JP2013028796A - Polyimide precursor, polyimide precursor solution composition, polyimide, polyimide solution composition, polyimide film, substrate, and molding - Google Patents
Polyimide precursor, polyimide precursor solution composition, polyimide, polyimide solution composition, polyimide film, substrate, and molding Download PDFInfo
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- JP2013028796A JP2013028796A JP2012135645A JP2012135645A JP2013028796A JP 2013028796 A JP2013028796 A JP 2013028796A JP 2012135645 A JP2012135645 A JP 2012135645A JP 2012135645 A JP2012135645 A JP 2012135645A JP 2013028796 A JP2013028796 A JP 2013028796A
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- Prior art keywords
- polyimide
- polyimide precursor
- chemical formula
- group
- solution composition
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 220
- 239000004642 Polyimide Substances 0.000 title claims abstract description 194
- 239000002243 precursor Substances 0.000 title claims abstract description 121
- 239000000203 mixture Substances 0.000 title claims description 48
- 239000000758 substrate Substances 0.000 title claims description 38
- 238000000465 moulding Methods 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 65
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 238000002834 transmittance Methods 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000005103 alkyl silyl group Chemical group 0.000 claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 150000004985 diamines Chemical class 0.000 description 38
- 239000010408 film Substances 0.000 description 32
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 24
- 239000002904 solvent Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000011521 glass Substances 0.000 description 12
- -1 1, 4- diamino- 2-n-propyl cyclohexane 1,4-diamino-2-isopropylcyclohexane Chemical compound 0.000 description 9
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- 239000002808 molecular sieve Substances 0.000 description 9
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- SIOVKLKJSOKLIF-HJWRWDBZSA-N trimethylsilyl (1z)-n-trimethylsilylethanimidate Chemical compound C[Si](C)(C)OC(/C)=N\[Si](C)(C)C SIOVKLKJSOKLIF-HJWRWDBZSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
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- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
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- 229920002647 polyamide Polymers 0.000 description 3
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- UIZIZIPEEWDBCL-UHFFFAOYSA-N (4-aminophenyl) 4-[4-(4-aminophenoxy)carbonylphenyl]benzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C=2C=CC(=CC=2)C(=O)OC=2C=CC(N)=CC=2)C=C1 UIZIZIPEEWDBCL-UHFFFAOYSA-N 0.000 description 2
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- MQZCBPWIFIEALZ-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1OC1=CC=CC=C1N MQZCBPWIFIEALZ-UHFFFAOYSA-N 0.000 description 1
- GNQHLRFTGRZHLH-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C(=CC=CC=2)N)C=1C(C)(C)C1=CC=CC=C1OC1=CC=CC=C1N GNQHLRFTGRZHLH-UHFFFAOYSA-N 0.000 description 1
- XMOJDDYUUPGBIT-UHFFFAOYSA-N 2-amino-6-[2-(3-amino-2-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound NC1=CC=CC(C(C=2C(=C(N)C=CC=2)O)(C(F)(F)F)C(F)(F)F)=C1O XMOJDDYUUPGBIT-UHFFFAOYSA-N 0.000 description 1
- IAEVEDMYEYMTSE-UHFFFAOYSA-N 2-butan-2-ylcyclohexane-1,4-diamine Chemical compound CCC(C)C1CC(N)CCC1N IAEVEDMYEYMTSE-UHFFFAOYSA-N 0.000 description 1
- HIEBSORULQQANM-UHFFFAOYSA-N 2-butylcyclohexane-1,4-diamine Chemical compound CCCCC1CC(N)CCC1N HIEBSORULQQANM-UHFFFAOYSA-N 0.000 description 1
- FMZFBOHWVULQIY-UHFFFAOYSA-N 2-ethylcyclohexane-1,4-diamine Chemical compound CCC1CC(N)CCC1N FMZFBOHWVULQIY-UHFFFAOYSA-N 0.000 description 1
- RLHGFJMGWQXPBW-UHFFFAOYSA-N 2-hydroxy-3-(1h-imidazol-5-ylmethyl)benzamide Chemical compound NC(=O)C1=CC=CC(CC=2NC=NC=2)=C1O RLHGFJMGWQXPBW-UHFFFAOYSA-N 0.000 description 1
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- RKBNPLYPKZRNEF-UHFFFAOYSA-N 2-tert-butylcyclohexane-1,4-diamine Chemical compound CC(C)(C)C1CC(N)CCC1N RKBNPLYPKZRNEF-UHFFFAOYSA-N 0.000 description 1
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical group C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 description 1
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- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
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- LVNPGQZSPDFZNC-UHFFFAOYSA-N 4-(4-amino-3-fluorophenyl)-2-fluoroaniline Chemical group C1=C(F)C(N)=CC=C1C1=CC=C(N)C(F)=C1 LVNPGQZSPDFZNC-UHFFFAOYSA-N 0.000 description 1
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- LXPPKGLPZFOHSK-UHFFFAOYSA-M CC(C=CC)(C=CC)N(C(c(cc1)c2cc1S(C)c(cc1C([N-]3)=O)ccc1C3=O)=O)C2=O Chemical compound CC(C=CC)(C=CC)N(C(c(cc1)c2cc1S(C)c(cc1C([N-]3)=O)ccc1C3=O)=O)C2=O LXPPKGLPZFOHSK-UHFFFAOYSA-M 0.000 description 1
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- LHUKBOMRMBTNBM-UHFFFAOYSA-N [4-[4-(4-aminobenzoyl)oxyphenyl]phenyl] 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1C(=O)OC1=CC=C(C=2C=CC(OC(=O)C=3C=CC(N)=CC=3)=CC=2)C=C1 LHUKBOMRMBTNBM-UHFFFAOYSA-N 0.000 description 1
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- 239000000010 aprotic solvent Substances 0.000 description 1
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- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- CFTXGNJIXHFHTH-UHFFFAOYSA-N bis(4-aminophenyl) benzene-1,4-dicarboxylate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(C(=O)OC=2C=CC(N)=CC=2)C=C1 CFTXGNJIXHFHTH-UHFFFAOYSA-N 0.000 description 1
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- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- 125000004427 diamine group Chemical group 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、高い透明性、高耐熱性を有するポリイミド、もしくはそれらの前駆体等に関する。 The present invention relates to a polyimide having high transparency and high heat resistance, or a precursor thereof.
近年、高度情報化社会の到来に伴い、光通信分野の光ファイバーや光導波路等、表示装置分野の液晶配向膜やカラーフィルター用保護膜等の光学材料の開発が進んでいる。特に表示装置分野で、ガラス基板代替として軽量でフレキシブル性に優れたプラスチック基板の検討が行なわれたり、曲げたり丸めたりすることが可能なディスプレイの開発が盛んに行われているおり、その様な用途に用いることができる、より高性能の光学材料が求められている。 In recent years, with the arrival of an advanced information society, development of optical materials such as a liquid crystal alignment film and a protective film for a color filter in the display device field, such as an optical fiber and an optical waveguide in the optical communication field, is progressing. Particularly in the field of display devices, plastic substrates that are lightweight and have excellent flexibility as glass substrate substitutes are being studied, and displays that can be bent and rolled are being actively developed. There is a need for higher performance optical materials that can be used in applications.
