無色透明性、耐熱性等の性能を損なわない範囲において、他の脂環式ジアミンを共重合化することも可能である。その際使用される量は、全ジアミン成分の30モル%以下、好ましくは10モル%以下である。また、これらの脂環式ジアミン化合物のほかに、本発明の特性を損なわない範囲で芳香族ジアミン、ジアミノシロキサン類、あるいは脂環式以外の脂肪族ジアミン等を共重合化することが可能である。その際使用される量も、同じく全ジアミン成分の30モル%以下、好ましくは10モル%以下である。これら共重合化に使用されるジアミン類は、単独でも2種以上を混合して用いても良い。
【0031】
また、本発明で使用される酸二無水物については、2種以上の芳香族テトラカルボン酸二無水物、脂肪族テトラカルボン酸二無水物を併用しても良い。
【0032】
本発明で使用されるポリアミド酸およびポリイミドは前記式(1)および(2)で表されるが、その分子末端は封止されていても、されていなくてもよい。
【0033】
また、本発明で使用されるポリアミド酸あるいはポリイミドの分子量は、以下の通りである。すなわち、ポリアミド酸の場合は、N−メチル−2−ピロリドン溶媒中、濃度0.5g/dl、35℃で測定した対数粘度の値が0.1から3.0dl/gであり、ポリイミドの場合はp-クロロフェノール/フェノール=9/1(重量)の混合溶媒中、濃度0.5g/dl、35℃で測定した対数粘度の値が0.1から3.0dl/gである。
【0034】
この様にして得られたポリイミドは無色透明性に優れ、かつ高い耐熱性を有するものである。従って、このポリイミドに色素を添加することで、高い耐熱性を有するポリイミド系色調フィルムを得ることが可能である。もし、従来知られるような黄〜赤褐色に着色したポリイミドであれば色調フィルムを得ることは不可能である。
【0035】
ポリイミドフィルムを着色する手法は幾つか考えられる。例えば、ポリイミドを溶融させた状態で色素を練り込んでいく方法や、無色透明のポリイミドフィルムの表面を色素で染色していく方法がある。しかしながら、これらの方法では、ポリイミドに安定した熱可塑性が必要となったり、あるいは、均一に染色していく高度な技術が必要になってくる。
【0036】
それに対し、本発明においてはポリイミドの前駆体であるポリアミド酸溶液の状態に、有機溶媒に可溶な有機系色素を溶解し、色素含有ポリアミド酸溶液とした後、塗工・加熱脱溶媒・イミド化することによってポリイミド系の色調フィルムとする。この方法に寄れば、均一の色調を有する色調フィルムが容易に得られる。
【0037】
ここで使用される有機系色素とは、耐熱性があり、かつポリアミド酸の溶液に溶解するものであればどのようなものでも良いが、溶媒に可溶で水には不要である染料系、所謂、分散染料(カラーインデックスで言うC.I.Disperse)や油溶染料(カラーインデックスで言うC.I.Solvent)が適している。
【0038】
それらの中でも例えば、赤色の有機系色素については一般式(5)(式中R1は有機基)で表されるアントラキノン系の色素、すなわち、カラーインデックスで言うC.I.Disperse Red60系統が、耐熱性およびポリアミド酸溶液に対する溶解性の観点から適している。
【0039】
黄色の有機系色素については一般式(6)(式中R2、R3は有機基)で表されるキノフタロン系の色素、すなわち、カラーインデックスで言うC.I.Disperse Yellow 149系統が、耐熱性およびポリアミド酸溶液に対する溶解性の観点から適している。
【0040】
更に、青色の有機系色素については一般式(7)(式中R4は有機基)で表されるフタロシアニン系の色素、すなわち、カラーインデックスで言うC.I.SolventBlue25系統が、耐熱性およびポリアミド酸溶液に対する溶解性の観点から適している。
【0041】
【化18】
Figure 0004908698
【0042】
尚、上記色素のほかにも、本発明の条件、すなわち耐熱性とポリアミド酸溶液に対する溶解度を満足するものであれば公知の色素は適用可能であり、カラーインデックスや染料便覧などに記載の色素が挙げられる。
【0043】
それらの色素について例示すると、赤色(レッド、マゼンタ)の有機色素については、C.I.Disperse Red1,4,5,7,9,11,12,13,15,17,43,52,53,54,55,56,58,59,65,72,73,74,75,76,80,82,84,88,90,91,92,97,99,100,101,103,104,112,113,116,117,122,125,126,127,128,129135,137,141,143,145,146,152,153,167,177,181,184,188,189,191,196,197,199,205,206,207,209,210,221,223,224,225,226,227,228,229,235,236,237,239,240,242,243,258,261,262,278,283,288,323,332,348,360、およびC.I.Solvent Red1,3,8,23,24,25,27,30,49,71,81,82,83,84,100,109,121,152,155,176,177,179等が挙げられる。黄色(イエロー)の有機色素については、C.I.Disperse Yellow1,3,4,5,7,8,23,31,33,42,49,50,51,54,56,60,61,64,66,71,72,76,78,79,82,83,86,88,90,92,93,98,99,100,102,103,104,105,108,114,117,119,120,123,124,126,132,146,150,155,156,160,163,164,165,166,169,170,172,192,198,224,226,234、およびC.I.Solvent Yellow2,6,14,15,16,19,21,33,44,56,61,80,98,104,105,112,113,114等が挙げられる。青色(ブルー、シアン)の有機色素については、C.I.Disperse Blue1,3,5,6,7,20,23,27,43,44,52,54,55,56,58,60,61,62,64,72,73,75,79,81,85,87,90,91,92,94,97,98,99,103,104,105,106,108,113,135,137,141,143,145,146,152,153,167,177,181,184,188,189,191,196,197,199,205,206,207,209,210,221,223,224,225,226,227,228,229,235,236,237,239,240,242,243,258,261,262,278,283,288,323,332,348,360、およびC.I.Solvent Blue2,11,12,35,36,55,73,78,94,95等が挙げられる。更に、上記赤・黄・青以外の中間色色素についても使用することができる。例えば、橙色(オレンジ)については、C.I.Disperse Orange1,3,5,11,13,20,21,30,32,41,43,46,49,50,51,55,57,61,72,73,76,97,103,108,110,112,114,120,127,148、およびC.I.Solvent Orange1,2,5,6,14,37,,40,44,45,63,68,72,78等が挙げられ、紫色(バイオレット)については、C.I.Disperse Violet1,4,8,10,18,23,24,26,28,30,33,37,38,43,46,48,56,69,70,71,77,97、およびC.I.Solvent Violet8,13,14,21,27,31,32,33等が挙げられ、緑色(グリーン)については、C.I.Disperse Green1,2,5,6,9、およびC.I.Solvent Green3,26等が挙げられる。しかしながら、上記に挙げた染料系色素に限定されるものではない。
【0044】
尚、これらの色素は2種以上を併用することによって、上記三原色、中間色以外の色調も可能である。
【0045】
ここで使用する有機系色素の使用量は、ポリマー100重量部に対して0.001〜10重量部程度である。これは、ポリアミド酸、ポリイミドともほぼ同等である。0.001重量部より少ない添加量であれば、望まれる発色が見られない。また、10重量部より多い量であれば、ポリイミドフィルムとしての物性が保持できない。