一般に、ポリイミドは分子内共役や電荷移動錯体の形成により本質的に黄褐色に着色する。その解決策として、例えばフッ素を導入したり、主鎖に屈曲性を与えたり、嵩高い側鎖を導入するなどして電荷移動錯体の形成阻害し透明性を発現させる方法が提案されている(非特許文献1)。また、原理的に電荷移動錯体を形成しない半脂環式または全脂環式ポリイミド樹脂を用いることにより透明性を発現させる方法も提案されている(特許文献1〜3、非特許文献2)。 In general, polyimide is essentially yellowish brown due to intramolecular conjugation and the formation of charge transfer complexes. As a solution for this, for example, a method for inhibiting the formation of a charge transfer complex and expressing transparency by introducing fluorine, imparting flexibility to the main chain, or introducing a bulky side chain has been proposed ( Non-patent document 1). In addition, a method for expressing transparency by using a semi-alicyclic or fully alicyclic polyimide resin that does not form a charge transfer complex in principle has been proposed (Patent Documents 1 to 3, Non-Patent Document 2).
特に、ジアミン成分として、トランス−1,4−ジアミノシクロヘキサン類、テトラカルボン酸成分として、3,3’,4,4’−ビフェニルテトラカルボン酸二無水物を用いた半脂環式ポリイミドは、透明性を維持しつつ、高耐熱性、低熱線膨張係数を兼ね備えることが知られている(特許文献3)。この半脂環式ポリイミドから得られる膜の透明性は比較的高いものの、光学材料としての用途を考えた場合には複屈折率が大きいため、画像が二重に見えたり、色がぼやけたりしてしまうということもあった(非特許文献2)。 In particular, transalicyclic polyimides using trans-1,4-diaminocyclohexanes as the diamine component and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as the tetracarboxylic acid component are transparent. It is known that it has high heat resistance and low thermal linear expansion coefficient while maintaining the properties (Patent Document 3). Although the transparency of the film obtained from this semi-alicyclic polyimide is relatively high, the birefringence is large when considering the use as an optical material, so the image may appear double or the color may be blurred. (Non-Patent Document 2).
また、酸二無水物に4,4’−(ジメチルシランジイル)ジフタル酸二無水物、ジアミンにオキシジアニリンを用いたポリイミドの報告がなされている(非特許文献3)。このポリイミドから得られる膜は比較的透明で耐熱性も高い。しかしながら、十分な透明性を有しているとは言いがたい。 In addition, there has been reported a polyimide using 4,4 '-(dimethylsilanediyl) diphthalic dianhydride as an acid dianhydride and oxydianiline as a diamine (Non-patent Document 3). A film obtained from this polyimide is relatively transparent and has high heat resistance. However, it is difficult to say that it has sufficient transparency.
以上のように、ポリイミドにおいて優れた透明性、高耐熱性を有することが強く求められ、低複屈折率等を求められることもあった。 As described above, polyimides are strongly required to have excellent transparency and high heat resistance, and low birefringence and the like are sometimes required.
本発明は、優れた透明性、高耐熱性等を有するポリイミドを提供することを目的とする。 An object of this invention is to provide the polyimide which has the outstanding transparency, high heat resistance, etc.
本発明は、以下の各項に関する。 The present invention relates to the following items.
1. 下記化学式(1)中のXが下記化学式(2)で表される群から選択される下記化学式(1)の単位構造を有するポリイミド前駆体であって、
このポリイミド前駆体から得られるポリイミドが、厚さ10μmのフィルムでの波長400nmの光透過率が75%以上であることを特徴とするポリイミド前駆体。
1. X in the following chemical formula (1) is a polyimide precursor having a unit structure of the following chemical formula (1) selected from the group represented by the following chemical formula (2),
The polyimide obtained from this polyimide precursor has a light transmittance of 75% or more at a wavelength of 400 nm in a 10 μm thick film.
〔式(2)中、R3〜R9はそれぞれ独立に水素原子、メチル基及びトリフルオロメチル基よりなる群から選択される1種以上を示す。〕
[In Formula (2), R < 3 > -R < 9 > shows 1 or more types selected from the group which consists of a hydrogen atom, a methyl group, and a trifluoromethyl group each independently. ]
2. 前記化学式(1)中のXが前記化学式(2)で表される群から選択される単位構造を2種以上有することを特徴とする前記項1に記載のポリイミド前駆体。 2. Item 2. The polyimide precursor according to Item 1, wherein X in the chemical formula (1) has two or more unit structures selected from the group represented by the chemical formula (2).
3. 前記化学式(1)中のXが前記化学式(2)で表される群から選択される単位構造を50モル%以上有することを特徴とする前記項1又は2に記載のポリイミド前駆体。 3. Item 3. The polyimide precursor according to Item 1 or 2, wherein X in the chemical formula (1) has 50 mol% or more of a unit structure selected from the group represented by the chemical formula (2).
4. 前記化学式(1)中のXが前記化学式(2)で表される群から選択される前記化学式(1)の単位構造を70モル%以上、下記化学式(3)で表される単位構造を30モル%以下有することを特徴とする前記項3に記載のポリイミド前駆体。 4). 70 in the chemical formula (1) is selected from the group represented by the chemical formula (2) where X in the chemical formula (1) is 70 mol% or more, and the unit structure represented by the following chemical formula (3) is 30 4. The polyimide precursor according to item 3, wherein the polyimide precursor has a mol% or less.
〔式(3)中、Zは2価の基を表し、R10、R11はいずれも独立に、水素原子又は、炭素数1〜6のアルキル基、炭素数3〜9のアルキルシリル基であり、Yは下記化学式(4)の構造の4価の基を表す。〕
[In Formula (3), Z represents a divalent group, and R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. Yes, Y represents a tetravalent group having the structure of the following chemical formula (4). ]
5. 30℃、0.5g/dLのN,N−ジメチルアセトアミド溶液における対数粘度が0.2dL/g以上であることを特徴とする前記項1〜4いずれかに記載のポリイミド前駆体。 5). Item 5. The polyimide precursor according to any one of Items 1 to 4, wherein a logarithmic viscosity in a 0.5 g / dL N, N-dimethylacetamide solution at 30 ° C. is 0.2 dL / g or more.
6. 得られたポリイミドの複屈折率が0.01以下であることを特徴とする前記項1〜5いずれかに記載のポリイミド前駆体。 6). Item 6. The polyimide precursor according to any one of Items 1 to 5, wherein the obtained polyimide has a birefringence of 0.01 or less.
7. 前記項1〜6いずれかに記載のポリイミド前駆体を用いたポリイミド前駆体溶液組成物。 7). A polyimide precursor solution composition using the polyimide precursor according to any one of Items 1 to 6.
8. 下記化学式(5)中のXが前記化学式(2)で表される群から選択される単位構造を有するポリイミドであって、
このポリイミドが、厚さ10μmのフィルムでの波長400nmの光透過率が75%以上であることを特徴とするポリイミド。
8). X in the following chemical formula (5) is a polyimide having a unit structure selected from the group represented by the chemical formula (2),
The polyimide is characterized in that the light transmittance at a wavelength of 400 nm in a film having a thickness of 10 μm is 75% or more.
9. 複屈折率が0.01以下であることを特徴とする前記項8に記載のポリイミド。 9. 9. The polyimide according to item 8, wherein the birefringence is 0.01 or less.