【0046】
本発明で使用される有機系色素とは、耐熱性があり、かつポリアミド酸の溶液に溶解するものであり、一般には溶媒に可溶で水には不要である染料系、所謂、分散染料(カラーインデックスで言うC.I.Disperse)や油溶染料(カラーインデックスで言うC.I.Solvent)が適している。しかしながら、本発明のポリイミド系色調フィルムの物性を損なわない範囲において、水や溶媒に溶けない色素、すなわち顔料(カラーインデックスで言うC.I.Pigment)や建染染料(カラーインデックスで言うC.I.Vat)等の、所謂顔料系の色素を混合して用いることも可能である。先に延べた染料系色素に対する顔料系色素の使用量は、染料系色素100重量部に対して、30重量部以下、好ましくは10重量部以下、更に好ましくは5重量部以下である。
【0047】
また、本発明において使用可能な顔料系色素としては以下のものが挙げられる。赤色(レッド、マゼンタ)についてはC.I.Pigment Red1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,21,22,23,30,31,32,37,38,39,40,41,48,49,50,51,52,53,54,55,57,58,60,63,64,68,81,83,87,88,89,90,112,114,123,163、およびC.I.Vat Red1,2,10,13,15,23,29,35等が挙げられる。黄色(イエロー)については、C.I.Pigment Yellow1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,65,73,83,108,109,147、およびC.I.Vat Yellow1,3,20等が挙げられる。青(ブルー、シアン)については、C.I.Pigment Blue1,2,3,15,16,17,22,25,60およびC.I.Vat Blue4,6,20,45等が挙げられる。橙色(オレンジ)については、C.I.Pigment Orange1,2,5,7,13,14,15,16,17,24,31、およびC.I.Vat Orange3,4,7,9等が挙げられる。紫色(バイオレット)については、C.I.Pigment Violet1,2,3,5,19,23,122、およびC.I.Vat Violet1,2,3,10等が挙げられる。緑色(グリーン)についてはC.I.Pigment Green1,2,7,8,10,12,36,37,38、およびC.I.Vat Green1,3等が挙げられる。しかしながら、上記に挙げた顔料系色素に限定されるものではない。
【0048】
本発明で使用されるポリアミド酸の溶液において、使用されている溶媒はポリアミド酸および前記有機系色素が溶解するならばどのような溶媒でもよいが、通常使用する溶媒としては、例えば
フェノール系溶媒である、フェノール、o−クロロフェノール、m−クロロフェノール、p−クロロフェノール、o−クレゾール、m−クレゾール、p−クレゾール、2,3−キシレノール、2,4−キシレノール、2,5−キシレノール、2,6−キシレノール、3,4−キシレノール、3,5−キシレノール、
非プロトン性アミド系溶媒である、
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,N−ジエチルアセトアミド、N−メチル−2−ピロリドン、1,3−ジメチル−2−イミダゾリジノン、N−メチルカプロラクタム、ヘキサメチルホスホロトリアミド、
エーテル系溶媒である、
1,2−ジメトキシエタン、ビス(2−メトキシエチル)エーテル、1,2−ビス(2−メトキシエトキシ)エタン、テトラヒドロフラン、ビス[2−(2−メトキシエトキシ)エチル]エーテル、1,4−ジオキサン、
アミン系溶媒である、
ピリジン、キノリン、イソキノリン、α−ピコリン、β−ピコリン、γ−ピコリン、イソホロン、ピペリジン、2,4−ルチジン、2,6−ルチジン、トリメチルアミン、トリエチルアミン、トリプロピルアミン、トリブチルアミンン
その他の溶媒である、
ジメチルスルホキシド、ジメチルスルホン、ジフェニルエーテル、スルホラン、ジフェニルスルホン、テトラメチル尿素、アニソール、
等が挙げられる。これらの溶媒は、単独または2種以上混合して用いても差し支えない。この中で、作業性、溶解性等を考慮した場合、アミド系溶剤である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,N−ジエチルアセトアミド、N−メチル−2−ピロリドン、1,3−ジメチル−2−イミダゾリジノン等が最も適している。
【0049】
尚、本発明においては、該ポリアミド酸の溶液に有機系色素を溶解するが、その溶解条件は、室温中で所定量を混合した後、室温下で攪拌することで達成される。その際の時間・圧力等については特に限定されない。
【0050】
この様にして得られた色素含有ポリアミド酸溶液からポリイミドフィルムを作成するわけであるが、フィルムの作成方法は従来公知の手法が全て適用できる。一般的には、該色素含有ポリアミド酸の溶液をガラス板等の基材の上に流延・塗工後、イナートオーブン等の電気炉中で脱溶媒・イミド化することによりポリイミド系の色調フィルムとする。 熱イミド化の反応温度、反応時間および反応圧力には、特に制限はなく公知の条件が適用できる。すなわち、反応温度は、80℃から400℃前後が適用でき、好ましくは100℃から300℃前後であり、実施面で最も好ましく実用的なのが150℃から250℃前後である。また、反応時間は使用する溶媒の種類やそれ以外の反応条件により異なるが、0.5から24時間が好ましく、更に好ましくは2から10時間前後である。更に、反応圧力は常圧で十分である。雰囲気は空気、窒素、ヘリウム、ネオン、アルゴンが用いられ特に制限はないが、好ましくは不活性気体である窒素やアルゴンを選択する。
【0051】
本発明のポリイミドは、本発明の目的を損なわない範囲で他の熱可塑性樹脂、例えばポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリブタジエン、ポリスチレン、ポリ酢酸ビニルABS樹脂、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリフェニレンオキシド、ポリカーボネート、PTFE、セルロイド、ポリアリレート、ポリエーテルニトリル、ポリアミド、ポリスルホン、ポリエーテルスルホン、ポリエーテルケトン、ポリフェニルスルフィド、ポリアミドイミド、ポリエーテルイミド、変性ポリフェニレンオキシド、および本発明以外のポリイミド、または他の熱硬化性樹脂、例えば熱硬化性ポリブタジエン、ホルムアルデヒド樹脂、アミノ樹脂、ポリウレタン、シリコン樹脂、SBR,NBR、不飽和ポリエステル、エポキシ樹脂、ポリシアネート、フェノール樹脂、およびポリビスマレイミド等と目的に応じて一種もしくは2種以上の樹脂を適当量ブレンド化またはアロイ化することも可能である。それらの方法は特に限定されず公知の方法が適用できる。
【0052】
本発明のポリイミドは、本発明の目的を損なわない範囲で各種充填剤もしくは添加剤と混合してもよい。それらの例を挙げると、グラファイト、カーボランダム、ケイ石粉、二硫化モリブデン、フッ素系樹脂などの耐摩耗性向上剤、三酸化アンチモン、炭酸マグネシウム、炭酸カルシウム等の難燃性向上剤、クレー、マイカ等の電気的特性向上剤、アスベスト、シリカ、グラファイト等の耐トラッキング向上剤、硫酸バリウム、シリカ、メタケイ酸カルシウム等の耐酸性向上剤、鉄粉、亜鉛粉、アルミニウム粉、銅粉等の熱伝導度向上剤、その他ガラスビーズ、ガラス球、タルク、ケイ藻土、アルミナ、シラスバルン、水和アルミナ、金属酸化物等である。混合方法は特に限定されず公知の方法が適用できる。
【0053】
本発明によって得られたポリイミド色調フィルムは、色素の含有によって特定波長の光の透過率を任意に制御することが可能であるから、光線カットフィルター等の光学的な用途に使用することが可能である。
【0054】
また、ポリイミド特有の耐熱性も兼ね備えることから、耐熱性が要求される用途にも適用できる。例えば、これまでも、ポリイミド系の耐熱接着フィルムが市販されているが、これまでのものはポリイミド特有の褐色に着色したテープであった。本発明のポリイミド色調フィルムを用いれば、様々な色調のポリイミド接着テープとすることができる。
【0055】
更に、本発明で使用されるポリイミドは、熱による融着性も兼ね備えている。従って、本発明のポリイミド系色調フィルムを熱融着させることにより、基材上に色調フィルムを張合わせることが可能である。一方、色素含有ポリアミド酸溶液についても、該溶液を基材上に塗布した後、脱溶媒・イミド化することで、複雑な形状にも色調ポリイミドをコーティングすることが可能である。
【0056】
【実施例】
以下、本発明を実施例により更に詳細に説明する。しかしながら、本発明はこれによって何ら制限を受けるものではない。
実施例中に共通する各種試験の試験方法は次に示すとおりである。
【0057】
1) ポリアミド酸の対数粘度;
ポリアミド酸の固形分濃度が0.5g/dlになるようにN−メチル−2−ピロリドンに溶解した後、35℃に冷却後測定。
【0058】
2) ガラス転移温度(Tg);
島津製作所社製DSC60シリーズを用い、窒素気流下、昇温速度16℃/分で測定。
【0059】
3) E型機械粘度;東京計機社製E型機械粘度計を使用し、25℃で測定。
【0060】
4) 光線透過率(T%)
島津製作所社製UV−265FWを用い、190〜900nmの領域を測定。
【0061】
5) ゲルパーミッションクロマトグラム(GPC)
Shodex社製GPC System−21シリーズを用いて測定。溶離液はN,N−ジメチルホルムアミド(LiBrおよびリン酸をそれぞれ6mM含有)を使用し、50℃で測定。
【0062】
また、今回ポリアミド酸の重合に使用した必須ジアミンNBDAの組成は以下の通りである。
NBDA;(2S,5S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン、(2S,5R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン、(2S,6R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン、および(2S,6S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタンの異性体混合体
(2S,5S)−NBDA;(2S,5S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン
(2S,5R)−NBDA;(2S,5R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン
(2S,6R)−NBDA;(2S,6R)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン
(2S,6S)−NBDA;(2S,6S)−ジアミノメチル−ビシクロ[2.2.1]ヘプタン
異性体混合比は、
(2S,5S)−NBDA:(2S,5R)−NBDA:(2S,6R)−NBDA:(2S,6S)−NBDA=26%:37%:18%:19%
である。
【0063】
合成例〜ポリアミド酸の合成
攪拌機、温度計および窒素導入管を備えたフラスコに、PMDA218.12g(1.00mol)とN,N−ジメチルアセトアミド(以下DMAc)600gを装入し、窒素気流下、室温で攪拌した。この反応系を10℃以下まで冷却した後、NBDA154.30g(1.00mol)およびDMAc154.30gの混合溶液を90分間で徐々に滴下した。その間、反応系が15℃以上に上昇しない様に冷却した。その後50℃まで昇温し、更に6時間攪拌した。冷却後、得られたポリアミド酸の対数粘度は0.68dl/g、E型機械粘度は31700mPa・sであった。また、ポリアミド酸のGPCの結果は、数平均分子量(Mn)が23100、重量平均分子量(Mw)が82600、分散度(Mw/Mn)が3.57であった。
得られたワニスを、ガラス板上にキャストし、窒素気流下で室温から250℃まで2時間、250℃で2時間焼成して厚さ約50μmのポリイミドフィルムを得た。得られたポリイミドフィルムの外観は無色透明でフレキシブルなものであり、400nmにおける光線透過率は85.1%であった。また、ガラス転移温度(Tg)は295℃であった。
尚、900〜400nmにおける各100nm毎の光線透過率を表1に、光線透過率の測定チャートを図1に示す。
【0064】
実施例1
合成例で得られたポリアミド酸溶液100g(ポリアミド酸30g含有)に、アントラキノン系の赤色色素C.I.Disperse Red60を0.15g(ポリアミド酸100重量部に対して0.5重量部)フラスコに装入し、室温、窒素気流下で約5時間攪拌した。得られた色素含有ポリアミド酸溶液は、赤色を呈していた。この色素含有ポリアミド酸溶液を合成例と同じくガラス板上にキャストし、窒素気流下・250℃で焼成し赤色を呈したポリイミド系色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は296℃であった。
色調フィルムの100nm毎の光線透過率を表1に、光線透過率の測定チャートを合成例の色素無添加の結果と併せて図1に示す。
【0065】
実施例2
実施例1における赤色色素C.I.Disperse Red60をキノフタロン系の黄色色素C.I.Disperse Yellow149に変更した以外は実施例1と全く同様にして、黄色を呈したポリアミド酸溶液、ポリイミド色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は300℃であった。同じく光線透過率および測定チャートを表1および図1に示す。
【0066】
実施例3
実施例1における赤色色素C.I.Disperse Red60をフタロシアニン系の青色色素C.I.Solvent Blue25に変更した以外は実施例1と全く同様にして、青色を呈したポリアミド酸溶液、ポリイミド色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は300℃であった。同じく光線透過率および測定チャートを表1および図1に示す。
【0067】
実施例4
実施例1における赤色色素C.I.Disperse Red60の半分(ポリアミド酸に対して0.25重量部)をキノフタロン系の黄色色素C.I.DisperseYellow149に変更した以外は実施例1と全く同様にして、橙色を呈したポリアミド酸溶液、ポリイミド色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は292℃であった。同じく光線透過率を表1に示す。
【0068】
実施例5
実施例2における黄色色素C.I.DisperseYellow149の半分(ポリアミド酸に対して0.25重量部)をフタロシアニン系の青色色素C.I.Solvent Blue25に変更した以外は実施例2と全く同様にして、緑色を呈したポリアミド酸溶液、ポリイミド色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は291℃であった。同じく光線透過率を表1に示す。
【0069】
実施例6
実施例3における青色色素C.I.Solvent Blue25の半分(ポリアミド酸に対して0.25重量部)をアントラキノン系の赤色色素C.I.Disperse Red60に変更した以外は実施例3と全く同様にして、紫色を呈したポリアミド酸溶液、ポリイミド色調フィルムを得た。得られたポリイミド系色調フィルムのガラス転移温度は291℃であった。同じく光線透過率を表1に示す。
【0070】
【表1】
Figure 0004908698
【0071】
【発明の効果】
耐熱性、機械特性、低吸湿性、電気特性等有し、かつ無色透明性を有する特異なポリイミドに有機系色素を添加することにより、色調をコントロールしたポリイミド系の色調フィルムを得ることが可能となった。また、その前駆体であるポリアミド酸に色素添加した色素含有ポリアミド酸を得ることが可能となった。
【図面の簡単な説明】
【図1】 色素無添加のポリイミドフィルム、および赤・黄・青の色素を添加したポリイミドフィルムの光線透過率を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyamic acid solution containing a specific organic dye, a polyimide color film obtained therefrom, and further to a method for producing a dye-containing polyamic acid solution and a polyimide color film.