10. 前記項1〜6のいずれかに記載のポリイミド前駆体から得られるポリイミド、前記項7に記載のポリイミド前駆体溶液組成物から得られるポリイミド、及び前記項8又は9に記載のポリイミドのいずれかのポリイミドを用いたポリイミド溶液組成物。 10. Any one of the polyimide obtained from the polyimide precursor in said claim | item 1-6, the polyimide obtained from the polyimide precursor solution composition of said claim | item 7, and the polyimide of said claim | item 8 or 9 A polyimide solution composition using polyimide.
11. 前記項1〜6のいずれかに記載のポリイミド前駆体、前記項7に記載のポリイミド前駆体溶液組成物、前記項8又は9に記載のポリイミド、及び前記項10に記載のポリイミド溶液組成物のいずれかを用いて得られたポリイミドフィルム。 11. The polyimide precursor according to any one of Items 1 to 6, the polyimide precursor solution composition according to Item 7, the polyimide according to Item 8 or 9, and the polyimide solution composition according to Item 10. A polyimide film obtained by using either.
12. 前記項1〜6のいずれかに記載のポリイミド前駆体、前記項7に記載のポリイミド前駆体溶液組成物、前記項8又は9に記載のポリイミド、及び前記項10に記載のポリイミド溶液組成物のいずれかを用いて形成させたことを特徴とするディスプレイ用、タッチパネル用、または太陽電池用の基板。 12 The polyimide precursor according to any one of Items 1 to 6, the polyimide precursor solution composition according to Item 7, the polyimide according to Item 8 or 9, and the polyimide solution composition according to Item 10. A substrate for a display, a touch panel, or a solar cell, characterized by being formed using any of the above.
13. 前記項1〜6のいずれかに記載のポリイミド前駆体、前記項7に記載のポリイミド前駆体溶液組成物、前記項8又は9に記載のポリイミド、及び前記項10に記載のポリイミド溶液組成物のいずれかを用いて得られた成形品。 13. The polyimide precursor according to any one of Items 1 to 6, the polyimide precursor solution composition according to Item 7, the polyimide according to Item 8 or 9, and the polyimide solution composition according to Item 10. Molded product obtained using either.
本発明によって、優れた透明性、高耐熱性等を有するポリイミド、及びその前駆体を提供することができる。本発明のポリイミドは、特にフレキシブルなディスプレイやタッチパネルなどの表示装置において透明性基板、太陽電池用基板として好適に用いることができる。 According to the present invention, a polyimide having excellent transparency, high heat resistance, and the like, and a precursor thereof can be provided. The polyimide of the present invention can be suitably used as a transparent substrate or a solar cell substrate in a display device such as a flexible display or a touch panel.
本発明のポリイミド前駆体は、前記化学式(1)で表される単位構造を有する。 The polyimide precursor of the present invention has a unit structure represented by the chemical formula (1).
本発明のポリイミド前駆体の前記化学式(1)中のXは、前記化学式(2)で表される2価の基の群から選択される2種類以上からなる。 X in the chemical formula (1) of the polyimide precursor of the present invention consists of two or more types selected from the group of divalent groups represented by the chemical formula (2).
本発明のポリイミド前駆体の前記化学式(2)中の左に記載の構造のR3は、水素原子又は、メチル基、トリフルオロメチル基の群から選択された1種である。得られるポリイミドの熱線膨張係数が低いことから、R3は水素原子であることがより好ましい。 R 3 of the structure described on the left in the chemical formula (2) of the polyimide precursor of the present invention is one selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. R 3 is more preferably a hydrogen atom because the resulting polyimide has a low coefficient of thermal expansion.
特にその限りではないが、本発明のポリイミド前駆体において、前記化学式(2)中のシクロヘキサンとアミノ基の置換位置は、好ましくは50%〜100%、より好ましくは80%〜100%、さらに好ましくは90%〜100%、特に好ましくは100%の1,4位置換体であることが好ましい。さらに1,4−シクロヘキサン置換体の異性体構造は、好ましくは50%〜100%、より好ましくは80%〜100%、さらに好ましくは90%〜100%、特に好ましくは100%のトランス異性体からなることが好適である。1,4−シクロヘキサン置換体や、トランス配置の異性体の含有率が低下すると、ポリイミド前駆体の分子量が上がりにくく、また得られるポリイミドの熱線膨張係数が大きくなったり、着色しやすくなることがある。 Although not particularly limited, in the polyimide precursor of the present invention, the substitution position of cyclohexane and amino group in the chemical formula (2) is preferably 50% to 100%, more preferably 80% to 100%, and still more preferably. Is preferably 90% to 100%, particularly preferably 100% 1,4-position substitution product. Furthermore, the isomeric structure of the 1,4-cyclohexane substituent is preferably from 50% to 100%, more preferably from 80% to 100%, even more preferably from 90% to 100%, particularly preferably from 100% trans isomer. It is preferable to become. When the content of 1,4-cyclohexane-substituted products or trans-configured isomers decreases, the molecular weight of the polyimide precursor is difficult to increase, and the thermal expansion coefficient of the resulting polyimide may increase or may be easily colored. .
本発明のポリイミド前駆体の前記化学式(2)中の中央に記載の構造のR4、R5、R6、及びR7は、水素原子又は、メチル基、トリフルオロメチル基の群から選択される1種である。得られるポリイミドの熱線膨張係数が低いことから、R4、R5、R6、及びR7は水素原子であることがより好ましい。 R 4 , R 5 , R 6 , and R 7 of the structure described in the center of the chemical formula (2) of the polyimide precursor of the present invention are selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. It is one kind. R 4 , R 5 , R 6 , and R 7 are more preferably hydrogen atoms because the resulting polyimide has a low coefficient of thermal linear expansion.
特にその限りではないが、本発明のポリイミド前駆体において、前記化学式(2)中のベンゼンに結合しているフルオレンとアミノ基の置換位置は、好ましくは50%〜100%、より好ましくは80%〜100%、さらに好ましくは90%〜100%、特に好ましくは100%の1,4位置換体であることが好ましい。1,4位置換体の含有率が低下すると、ポリイミド前駆体の分子量が上がりにくくなることがある。 Although not particularly limited, in the polyimide precursor of the present invention, the substitution position of fluorene and amino group bonded to benzene in the chemical formula (2) is preferably 50% to 100%, more preferably 80%. It is preferable to be a 1,4-position substitution product of -100%, more preferably 90% -100%, particularly preferably 100%. When the content of the 1,4-position substitution product decreases, the molecular weight of the polyimide precursor may be difficult to increase.
本発明のポリイミド前駆体の前記化学式(2)中の右に記載の構造のR8、及びR9は、水素原子又は、メチル基、トリフルオロメチル基の群から選択された1種である。得られるポリイミドの熱線膨張係数が低いこと、また、透過率が高いことから、R8、及びR9はトリフルオロメチル基であることがより好ましい。 R 8 and R 9 in the structure described on the right side of the chemical formula (2) of the polyimide precursor of the present invention are one selected from the group consisting of a hydrogen atom, a methyl group, and a trifluoromethyl group. R 8 and R 9 are more preferably a trifluoromethyl group because the resulting polyimide has a low coefficient of thermal expansion and a high transmittance.