[0002]
[Prior art]
Conventionally, polyimide is widely used in various fields as a molding material, a composite material, and an electric / electronic material because of its excellent heat resistance, mechanical properties, electrical properties, and the like.
[0003]
For example, as a typical polyimide, the formula (A) or the formula (B)
The polyimide is known. These polyimide films are widely used in the field of electronic materials because of their excellent heat resistance and mechanical properties, but they are colored yellow to reddish brown, and the color tone is controlled by applying modifications such as mixing pigments. It is very difficult to obtain a finished film.
[Chemical 7]
Figure 0004908698
[0004]
In addition, the polyetherimide represented by the formula (C) has a colorless transparency that is significantly improved compared to the polyimides of the formulas (A) and (B), but it is still slightly pale yellow, and the color tone was controlled. Use as a film is difficult. Further, this polyetherimide has a glass transition temperature of about 215 ° C. and is not very attractive as a heat resistant resin.
[0005]
Furthermore, attempts have been made to improve colorless transparency by introducing a fluoro group or a trifluoromethyl group into the main chain skeleton of polyimide. For example, the A.A. K. St. Clair et al., Polymeric Materials Science and Engineering, vol. 59, pp28 (1988) and European Patent 0299865, Yamashita et al. Disclose various polyimides in US Pat. Since these polyimides are highly colorless and transparent, it is possible to obtain a polyimide film with a controlled color tone. However, these polyimides must use very expensive raw materials in order to introduce essential substituents such as a fluoro group and a trifluoromethyl group, which is a big barrier in practical use.
[0006]
On the other hand, a polyimide containing a pigment or the like is already known as a color filter of a color liquid crystal display device. For example, JP-A-58-46325, JP-A-60-184202, JP-A-60-184203, JP-A-61-2254905, JP-A-2-4201, JP-A-7- No. 11132, JP-A-7-13012, JP-A-7-198929, JP-A-8-152617, JP-A-9-20865, JP-A-10-63193, and the like. However, the pigments contained therein (C.I. Pigment in the color index) are basically insoluble in the solvent and exist in a dispersed form in the polyimide layer. Therefore, the dispersibility becomes a problem. Moreover, these prior arts are a part of the layer which comprises a liquid crystal display element, and are not utilized as a single film. Furthermore, the polyimide itself used in these prior arts is basically an aromatic polyimide, and the colorless transparency as a polyimide film is not so good.
[0007]
Therefore, a polyimide-based color tone film using a colorless and transparent polyimide and further adding a pigment or the like to control the color tone has not been realized yet.
[0008]
[Problems to be solved by the invention]
The object of the present invention is a polyimide-based color tone film in which the color tone is controlled by adding an organic dye to a specific polyimide having heat resistance, mechanical properties, chemical resistance, electrical properties, etc. and having colorless transparency. Is to provide. Another object of the present invention is to provide a dye-containing polyamic acid obtained by adding a dye to the precursor polyamic acid.
[0009]
[Means for Solving the Problems]
As a result of intensive investigations to achieve the above object, the present inventors have formed a dye-containing polyamic acid by adding an organic dye to a solution of a polyamic acid having a specific structure, and formed a color tone by forming a film. The inventors have found that it is possible to obtain a polyimide-based color tone film in which the above is controlled, and have completed the present invention.
[0010]
That is, the present inventionIncludes:
[0011]
[1]
  General formula (1)
[Chemical 1]
Figure 0004908698
A solution of a polyamic acid having a repeating structural unit represented by:
An organic dye dissolved in the solution,
The solution isSelected from the group consisting of phenolic solvents, aprotic amide solvents, ether solvents and amine solventsThe organic dye is solubleContains organic solventTo
Dye-containing polyamic acid solution (wherein R has 4 to 27 carbon atoms, and aliphatic group, monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic group) A tetravalent group selected from the group consisting of a non-condensed polycyclic aliphatic group or an aromatic group in which an aromatic group, a cyclic aliphatic group, or an aromatic group are connected to each other directly or by a crosslinking member. ).
[2]
  Formula (2)
[Chemical 2]
Figure 0004908698
The dye-containing polyamic acid solution according to [1], comprising a solution of a polyamic acid having a repeating structural unit represented by formula (I) and the organic dye.
[3]
  The dye-containing polyamic acid solution according to [1] or [2], comprising 0.001 to 10.0 parts by weight of at least one organic dye based on 100 parts by weight of the polymer.
[4]
  A polyimide color film obtained from the dye-containing polyamic acid solution according to [1],
  General formula (3)
[Chemical Formula 3]
Figure 0004908698
A colorless and transparent polyimide having a repeating structural unit represented by: an organic dye soluble in an organic solvent selected from the group consisting of a phenolic solvent, an aprotic amide solvent, an ether solvent, and an amine solvent; Containing polyimide color tone film (wherein R has 4 to 27 carbon atoms, and aliphatic group, monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed) A tetravalent group selected from the group consisting of a non-condensed polycyclic aliphatic group or aromatic group in which a polycyclic aromatic group, a cyclic aliphatic group or an aromatic group are connected to each other directly or by a bridging member Is shown.)
[5]
  Formula (4)
[Formula 4]
Figure 0004908698
The polyimide-type color tone film of Claim 4 formed by containing the colorless and transparent polyimide which has a repeating structural unit represented, and the said organic type pigment | dye.
[6]
  The polyimide color tone film according to claim 4 or 5, comprising 0.001 to 10.0 parts by weight of at least one organic dye based on 100 parts by weight of the polymer.
[7]
  Polyamic acid solutionAddHeat treatmentBy doingSolvent removalas well asAnd imidizing,
  The said polyamic-acid solution is a manufacturing method of the polyimide-type color tone film which is a pigment | dye containing polyamic-acid solution of any one of [1] to [3].