特にその限りではないが、本発明のポリイミド前駆体において、前記化学式(2)中のビフェニルに結合している2つのアミノ基の置換位置は、好ましくは50%〜100%、より好ましくは80%〜100%、さらに好ましくは90%〜100%、特に好ましくは100%の4,4’位置換体であることが好ましい。4,4’位置換体の含有率が低下すると、ポリイミド前駆体の分子量が上がりにくくなることがある。 Although not particularly limited, in the polyimide precursor of the present invention, the substitution position of two amino groups bonded to biphenyl in the chemical formula (2) is preferably 50% to 100%, more preferably 80%. It is preferable that the 4,4′-substituted product is ˜100%, more preferably 90% to 100%, particularly preferably 100%. If the content of the 4,4′-substituted product decreases, the molecular weight of the polyimide precursor may be difficult to increase.
本発明のポリイミド前駆体の前記化学式(1)中のXは前記化学式(2)で表される2価の基であれば特に限定はなく、例えば、1,4−ジアミノシクロへキサン、1,4−ジアミノ−2−メチルシクロヘキサン、1,3−ジアミノシクロへキサン、1,3−ジアミノ−2−メチルシクロヘキサン、1,2−ジアミノシクロへキサン、ベンジジン、o − トリジン、m − トリジン、2,2’−ビス(トリフルオロメチル)ベンジジン、3,3’−ビス(トリフルオロメチル)ベンジジン、3 , 3 '− ジアミノ− ビフェニル、オクタフルオロベンジジン、3 , 3 '− ジメチル− 4 , 4 '− ジアミノビフェニル、4, 4’‐(9‐ フルオレンジイル)ジアミン、3, 3’‐(9‐ フルオレンジイル)ジアミン、3, 4’‐(9‐ フルオレンジイル)ジアミン等のジアミン部分を除いた2価の基が挙げられる。これらのうち、得られるポリイミドフィルムの透明性が高く、複屈折率が低いことから、1,4−ジアミノシクロヘキサン、2,2’−ビス(トリフルオロメチル)ベンジジン、4, 4’‐(9‐ フルオレンジイル)ジアミンが特に好ましい。また、上記の1,4−シクロヘキサン構造を有するジアミンの1,4位の立体構造は、特に限定されないが、トランス構造であることが好ましい。シス構造では着色しやすくなるなどの不具合が生じることがある。 X in the chemical formula (1) of the polyimide precursor of the present invention is not particularly limited as long as it is a divalent group represented by the chemical formula (2). For example, 1,4-diaminocyclohexane, 1, 4-diamino-2-methylcyclohexane, 1,3-diaminocyclohexane, 1,3-diamino-2-methylcyclohexane, 1,2-diaminocyclohexane, benzidine, o-tolidine, m-tolidine, 2, 2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 3,3'-diamino-biphenyl, octafluorobenzidine, 3,3'-dimethyl-4,4'-diamino Biphenyl, 4,4 '-(9-Fluorangeyl) diamine, 3,3'-(9-Fluoylyl) diamine, 3,4 '-(9-Fluorangei) ) A divalent group obtained by removing a diamine moiety, such as diamines. Among these, since the obtained polyimide film has high transparency and low birefringence, 1,4-diaminocyclohexane, 2,2′-bis (trifluoromethyl) benzidine, 4, 4 ′-(9- Fully orangeyl) diamine is particularly preferred. The steric structure at the 1,4-position of the diamine having the 1,4-cyclohexane structure is not particularly limited, but is preferably a trans structure. The cis structure may cause problems such as easy coloring.
本発明のポリイミド前駆体は、前記化学式(1)中のXが前記化学式(2)で表される群から選択される単位構造を好ましくは50モル%以上、さらに好ましくは70モル%以上、特に好ましくは90モル%以上有する。前記化学式(1)中のXが前記化学式(2)で表される群から選択される単位構造の含有量が減少すると得られるポリイミドの透過率が低下したり、複屈折率が大きくなることがある。 The polyimide precursor of the present invention preferably has a unit structure in which X in the chemical formula (1) is selected from the group represented by the chemical formula (2), preferably 50 mol% or more, more preferably 70 mol% or more, particularly Preferably it has 90 mol% or more. If the content of a unit structure selected from the group represented by the chemical formula (2) is X in the chemical formula (1), the transmittance of the resulting polyimide may decrease or the birefringence may increase. is there.
本発明のポリイミド前駆体は、前記化学式(1)と前記化学式(3)で表される単位構造を有する。但し、前記化学式(1)と前記化学式(3)とは、同一ではない。 The polyimide precursor of the present invention has a unit structure represented by the chemical formula (1) and the chemical formula (3). However, the chemical formula (1) and the chemical formula (3) are not the same.
本発明のポリイミド前駆体の前記化学式(3)のZであるジアミン成分としては、特に限定はなく 例えば、1,4−ジアミノ−2−エチルシクロヘキサン、1,4−ジアミノ−2−n−プロピルシクロヘキサン、1,4−ジアミノ−2−イソプロピルシクロヘキサン、1,4−ジアミノ−2−n−ブチルシクロヘキサン、1,4−ジアミノ−2−イソブチルシクロヘキサン、1,4−ジアミノ−2―sec―ブチルシクロヘキサン、1,4−ジアミノ−2―tert―ブチルシクロヘキサン、オキシジアニリン、p−フェニレンジアミン、m−フェニレンジアミン、p−メチレンビス(フェニレンジアミン)、ビス(アミノフェノキシ)ベンゼン、ビス((アミノフェノキシ)フェニル)ヘキサフルオロプロパン、ビス((アミノフェニル)ヘキサフルオロ)プロパン、ビス(アミノフェニル)スルホン、ビス((アミノフェノキシ)フェニル)プロパン、ビス(アミノヒドロキシフェニル)ヘキサフルオロプロパン、ビス((アミノフェノキシ)ジフェニル)スルホン、3 , 3 '− ジメトキシ− 4 , 4 '− ジアミノビフェニル、3 , 3 '− ジクロロ− 4 , 4 '− ジアミノビフェニル、3 , 3 '−ジフルオロ− 4 , 4 '− ジアミノビフェニル、4,4’−ジアミノベンズアニリド、N,N’−ビス(4−アミノフェニル)テレフタルアミド、N,N’−p−フェニレンビス(p−アミノベンズアミド)、4,4’−ジアミノベンゾエート、ビス(4−アミノフェニル)テレフタレート、ビフェニル−4,4’−ジカルボン酸ビス(4−アミノフェニル)エステル、p−フェニレンビス(p−アミノベンゾエート)、ビス(4−アミノフェニル)-[1,1'-ビフェニル]-4, 4'-ジカルボキシレート、[1,1'-ビフェニル]-4, 4'-ジイル ビス(4-アミノベンゾエート)等やこれらの誘導体が挙げられる。 There is no limitation in particular as a diamine component which is Z of the said Chemical formula (3) of the polyimide precursor of this invention, For example, 1, 4- diamino- 2-ethylcyclohexane, 1, 4- diamino- 2-n-propyl cyclohexane 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-isobutylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1 , 4-Diamino-2-tert-butylcyclohexane, oxydianiline, p-phenylenediamine, m-phenylenediamine, p-methylenebis (phenylenediamine), bis (aminophenoxy) benzene, bis ((aminophenoxy) phenyl) hexa Fluoropropane, bis ((aminophenyl Hexafluoro) propane, bis (aminophenyl) sulfone, bis ((aminophenoxy) phenyl) propane, bis (aminohydroxyphenyl) hexafluoropropane, bis ((aminophenoxy) diphenyl) sulfone, 3,3′-dimethoxy-4 , 4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, N, N ′ -Bis (4-aminophenyl) terephthalamide, N, N'-p-phenylenebis (p-aminobenzamide), 4,4'-diaminobenzoate, bis (4-aminophenyl) terephthalate, biphenyl-4,4 ' -Dicarboxylic acid bis (4-aminophenyl) ester, p-ph Nylene bis (p-aminobenzoate), bis (4-aminophenyl)-[1,1′-biphenyl] -4,4′-dicarboxylate, [1,1′-biphenyl] -4,4′-diyl bis (4-aminobenzoate) and the like and derivatives thereof.
本発明のポリイミド前駆体のテトラカルボン酸成分としては、前記化学式(1)のテトラカルボン酸成分を構成する4,4’−(ジメチルシランジイル)ジフタル酸類が用いられる。
さらにポリイミド前駆体のテトラカルボン酸成分としては、前記化学式(1)のテトラカルボン酸成分を構成する4,4’−(ジメチルシランジイル)ジフタル酸類と、前記化学式(3)のテトラカルボン酸成分である、Yから構成される。
前記化学式(3)のテトラカルボン酸成分としては、前記化学式(4)に記載の3,3’,4,4’−ビフェニルテトラカルボン酸類、2,3,3’,4’−ビフェニルテトラカルボン酸類、2,2’,3,3’−ビフェニルテトラカルボン酸類、ピロメリット酸類、オキシジフタル酸類、3,3’,4,4’−ベンゾフェノンテトラカルボン酸類、3,3’,4,4’−ジフェニルスルホンテトラカルボン酸類、m−ターフェニル−3,3’,4,4’−テトラカルボン酸類、2,2’−ビス(3,4−ジカルボキシフェニル)プロパン類などが挙げられ、より好ましくは2,3,3’,4’−ビフェニルテトラカルボン酸類、2,2’,3,3’−ビフェニルテトラカルボン酸類を好適に挙げることができる。
As the tetracarboxylic acid component of the polyimide precursor of the present invention, 4,4 ′-(dimethylsilanediyl) diphthalic acid constituting the tetracarboxylic acid component of the chemical formula (1) is used.
Further, as the tetracarboxylic acid component of the polyimide precursor, 4,4 ′-(dimethylsilanediyl) diphthalic acid constituting the tetracarboxylic acid component of the chemical formula (1) and the tetracarboxylic acid component of the chemical formula (3) It is composed of Y.
Examples of the tetracarboxylic acid component of the chemical formula (3) include 3,3 ′, 4,4′-biphenyltetracarboxylic acids and 2,3,3 ′, 4′-biphenyltetracarboxylic acids described in the chemical formula (4). 2,2 ′, 3,3′-biphenyltetracarboxylic acids, pyromellitic acids, oxydiphthalic acids, 3,3 ′, 4,4′-benzophenone tetracarboxylic acids, 3,3 ′, 4,4′-diphenylsulfone And tetracarboxylic acids, m-terphenyl-3,3 ′, 4,4′-tetracarboxylic acids, 2,2′-bis (3,4-dicarboxyphenyl) propane, and the like, more preferably 2, Preferable examples include 3,3 ′, 4′-biphenyltetracarboxylic acids and 2,2 ′, 3,3′-biphenyltetracarboxylic acids.
本発明のポリイミド前駆体の前記化学式(1)、前記化学式(3)中のR1、R2、R10、R11は、特に限定されないが、水素原子あるいは、炭素数1〜6のアルキル基の場合、メチル基、エチル基、n−プロピル基、iso−プロピル基、n−ブチル基、iso−ブチル基、sec−ブチル基等、炭素数3〜9のアルキルシリル基の場合、トリメチルシリル基、ジメチルイソプロピルシリル基、tert−ブチルジメチルシリル基、トリイソプロピルシリル基が挙げられる。経済性からアルキルシリル基の場合はトリメチルシリル基がより好ましい。 R 1 , R 2 , R 10 and R 11 in the chemical formula (1) and chemical formula (3) of the polyimide precursor of the present invention are not particularly limited, but are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In the case of an alkylsilyl group having 3 to 9 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a trimethylsilyl group, Examples thereof include a dimethylisopropylsilyl group, a tert-butyldimethylsilyl group, and a triisopropylsilyl group. In the case of an alkylsilyl group, a trimethylsilyl group is more preferable from the viewpoint of economy.
さらに、前記化学式(1)のR1,R2の少なくともどちらか一方が、炭素数1〜6のアルキル基もしくは、炭素数3〜9のアルキルシリル基であり、前記化学式(3)のR10、R11の少なくともどちらか一方が、炭素数1〜6のアルキル基、炭素数3〜9のアルキルシリル基であることが好ましい。R1、R2、R10、R11の一部がアルキル基、アルキルシリル基である場合、ポリアミック酸製造時に析出などの不具合が改善されるとともに、イミド化の過程で生じる分子量低下を防ぐことができ、ポリイミドの靭性(破断伸度)が向上する。 Furthermore, at least one of R 1 and R 2 in the chemical formula (1) is an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms, and R 10 in the chemical formula (3). , R 11 is preferably an alkyl group having 1 to 6 carbon atoms or an alkylsilyl group having 3 to 9 carbon atoms. When a part of R 1 , R 2 , R 10 and R 11 is an alkyl group or an alkylsilyl group, problems such as precipitation during the production of polyamic acid are improved, and a decrease in molecular weight that occurs during the imidization process is prevented. And the toughness (breaking elongation) of the polyimide is improved.
本発明のポリイミド前駆体の対数粘度は、特に限定されないが、30℃での0.5g/dL N,N−ジメチルアセトアミド溶液における対数粘度が0.2dL/g以上、好ましくは0.5dL/g、より好ましくは1.0dL/g以上である。0.2dL/g以下では、ポリイミド前駆体の分子量が低く、得られるポリイミド膜の機械強度や耐熱性が低下する。 The logarithmic viscosity of the polyimide precursor of the present invention is not particularly limited, but the logarithmic viscosity in a 0.5 g / dL N, N-dimethylacetamide solution at 30 ° C. is 0.2 dL / g or more, preferably 0.5 dL / g. More preferably, it is 1.0 dL / g or more. If it is 0.2 dL / g or less, the molecular weight of the polyimide precursor is low, and the mechanical strength and heat resistance of the resulting polyimide film are lowered.