[0023]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the repeating unit structure of the base polyimide and the polyamic acid precursor thereof is as follows:
[0024]
Embedded image
Figure 0004908698
[0025]
Embedded image
Figure 0004908698
[0026]
(Wherein R is the same as above), preferably the structure of polyimide and its precursor polyamic acid is
[0027]
Embedded image
Figure 0004908698
[0028]
Embedded image
Figure 0004908698
[0029]
The polyimide having repeating structural units represented by formulas (3) and (4) has excellent physical properties inherent to polyimide, that is, physical properties such as heat resistance, mechanical properties, and electrical properties, and excellent colorlessness. It is a resin having transparency (described in Japanese Patent Application No. 12-226324). This polyimide is composed of diaminomethyl-bicyclo [2.2.1] heptane (hereinafter NBDA) and tetracarboxylic dianhydride as essential monomers. Here, NBDA may be a single structure or a mixture of structural isomers. The structural isomers included are mainly (2S, 5S) -diaminomethyl-bicyclo [2.2.1] heptane ((2S, 5S) -NBDA), (2S, 5R) -diaminomethyl-bicyclo [2 2.1] heptane ((2S, 5R) -NBDA), (2S, 6R) -diaminomethyl-bicyclo [2.2.1] heptane ((2S, 6R) -NBDA), and (2S, 6S) -Diaminomethyl-bicyclo [2.2.1] heptane ((2S, 6S) -NBDA) and the like, but other structural isomers may be contained. Further, any composition may be used for the composition ratio. As the tetracarboxylic dianhydride, a high purity dianhydride is generally used, but a ring-opened product or an esterified product may be used. At this time, when the tetracarboxylic dianhydride is pyromellitic dianhydride, the polyamic acid represented by the formula (2) and the polyimide represented by the formula (3) are obtained.
[0030]
Furthermore, it is also possible to copolymerize other alicyclic diamines within a range that does not impair the performance such as colorless transparency and heat resistance inherent in the polyimide used in the present invention. The amount used is 30 mol% or less, preferably 10 mol% or less of the total diamine component. In addition to these alicyclic diamine compounds, aromatic diamines, diaminosiloxanes, or non-alicyclic aliphatic diamines can be copolymerized within a range that does not impair the characteristics of the present invention. . The amount used in that case is also 30 mol% or less, preferably 10 mol% or less of the total diamine component. These diamines used for copolymerization may be used alone or in admixture of two or more.
[0031]
Moreover, about the acid dianhydride used by this invention, you may use together 2 or more types of aromatic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride.
[0032]
The polyamic acid and polyimide used in the present invention are represented by the above formulas (1) and (2), but the molecular ends may or may not be sealed.
[0033]
The molecular weight of the polyamic acid or polyimide used in the present invention is as follows. That is, in the case of polyamic acid, the value of logarithmic viscosity measured at 35 ° C. in a concentration of 0.5 g / dl in N-methyl-2-pyrrolidone solvent is 0.1 to 3.0 dl / g. Has a logarithmic viscosity value of 0.1 to 3.0 dl / g measured at 35 ° C. in a mixed solvent of p-chlorophenol / phenol = 9/1 (weight) at a concentration of 0.5 g / dl.
[0034]
The polyimide thus obtained has excellent colorless transparency and high heat resistance. Therefore, it is possible to obtain a polyimide color tone film having high heat resistance by adding a dye to this polyimide. If the polyimide is colored yellow to reddish brown as conventionally known, it is impossible to obtain a color tone film.
[0035]
Several methods for coloring the polyimide film are conceivable. For example, there are a method of kneading a pigment in a state where polyimide is melted, and a method of dyeing the surface of a colorless and transparent polyimide film with a pigment. However, in these methods, stable thermoplasticity is required for polyimide, or advanced techniques for uniformly dyeing are required.
[0036]
On the other hand, in the present invention, in the state of the polyamic acid solution which is a polyimide precursor, an organic dye soluble in an organic solvent is dissolved to obtain a dye-containing polyamic acid solution, followed by coating, heating desolvation, and imide To obtain a polyimide color tone film. According to this method, a color film having a uniform color tone can be easily obtained.
[0037]
The organic dye used here may be any dye that has heat resistance and is soluble in a solution of polyamic acid, but is soluble in a solvent and unnecessary for water, So-called disperse dyes (CIDisperse in the color index) and oil-soluble dyes (CISolvent in the color index) are suitable.
[0038]
Among them, for example, a red organic dye is represented by the general formula (5) (wherein R1Is an anthraquinone dye represented by an organic group), that is, the C.I. Disperse Red 60 system referred to by a color index is suitable from the viewpoint of heat resistance and solubility in a polyamic acid solution.
[0039]
The yellow organic dye is represented by the general formula (6) (wherein R2, RThreeIs an organic group), that is, C.I. Disperse Yellow 149, which is referred to as a color index, is suitable from the viewpoint of heat resistance and solubility in a polyamic acid solution.
[0040]
Further, for the blue organic dye, the general formula (7) (wherein RFourIs a phthalocyanine-based dye represented by an organic group), that is, the C.I. SolventBlue 25 system referred to as a color index is suitable from the viewpoint of heat resistance and solubility in a polyamic acid solution.
[0041]
Embedded image
Figure 0004908698
[0042]
In addition to the above dyes, known dyes can be applied as long as they satisfy the conditions of the present invention, that is, heat resistance and solubility in a polyamic acid solution, and the dyes described in the color index, dye manual, etc. Can be mentioned.