本発明のポリイミド前駆体は、R1、R2、R10、及びR11が取る化学構造に従って、1)ポリアミド酸(R1、R2、R10、及びR11が水素)、2)ポリアミド酸エステル(R1、R2の少なくとも一部、もしくはR10、R11の少なくとも一部がアルキル基)、3)4)ポリアミド酸シリルエステル(R1、R2の少なくとも一部、もしくはR10、R11の少なくとも一部がアルキルシリル基)に化学構造として分類することができる。そして前記分類ごとに、以下の製造方法により容易に製造することができる。ただし、本発明のポリイミド前駆体の製造方法は、以下の製造方法に限定されるわけではない。 Polyimide precursors of the present invention, according to the chemical structure R 1, R 2, R 10, where and R 11 taken, 1) a polyamic acid (R 1, R 2, R 10, and R 11 is hydrogen), 2) polyamide Acid ester (at least part of R 1 and R 2 or at least part of R 10 and R 11 is an alkyl group), 3) 4) polyamic acid silyl ester (at least part of R 1 and R 2 , or R 10 , At least a portion of R 11 can be classified as a chemical structure. And it can manufacture easily with the following manufacturing methods for every said classification. However, the manufacturing method of the polyimide precursor of this invention is not necessarily limited to the following manufacturing methods.
1)ポリアミド酸
本発明のポリイミド前駆体は、溶媒中でテトラカルボン酸成分としてのテトラカルボン酸二無水物とジアミン成分とを略等モル、好ましくはテトラカルボン酸成分に対するジアミン成分のモル比[ジアミン成分のモル数/テトラカルボン酸成分のモル数]が好ましくは0.90〜1.10、より好ましくは0.95〜1.05の割合で、例えば120℃以下の比較的低温度でイミド化を抑制しながら反応することによって、ポリイミド前駆体溶液組成物として好適に得ることができる。
1) Polyamic acid The polyimide precursor of the present invention comprises a tetracarboxylic dianhydride as a tetracarboxylic acid component and a diamine component in a solvent in an approximately equimolar amount, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [diamine. The number of moles of component / number of moles of tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, imidization at a relatively low temperature of 120 ° C. or less. It can obtain suitably as a polyimide precursor solution composition by reacting, suppressing.
限定するものではないが、より具体的には、有機溶剤にジアミンを溶解し、この溶液に攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、0〜120℃、好ましくは5〜80℃の範囲で1〜72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。上記製造方法でのジアミンとテトラカルボン酸二無水物の添加順序は、ポリイミド前駆体の分子量が上がりやすいため、好ましい。また、上記製造方法のジアミンとテトラカルボン酸二無水物の添加順序を逆にすることも可能であり、析出物が低減することから、好ましい。 Although it does not limit, more specifically, diamine is melt | dissolved in an organic solvent, Tetracarboxylic dianhydride is added gradually, stirring to this solution, 0-120 degreeC, Preferably it is 5-80. A polyimide precursor is obtained by stirring for 1 to 72 hours in the range of ° C. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. The order of addition of diamine and tetracarboxylic dianhydride in the above production method is preferable because the molecular weight of the polyimide precursor is likely to increase. Moreover, it is also possible to reverse the order of addition of the diamine and tetracarboxylic dianhydride in the above production method, and this is preferable because precipitates are reduced.
また、テトラカルボン酸成分とジアミン成分のモル比がジアミン成分過剰である場合、必要に応じて、ジアミン成分の過剰モル数に略相当する量のカルボン酸誘導体を添加し、テトラカルボン酸成分とジアミン成分のモル比を略当量に近づけることができる。ここでのカルボン酸誘導体としては、実質的にポリイミド前駆体溶液の粘度を増加させない、つまり実質的に分子鎖延長に関与しないテトラカルボン酸、もしくは末端停止剤として機能するトリカルボン酸とその無水物、ジカルボン酸とその無水物などが好適である。 Moreover, when the molar ratio of the tetracarboxylic acid component and the diamine component is an excess of the diamine component, if necessary, an amount of a carboxylic acid derivative substantially corresponding to the excess mole number of the diamine component is added, and the tetracarboxylic acid component and the diamine are added. The molar ratio of the components can be approximated to the equivalent. As the carboxylic acid derivative herein, a tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, substantially does not participate in molecular chain extension, or a tricarboxylic acid that functions as a terminal terminator and its anhydride, Dicarboxylic acid and its anhydride are preferred.
2)ポリアミド酸エステル
テトラカルボン酸二無水物を任意のアルコールと反応させ、ジエステルジカルボン酸を得た後、塩素化試薬(チオニルクロライド、オキサリルクロライドなど)と反応させ、ジエステルジカルボン酸クロライドを得る。このジエステルジカルボン酸クロライドとジアミンを−20〜120℃、好ましくは−5〜80℃の範囲で1〜72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。また、ジエステルジカルボン酸とジアミンを、リン系縮合剤や、カルボジイミド縮合剤などを用いて脱水縮合することでも、簡便にポリイミド前駆体が得られる。
2) Polyamic acid ester After reacting tetracarboxylic dianhydride with an arbitrary alcohol to obtain a diester dicarboxylic acid, it is reacted with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain a diester dicarboxylic acid chloride. The polyimide precursor is obtained by stirring the diester dicarboxylic acid chloride and the diamine in the range of -20 to 120 ° C, preferably -5 to 80 ° C for 1 to 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably. Alternatively, a polyimide precursor can be easily obtained by dehydrating and condensing diester dicarboxylic acid and diamine using a phosphorus condensing agent or a carbodiimide condensing agent.
この方法で得られるポリイミド前駆体は、安定なため、水やアルコールなどの溶剤を加えて再沈殿などの精製を行うこともできる。 Since the polyimide precursor obtained by this method is stable, it can be purified by reprecipitation by adding a solvent such as water or alcohol.
3)ポリアミド酸シリルエステル(間接法)
あらかじめ、ジアミンとシリル化剤を反応させ、シリル化されたジアミンを得る。必要に応じて、蒸留等により、シリル化されたジアミンの精製を行う。そして、脱水された溶剤中にシリル化されたジアミンを溶解させておき、攪拌しながら、テトラカルボン酸二無水物を徐々に添加し、0〜120℃、好ましくは5〜80℃の範囲で1〜72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
3) Polyamide acid silyl ester (indirect method)
A diamine and a silylating agent are reacted in advance to obtain a silylated diamine. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and tetracarboxylic dianhydride is gradually added while stirring, and the temperature is 0 to 120 ° C., preferably 5 to 80 ° C. A polyimide precursor is obtained by stirring for 72 hours. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
ここで用いるシリル化剤として、塩素を含有しないシリル化剤を用いることは、シリル化されたジアミンを精製する必要がないため、好適である。塩素原子を含まないシリル化剤としては、N,O−ビス(トリメチルシリル)トリフルオロアセトアミド、N,O−ビス(トリメチルシリル)アセトアミド、ヘキサメチルジシラザンが挙げられる。フッ素原子を含まず低コストであることから、N,O−ビス(トリメチルシリル)アセトアミド、ヘキサメチルジシラザンが特に好ましい。 As the silylating agent used here, it is preferable to use a silylating agent not containing chlorine because it is not necessary to purify the silylated diamine. Examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.
また、ジアミンのシリル化反応には、反応を促進するために、ピリジン、ピペリジン、トリエチルアミンなどのアミン系触媒を用いることができる。この触媒はポリイミド前駆体の重合触媒として、そのまま使用することができる。 In addition, amine-based catalysts such as pyridine, piperidine and triethylamine can be used in the silylation reaction of diamine in order to accelerate the reaction. This catalyst can be used as it is as a polymerization catalyst for the polyimide precursor.
4)ポリアミド酸シリルエステル(直接法)
1)の方法で得られたポリアミド酸溶液とシリル化剤を混合し、0〜120℃、好ましくは5〜80℃の範囲で1〜72時間攪拌することで、ポリイミド前駆体が得られる。80℃以上で反応させる場合、分子量が重合時の温度履歴に依存して変動し、また熱によりイミド化が進行することから、ポリイミド前駆体を安定して製造できなくなる可能性がある。
4) Polyamide acid silyl ester (direct method)
The polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method 1) and the silylating agent and stirring for 1 to 72 hours in the range of 0 to 120 ° C, preferably 5 to 80 ° C. When the reaction is carried out at 80 ° C. or higher, the molecular weight varies depending on the temperature history at the time of polymerization, and imidization proceeds due to heat, so there is a possibility that the polyimide precursor cannot be produced stably.
ここで用いるシリル化剤として、塩素を含有しないシリル化剤を用いることは、シリル化されたジアミンを精製する必要がないため、好適である。塩素原子を含まないシリル化剤としては、N,O−ビス(トリメチルシリル)トリフルオロアセトアミド、N,O−ビス(トリメチルシリル)アセトアミド、ヘキサメチルジシラザンが挙げられる。フッ素原子を含まず低コストであることから、N,O−ビス(トリメチルシリル)アセトアミド、ヘキサメチルジシラザンが特に好ましい。 As the silylating agent used here, it is preferable to use a silylating agent not containing chlorine because it is not necessary to purify the silylated diamine. Examples of the silylating agent not containing a chlorine atom include N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (trimethylsilyl) acetamide, and hexamethyldisilazane. N, O-bis (trimethylsilyl) acetamide and hexamethyldisilazane are particularly preferred because they do not contain fluorine atoms and are low in cost.
5)部分イミド化ポリイミド前駆体
あらかじめテトラカルボン酸誘導体とジアミン誘導体を反応、イミド化させ、末端基がテトラカルボン酸誘導体、もしくはジアミン誘導体としたイミド基含有モノマーもしくはオリゴマーを用いて、上記1)〜4)の前駆体をそれぞれの方法で得ることができる。
5) Partially imidized polyimide precursor A tetracarboxylic acid derivative and a diamine derivative are reacted and imidized in advance, and the terminal group is a tetracarboxylic acid derivative or an imide group-containing monomer or oligomer in which the diamine derivative is used. The precursor of 4) can be obtained by each method.
また、前記製造方法は、いずれも低温で有機溶媒中にて好適に行なうことができるので、その結果として、本発明のポリイミド前駆体溶液組成物を容易に得ることができる。 Moreover, since the said manufacturing method can be suitably performed in an organic solvent at low temperature, as a result, the polyimide precursor solution composition of this invention can be obtained easily.
これらの製造方法においては、いずれも、テトラカルボン酸成分/ジアミン成分のモル比は、必要とするポリイミド前駆体の粘度により任意に設定できるが、好ましくは0.90〜1.10、より好ましくは0.95〜1.05である。
含み、前記製造方法の原料として好適な化学構造の化合物として用いられる。
In any of these production methods, the molar ratio of the tetracarboxylic acid component / diamine component can be arbitrarily set depending on the required viscosity of the polyimide precursor, preferably 0.90 to 1.10, more preferably 0.95 to 1.05.
In addition, it is used as a compound having a chemical structure suitable as a raw material for the production method.
前記製造方法で使用する有機溶媒は、具体的にはN,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチル−2−ピロリドン、ジメチルスルホオキシド等の非プロトン性溶媒が好ましいが、原料モノマーと生成するポリイミド前駆体が溶解すれば問題はなく使用できるので、特にその構造には限定されない。N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン等のアミド溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、m−クレゾール、p−クレゾール、3−クロロフェノール、4−クロロフェノール等のフェノール系溶媒、アセトフェノン、1,3−ジメチル−2−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、0−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、プチルセロソルブ、2−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。 Specifically, the organic solvent used in the production method is preferably an aprotic solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, etc. There is no problem as long as the monomer and the polyimide precursor to be produced are dissolved, and the structure is not particularly limited. Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ -Cyclic ester solvents such as butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, Acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. In addition, other common organic solvents such as phenol, 0-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, ptyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, Petroleum naphtha solvents can also be used.
本発明の製造方法において、テトラカルボン酸成分とジアミン成分のモル比がジアミン成分過剰である場合、必要に応じて、過剰ジアミン分のモル数に概略相当する量のカルボン酸誘導体を添加し、テトラカルボン酸成分とジアミン成分のモル比を当量に近づけることができる。ここでのカルボン酸誘導体としては、実質的にポリイミド前駆体溶液の粘度を増加させない(つまり実質的に分子鎖延長に関与しない)テトラカルボン酸もしくは、末端停止剤として機能するトリカルボン酸とその無水物、ジカルボン酸とその無水物である。 In the production method of the present invention, when the molar ratio of the tetracarboxylic acid component to the diamine component is excessive, the carboxylic acid derivative in an amount roughly corresponding to the number of moles of excess diamine is added as necessary. The molar ratio of the carboxylic acid component and the diamine component can be brought close to the equivalent. As the carboxylic acid derivative here, a tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution (that is, it does not substantially participate in molecular chain extension), or a tricarboxylic acid that functions as a terminal terminator and its anhydride. Dicarboxylic acid and its anhydride.
テトラカルボン酸誘導体としては、3,3’,4,4’−ビフェニルテトラカルボン酸、2,3,3’,4’−ビフェニルテトラカルボン酸、2,2’,3,3’−ビフェニルテトラカルボン酸、1,2,3,4−ブタンテトラカルボン酸、ベンゼン−1,2,4,5−テトラカルボン酸、トリカルボン酸としては、トリメリット酸、シクロヘキサン−1,2,4−トリカルボン酸と、これらの酸無水物、ジカルボン酸としては、フタル酸、テトラハイドロフタル酸、シス−ノルボルネン−エンド−2,3−ジカルボン酸、シクロヘキサンジカルボン酸、コハク酸、マレイン酸と、これらの酸無水物を挙げることができる。これらのカルボン酸誘導体を用いることで、加熱時の熱着色、熱劣化を防止できることがある。特に、ビフェニルテトラカルボン酸などのテトラカルボン酸誘導体や、反応性官能基を有するカルボン酸誘導体は、イミド化する際反応し、耐熱性を向上させることができるため、好ましい。 Examples of tetracarboxylic acid derivatives include 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. As acid, 1,2,3,4-butanetetracarboxylic acid, benzene-1,2,4,5-tetracarboxylic acid, and tricarboxylic acid, trimellitic acid, cyclohexane-1,2,4-tricarboxylic acid, Examples of these acid anhydrides and dicarboxylic acids include phthalic acid, tetrahydrophthalic acid, cis-norbornene-endo-2,3-dicarboxylic acid, cyclohexanedicarboxylic acid, succinic acid, maleic acid, and these acid anhydrides. be able to. By using these carboxylic acid derivatives, thermal coloring and thermal deterioration during heating may be prevented. In particular, tetracarboxylic acid derivatives such as biphenyltetracarboxylic acid and carboxylic acid derivatives having a reactive functional group are preferable because they can react when imidized to improve heat resistance.