[0043]
Examples of these dyes are red (red, magenta) organic dyes such as CI Disperse Red 1, 4, 5, 7, 9, 11, 12, 13, 15, 17, 43, 52, 53, 54, 55. , 56, 58, 59, 65, 72, 73, 74, 75, 76, 80, 82, 84, 88, 90, 91, 92, 97, 99, 100, 101, 103, 104, 112, 113, 116 117,122,125,126,127,128,129135,137,141,143,145,146,152,153,167,177,181,184,188,189,191,196,197,199,205 , 206, 207, 209, 210, 221, 223, 224, 225, 226, 227, 228, 229, 235, 236, 237, 239, 240, 242, 243, 258, 261, 262, 278, 283, 288, 323, 332, 348, 360, and CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 71, 81 , 82, 83, 84, 100, 109, 121, 152, 155, 176, 177, 179 and the like. For yellow (yellow) organic dyes, CI Disperse Yellow 1, 3, 4, 5, 7, 8, 23, 31, 33, 42, 49, 50, 51, 54, 56, 60, 61, 64, 66, 71, 72, 76, 78, 79, 82, 83, 86, 88, 90, 92, 93, 98, 99, 100, 102, 103, 104, 105, 108, 114, 117, 119, 120, 123, 124, 126, 132, 146, 150, 155, 156, 160, 163, 164, 165, 166, 169, 170, 172, 192, 198, 224, 226, 234, and CI Solvent Yellow 2, 6, 14, 15 16, 19, 21, 33, 44, 56, 61, 80, 98, 104, 105, 112, 113, 114, and the like. For blue (blue, cyan) organic dyes, CI Disperse Blue 1, 3, 5, 6, 7, 20, 23, 27, 43, 44, 52, 54, 55, 56, 58, 60, 61, 62, 64, 72, 73, 75, 79, 81, 85, 87, 90, 91, 92, 94, 97, 98, 99, 103, 104, 105, 106, 108, 113, 135, 137, 141, 143 145,146,152,153,167,177,181,184,188,189,191,196,197,199,205,206,207,209,210,221,223,224,225,226,227, 228,229,235,236,237,239,240,242,243,258,261,262,278,283,288,323,332,348 360, and C. I. Solvent Blue2,11,12,35,36,55,73,78,94,95 like. Furthermore, intermediate color pigments other than the above red, yellow, and blue can also be used. For example, for orange (orange), CI Disperse Orange 1, 3, 5, 11, 13, 20, 21, 30, 32, 41, 43, 46, 49, 50, 51, 55, 57, 61, 72, 73 76, 97, 103, 108, 110, 112, 114, 120, 127, 148, and CISolvent Orange 1, 2, 5, 6, 14, 37, 40, 44, 45, 63, 68, 72, 78 For purple (violet), CIDisperse Violet 1, 4, 8, 10, 18, 23, 24, 26, 28, 30, 33, 37, 38, 43, 46, 48, 56, 69, 70, 71, 77, 97, and CISolvent Violet 8, 13, 14, 21, 27, 31, 32, 33, and the like. For green (green), CI Disperse Green 1, 2, 5, 6, 9, And CI Solvent Green 3,26 etc. are mentioned. However, it is not limited to the dye pigments listed above.
[0044]
In addition, by using two or more kinds of these pigments in combination, color tones other than the above three primary colors and intermediate colors are possible.
[0045]
The usage-amount of the organic pigment | dye used here is about 0.001-10 weight part with respect to 100 weight part of polymers. This is almost the same for polyamic acid and polyimide. If the addition amount is less than 0.001 part by weight, the desired color development is not observed. Moreover, if it is more than 10 weight part, the physical property as a polyimide film cannot be hold | maintained.
[0046]
The organic colorant used in the present invention is a dye system which is heat resistant and dissolves in a solution of polyamic acid, and is generally soluble in a solvent and not necessary for water, so-called disperse dye ( CIdisperse (color index) and oil-soluble dyes (CISolvent) are suitable. However, as long as the physical properties of the polyimide color tone film of the present invention are not impaired, pigments that are not soluble in water or solvents, that is, pigments (CIPigment in terms of color index) and vat dyes (in terms of color index, CIVat), It is also possible to mix so-called pigment-based dyes. The amount of the pigment-based dye used with respect to the dye-based dye previously described is 30 parts by weight or less, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less with respect to 100 parts by weight of the dye-based dye.
[0047]
In addition, examples of pigment-based dyes that can be used in the present invention include the following. For red (red, magenta), CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 123, 163, CIVat Red 1, 2, 10, 13, 15, 23, 29, 35, and the like. About yellow (yellow), CIPigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,15,16,17,23,65,73,83,108,109 , 147, and CIVat Yellow 1, 3, 20 and the like. Examples of blue (blue, cyan) include C.I. Pigment Blue 1, 2, 3, 15, 16, 17, 22, 25, 60, C.I. Vat Blue 4, 6, 20, 45, and the like. About orange (orange), C.I.Pigment Orange1,2,5,7,13,14,15,16,17,24,31, C.I.Vat Orange3,4,7,9 etc. are mentioned. Examples of purple (violet) include C.I. Pigment Violet 1, 2, 3, 5, 19, 23, 122, C.I. Vat Violet 1, 2, 3, 10, and the like. Examples of green include C.I. Pigment Green 1, 2, 7, 8, 10, 12, 36, 37, 38, C.I. Vat Green 1, 3, and the like. However, it is not limited to the pigment-based dyes listed above.
[0048]
In the polyamic acid solution used in the present invention, the solvent used may be any solvent as long as the polyamic acid and the organic dye are dissolved.
Phenol solvents, phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5 -Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol,
An aprotic amide solvent,
N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, hexamethylphosphorotri Amide,
An ether solvent,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, tetrahydrofuran, bis [2- (2-methoxyethoxy) ethyl] ether, 1,4-dioxane ,
An amine solvent,
Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine
Other solvents,
Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulfolane, diphenyl sulfone, tetramethyl urea, anisole,
Etc. These solvents may be used alone or in combination of two or more. Among these, in consideration of workability, solubility and the like, amide solvents N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, 1 , 3-dimethyl-2-imidazolidinone and the like are most suitable.
[0049]
In the present invention, the organic dye is dissolved in the polyamic acid solution. The dissolution condition is achieved by mixing a predetermined amount at room temperature and then stirring at room temperature. There are no particular limitations on the time, pressure, etc. at that time.
[0050]
A polyimide film is prepared from the dye-containing polyamic acid solution obtained in this manner, and all known methods can be applied to the film preparation method. In general, after casting and coating the dye-containing polyamic acid solution on a substrate such as a glass plate, it is desolvated and imidized in an electric furnace such as an inert oven, thereby producing a polyimide color tone film. And There are no particular limitations on the reaction temperature, reaction time, and reaction pressure for thermal imidization, and known conditions can be applied. That is, a reaction temperature of about 80 ° C. to about 400 ° C. can be applied, preferably about 100 ° C. to about 300 ° C., and most preferably practical is about 150 ° C. to about 250 ° C. The reaction time varies depending on the type of solvent used and other reaction conditions, but is preferably 0.5 to 24 hours, more preferably about 2 to 10 hours. Furthermore, a normal pressure is sufficient as the reaction pressure. The atmosphere is air, nitrogen, helium, neon, or argon, and is not particularly limited. However, nitrogen or argon which is an inert gas is preferably selected.
[0051]
The polyimide of the present invention is not limited to the purpose of the present invention, and other thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate ABS resin, polybutylene terephthalate, polyethylene terephthalate. , Polyphenylene oxide, polycarbonate, PTFE, celluloid, polyarylate, polyether nitrile, polyamide, polysulfone, polyether sulfone, polyether ketone, polyphenyl sulfide, polyamide imide, polyether imide, modified polyphenylene oxide, and polyimides other than the present invention , Or other thermosetting resins such as thermosetting polybutadiene, formaldehyde resin, amino resin, polyurethane, silicone resin, SBR NBR, unsaturated polyester, epoxy resin, polycyanate, phenolic resin, and can be an appropriate amount blending or alloying the one or two or more resins according to poly bismaleimide and purpose. Those methods are not particularly limited, and known methods can be applied.
[0052]
The polyimide of the present invention may be mixed with various fillers or additives as long as the object of the present invention is not impaired. Examples of these are wear resistance improvers such as graphite, carborundum, silica stone powder, molybdenum disulfide, and fluorine resins, flame retardant improvers such as antimony trioxide, magnesium carbonate, calcium carbonate, clay, mica Electrical property improvers such as asbestos, silica, graphite and other tracking resistance improvers, acid resistance improvers such as barium sulfate, silica and calcium metasilicate, heat conduction of iron powder, zinc powder, aluminum powder, copper powder, etc. Such as glass bead, glass sphere, talc, diatomaceous earth, alumina, shirasu balun, hydrated alumina, metal oxide and the like. A mixing method is not particularly limited, and a known method can be applied.
[0053]
Since the polyimide color tone film obtained by the present invention can arbitrarily control the transmittance of light of a specific wavelength by containing a pigment, it can be used for optical applications such as a light cut filter. is there.
[0054]
Moreover, since it also has the heat resistance peculiar to a polyimide, it is applicable also to the use for which heat resistance is requested | required. For example, polyimide heat-resistant adhesive films have been commercially available so far, but the ones so far have been colored brown tapes specific to polyimide. If the polyimide color tone film of this invention is used, it can be set as the polyimide adhesive tape of various color tone.
[0055]
Furthermore, the polyimide used in the present invention also has heat fusion properties. Therefore, the color tone film can be laminated on the substrate by heat-sealing the polyimide color tone film of the present invention. On the other hand, with respect to the dye-containing polyamic acid solution, it is possible to coat a polyimide with a complex shape by applying the solution on a substrate and then removing the solvent and imidizing it.
[0056]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by this.
Test methods for various tests common to the examples are as follows.
[0057]
1) Logarithmic viscosity of polyamic acid;
Measured after dissolving in N-methyl-2-pyrrolidone so that the solid content concentration of the polyamic acid is 0.5 g / dl, and cooling to 35 ° C.
[0058]
2) Glass transition temperature (Tg);
Measured using a DSC60 series manufactured by Shimadzu Corporation under a nitrogen stream at a rate of temperature increase of 16 ° C / min.
[0059]
3) E-type mechanical viscosity; measured at 25 ° C. using an E-type mechanical viscometer manufactured by Tokyo Keiki Co., Ltd.
[0060]
4) Light transmittance (T%)
Using a Shimadzu UV-265FW, a region of 190 to 900 nm was measured.
[0061]
5) Gel permission chromatogram (GPC)
Measured using GPC System-21 series manufactured by Shodex. The eluent was measured at 50 ° C. using N, N-dimethylformamide (containing 6 mM each of LiBr and phosphoric acid).
[0062]
In addition, the composition of the essential diamine NBDA used for the polymerization of the polyamic acid this time is as follows.
NBDA; (2S, 5S) -diaminomethyl-bicyclo [2.2.1] heptane, (2S, 5R) -diaminomethyl-bicyclo [2.2.1] heptane, (2S, 6R) -diaminomethyl-bicyclo [2.2.1] heptane and (2S, 6S) -diaminomethyl-bicyclo [2.2.1] heptane isomeric mixture
(2S, 5S) -NBDA; (2S, 5S) -diaminomethyl-bicyclo [2.2.1] heptane
(2S, 5R) -NBDA; (2S, 5R) -Diaminomethyl-bicyclo [2.2.1] heptane
(2S, 6R) -NBDA; (2S, 6R) -diaminomethyl-bicyclo [2.2.1] heptane
(2S, 6S) -NBDA; (2S, 6S) -diaminomethyl-bicyclo [2.2.1] heptane
The isomer mixing ratio is
(2S, 5S) -NBDA: (2S, 5R) -NBDA: (2S, 6R) -NBDA: (2S, 6S) -NBDA = 26%: 37%: 18%: 19%
It is.
[0063]
Synthesis Example-Synthesis of Polyamic Acid
A flask equipped with a stirrer, a thermometer and a nitrogen introduction tube was charged with 218.12 g (1.00 mol) of PMDA and 600 g of N, N-dimethylacetamide (hereinafter referred to as DMAc), and stirred at room temperature under a nitrogen stream. After cooling this reaction system to 10 ° C. or lower, a mixed solution of 154.30 g (1.00 mol) of NBDA and 154.30 g of DMAc was gradually added dropwise over 90 minutes. Meanwhile, the reaction system was cooled so as not to rise above 15 ° C. Thereafter, the temperature was raised to 50 ° C., and the mixture was further stirred for 6 hours. After cooling, the polyamic acid obtained had a logarithmic viscosity of 0.68 dl / g and an E-type mechanical viscosity of 31700 mPa · s. As a result of GPC of polyamic acid, the number average molecular weight (Mn) was 23100, the weight average molecular weight (Mw) was 82600, and the dispersity (Mw / Mn) was 3.57.
The obtained varnish was cast on a glass plate and fired in a nitrogen stream from room temperature to 250 ° C. for 2 hours and at 250 ° C. for 2 hours to obtain a polyimide film having a thickness of about 50 μm. The appearance of the obtained polyimide film was colorless, transparent and flexible, and the light transmittance at 400 nm was 85.1%. Moreover, the glass transition temperature (Tg) was 295 degreeC.
In addition, the light transmittance for every 100 nm in 900-400 nm is shown in Table 1, and the measurement chart of light transmittance is shown in FIG.
[0064]
Example 1
100 g of the polyamic acid solution obtained in the synthesis example (containing 30 g of polyamic acid) was charged with 0.15 g of anthraquinone red pigment CI Disperse Red 60 (0.5 parts by weight with respect to 100 parts by weight of polyamic acid) in a flask. The mixture was stirred for about 5 hours at room temperature under a nitrogen stream. The obtained dye-containing polyamic acid solution was red. This dye-containing polyamic acid solution was cast on a glass plate in the same manner as in the synthesis example, and fired at 250 ° C. in a nitrogen stream to obtain a polyimide-based color film having a red color. The glass transition temperature of the obtained polyimide color film was 296 ° C.
The light transmittance for each 100 nm of the color tone film is shown in Table 1, and a measurement chart of the light transmittance is shown in FIG.
[0065]
Example 2
A polyamic acid solution and a polyimide color film having a yellow color were obtained in the same manner as in Example 1 except that the red pigment C.I.Disperse Red 60 in Example 1 was changed to the quinophthalone yellow pigment C.I.Disperse Yellow149. The glass transition temperature of the obtained polyimide color film was 300 ° C. Similarly, the light transmittance and the measurement chart are shown in Table 1 and FIG.
[0066]
Example 3
A polyamic acid solution exhibiting a blue color and a polyimide color film were obtained in the same manner as in Example 1 except that the red pigment C.I.Disperse Red 60 in Example 1 was changed to a phthalocyanine-based blue pigment C.I.Solvent Blue25. The glass transition temperature of the obtained polyimide color film was 300 ° C. Similarly, the light transmittance and the measurement chart are shown in Table 1 and FIG.
[0067]
Example 4
A polyamide exhibiting an orange color in exactly the same manner as in Example 1 except that half of the red pigment CIdisperse Red 60 in Example 1 (0.25 part by weight based on the polyamic acid) was changed to a quinophthalone yellow pigment CIdisperse Yellow 149. An acid solution and a polyimide color film were obtained. The resulting polyimide color film had a glass transition temperature of 292 ° C. Similarly, the light transmittance is shown in Table 1.
[0068]
Example 5
A polyamide exhibiting a green color in exactly the same manner as in Example 2, except that half of the yellow pigment CIdisperseYellow149 in Example 2 (0.25 part by weight relative to the polyamic acid) was changed to the phthalocyanine-based blue pigment CISolvent Blue25 An acid solution and a polyimide color film were obtained. The resulting polyimide color film had a glass transition temperature of 291 ° C. Similarly, the light transmittance is shown in Table 1.
[0069]
Example 6
A purple color was exhibited in exactly the same manner as in Example 3 except that half of the blue pigment CISolvent Blue 25 in Example 3 (0.25 part by weight based on polyamic acid) was changed to an anthraquinone red pigment CI Disperse Red 60. A polyamic acid solution and a polyimide color film were obtained. The resulting polyimide color film had a glass transition temperature of 291 ° C. Similarly, the light transmittance is shown in Table 1.
[0070]
[Table 1]
Figure 0004908698
[0071]
【The invention's effect】
By adding an organic dye to a unique polyimide that has heat resistance, mechanical properties, low hygroscopicity, electrical properties, etc. and has colorless transparency, it is possible to obtain a polyimide-based color tone film with controlled color tone became. Further, it is possible to obtain a dye-containing polyamic acid obtained by adding a dye to the precursor polyamic acid.
[Brief description of the drawings]
FIG. 1 shows the light transmittance of a polyimide film containing no pigment and a polyimide film added with red, yellow and blue pigments.

Claims (7)

一般式(1)
Figure 0004908698
で表される繰り返し構造単位を有するポリアミド酸の溶液と、
前記溶液に溶解している有機系色素と、を含み、
前記溶液は、フェノール系溶媒、非プロトン性アミド系溶媒、エーテル系溶媒およびアミン系溶媒からなる群から選ばれており、前記有機系色素を可溶とする有機溶剤を含有する、
色素含有ポリアミド酸溶液(式中、Rは炭素数4〜27であり、かつ脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、環式脂肪族基または芳香族基が直接または架橋員により相互に連結された非縮合多環式脂肪族基または芳香族基からなる群より選ばれた4価の基を示す。)。
General formula (1)
Figure 0004908698
A solution of a polyamic acid having a repeating structural unit represented by:
An organic dye dissolved in the solution,
The solution is selected from the group consisting of a phenol solvent, an aprotic amide solvent, an ether solvent and an amine solvent, and contains an organic solvent that makes the organic dye soluble ,
Dye-containing polyamic acid solution (wherein R has 4 to 27 carbon atoms, and aliphatic group, monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed polycyclic group) A tetravalent group selected from the group consisting of a non-condensed polycyclic aliphatic group or an aromatic group in which an aromatic group, a cyclic aliphatic group, or an aromatic group are connected to each other directly or by a crosslinking member. ).
式(2)
Figure 0004908698
で表される繰り返し構造単位を有するポリアミド酸の溶液と、前記有機系色素と、を含有してなる請求項1に記載の色素含有ポリアミド酸溶液。
Formula (2)
Figure 0004908698
The dye-containing polyamic acid solution according to claim 1, comprising a solution of a polyamic acid having a repeating structural unit represented by formula (I) and the organic dye.
ポリマー100重量部に対して少なくとも1種以上の前記有機系色素を0.001〜10.0重量部含有してなる請求項1または2に記載の色素含有ポリアミド酸溶液。  The dye-containing polyamic acid solution according to claim 1 or 2, comprising 0.001 to 10.0 parts by weight of at least one organic dye based on 100 parts by weight of the polymer. 請求項1に記載の色素含有ポリアミド酸溶液から得られるポリイミド系色調フィルムであって、
一般式(3)
Figure 0004908698
で表される繰り返し構造単位を有する無色透明ポリイミドと、フェノール系溶媒、非プロトン性アミド系溶媒、エーテル系溶媒およびアミン系溶媒からなる群から選ばれる有機溶剤に可溶な有機系色素と、を含有してなるポリイミド系色調フィルム(式中、Rは炭素数4〜27であり、かつ脂肪族基、単環式脂肪族基、縮合多環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、環式脂肪族基または芳香族基が直接または架橋員により相互に連結された非縮合多環式脂肪族基または芳香族基からなる群より選ばれた4価の基を示す。)。
A polyimide-based color tone film obtained from the dye-containing polyamic acid solution according to claim 1,
General formula (3)
Figure 0004908698
A colorless and transparent polyimide having a repeating structural unit represented by: an organic dye soluble in an organic solvent selected from the group consisting of a phenolic solvent, an aprotic amide solvent, an ether solvent, and an amine solvent; Containing polyimide color tone film (wherein R has 4 to 27 carbon atoms, and aliphatic group, monocyclic aliphatic group, condensed polycyclic aliphatic group, monocyclic aromatic group, condensed) A tetravalent group selected from the group consisting of a non-condensed polycyclic aliphatic group or aromatic group in which a polycyclic aromatic group, a cyclic aliphatic group or an aromatic group are connected to each other directly or by a bridging member Is shown.)
式(4)
Figure 0004908698
で表される繰り返し構造単位を有する無色透明ポリイミドと、前記有機系色素と、を含有してなる請求項4に記載のポリイミド系色調フィルム。
Formula (4)
Figure 0004908698
The polyimide-type color tone film of Claim 4 formed by containing the colorless and transparent polyimide which has a repeating structural unit represented, and the said organic type pigment | dye.
ポリマー100重量部に対して少なくとも1種以上の前記有機系色素を0.001〜10.0重量部含有してなる請求項4または5に記載のポリイミド系色調フィルム。  The polyimide color tone film according to claim 4 or 5, comprising 0.001 to 10.0 parts by weight of at least one organic dye based on 100 parts by weight of the polymer. ポリアミド酸溶液を加熱処理することにより、脱溶媒及びイミド化する工程と、を含み、
前記ポリアミド酸溶液は、請求項1から3のいずれか1項に記載の色素含有ポリアミド酸溶液である、ポリイミド系色調フィルムの製造方法。
By pressing heat-treating the polyamic acid solution, comprising the steps of removing the solvent and imidization, to,
The said polyamic-acid solution is a manufacturing method of the polyimide-type color tone film which is the pigment | dye containing polyamic-acid solution of any one of Claim 1 to 3.
JP2001270557A 2001-09-06 2001-09-06 DYE-CONTAINING POLYAMIDE ACID SOLUTION AND POLYIMIDE-TYPE TONE FILM, AND METHOD FOR PRODUCING POLYIMIDE-TYPE TONE FILM Expired - Lifetime JP4908698B2 (en)

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