本発明のポリイミド前駆体溶液組成物は、少なくとも本発明のポリイミド前駆体と溶媒とからなり、溶媒とテトラカルボン酸成分とジアミン成分との合計量に対して、テトラカルボン酸成分とジアミン成分との合計量が5質量%以上、好ましくは10質量%以上、より好ましくは15質量%以上の割合であることが好適である。なお、通常は60質量%以下、好ましくは50質量%以下であることが好適である。5質量%以下であると得られるポリイミドフィルムの膜厚の制御が難しくなることがある。 The polyimide precursor solution composition of the present invention comprises at least the polyimide precursor of the present invention and a solvent. The total amount of the solvent, the tetracarboxylic acid component, and the diamine component is a combination of the tetracarboxylic acid component and the diamine component. The total amount is preferably 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more. In general, the content is preferably 60% by mass or less, and preferably 50% by mass or less. Control of the film thickness of the polyimide film obtained as it is 5 mass% or less may become difficult.
本発明のポリイミド前駆体溶液組成物に用いる溶媒としては、ポリイミド前駆体が溶解すれば問題はなく、特にその構造には限定されない。N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルピロリドン等のアミド溶媒、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、γ−カプロラクトン、ε−カプロラクトン、α−メチル−γ−ブチロラクトン等の環状エステル溶媒、エチレンカーボネート、プロピレンカーボネート等のカーボネート溶媒、トリエチレングリコール等のグリコール系溶媒、m−クレゾール、p−クレゾール、3−クロロフェノール、4−クロロフェノール等のフェノール系溶媒、アセトフェノン、1,3−ジメチル−2−イミダゾリジノン、スルホラン、ジメチルスルホキシドなどが好ましく採用される。さらに、その他の一般的な有機溶剤、即ちフェノール、0−クレゾール、酢酸ブチル、酢酸エチル、酢酸イソブチル、プロピレングリコールメチルアセテート、エチルセロソルブ、プチルセロソルブ、2−メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルセロソルブアセテート、テトラヒドロフラン、ジメトキシエタン、ジエトキシエタン、ジブチルエーテル、ジエチレングリコールジメチルエーテル、メチルイソブチルケトン、ジイソブチルケトン、シクロペンタノン、シクロへキサノン、メチルエチルケトン、アセトン、ブタノール、エタノール、キシレン、トルエン、クロルベンゼン、ターペン、ミネラルスピリット、石油ナフサ系溶媒なども使用できる。また、これらを複数組み合わせて使用することもできる。 The solvent used in the polyimide precursor solution composition of the present invention is not a problem as long as the polyimide precursor is dissolved, and is not particularly limited to its structure. Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ -Cyclic ester solvents such as butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, phenol solvents such as m-cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, Acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide and the like are preferably employed. In addition, other common organic solvents such as phenol, 0-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, ptyl cellosolve, 2-methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, Tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorobenzene, terpene, mineral spirit, Petroleum naphtha solvents can also be used. A combination of these can also be used.
本発明のポリイミド前駆体溶液組成物は、必要に応じて、化学イミド化剤(無水酢酸などの酸無水物や、ピリジン、イソキノリンなどのアミン化合物)、酸化防止剤、フィラー、染料、無機顔料、シランカップリング剤、難燃材、消泡剤、レベリング剤、レオロジーコントロール剤(流動補助剤)、剥離剤などを添加することができる。 The polyimide precursor solution composition of the present invention may contain a chemical imidizing agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, a filler, a dye, an inorganic pigment, if necessary. Silane coupling agents, flame retardants, antifoaming agents, leveling agents, rheology control agents (flow aids), release agents and the like can be added.
本発明のポリイミドは、本発明のポリイミド前駆体を脱水閉環反応(イミド化反応)することで製造することができる。イミド化の方法は特に限定されず、公知の熱イミド化、化学イミド化方法を適用することができる。得られるポリイミドの形態は、フィルム、ポリイミド積層体、粉末、ビーズ、成型体、発泡体およびワニスなどを好適に挙げることができる。 The polyimide of the present invention can be produced by subjecting the polyimide precursor of the present invention to a dehydration ring closure reaction (imidation reaction). The imidization method is not particularly limited, and known thermal imidization and chemical imidization methods can be applied. The form of the obtained polyimide can mention a film, a polyimide laminated body, a powder, a bead, a molded object, a foam, a varnish, etc. suitably.
以下では、本発明のポリイミドフィルム、及びそれを基板に積層した基板積層体の製造方法について述べる。ただし、以下の方法に限定されるものではない。
例えばセラミック(ガラス、シリコン、アルミナ)、金属(銅、アルミニウム、ステンレス)、耐熱プラスチックフィルム(ポリイミド)などの基板に、本発明のポリイミド前駆体溶液組成物を流延し、真空中、窒素等の不活性ガス中、あるいは空気中で、熱風もしくは赤外線を用い、20〜180℃、好ましくは20〜150℃で乾燥する。次に得られたポリイミド前駆体を基板上で、もしくはポリイミド前駆体(フィルム)を剥離し、そのフィルム端部を固定した状態で、真空中、窒素等の不活性ガス中、あるいは空気中で、熱風もしくは赤外線を用い、200〜500℃、より好ましくは250〜450℃で加熱することでポリイミド/基板積層体、もしくはポリイミドフィルムを製造することができる。得られるポリイミドが酸化劣化するのを防ぐため、イミド化は真空中あるいは不活性ガス中で行うことが望ましい。イミド化温度が高すぎなければ空気中で行なっても差し支えない。
Below, the polyimide film of this invention and the manufacturing method of the board | substrate laminated body which laminated | stacked it on the board | substrate are described. However, it is not limited to the following method.
For example, the polyimide precursor solution composition of the present invention is cast on a substrate such as ceramic (glass, silicon, alumina), metal (copper, aluminum, stainless steel), heat-resistant plastic film (polyimide), etc. Drying is performed at 20 to 180 ° C., preferably 20 to 150 ° C. using hot air or infrared rays in an inert gas or air. Next, the obtained polyimide precursor is peeled off on the substrate or the polyimide precursor (film), and the film end is fixed, in vacuum, in an inert gas such as nitrogen, or in air, A polyimide / substrate laminate or a polyimide film can be produced by heating at 200 to 500 ° C., more preferably 250 to 450 ° C., using hot air or infrared rays. In order to prevent the resulting polyimide from being oxidized and deteriorated, it is desirable to perform imidization in a vacuum or in an inert gas. If the imidization temperature is not too high, it may be carried out in air.
またイミド化反応は、前記のような熱処理に代えて、ポリイミド前駆体をピリジンやトリエチルアミン等の3級アミン存在下、無水酢酸等の脱水環化試薬を含有する溶液に浸漬することによって行うことも可能である。また、これらの脱水環化試薬をあらかじめ、ポリイミド前駆体溶液組成物中に投入・攪拌し、それを基板上に流延・乾燥することで、部分的にイミド化したポリイミド前駆体を作製することもでき、これを更に前記のようにして熱処理することでもポリイミド/基板積層体、もしくはポリイミドフィルムを得ることができる。 The imidation reaction may be performed by immersing the polyimide precursor in a solution containing a dehydrating cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine instead of the heat treatment as described above. Is possible. In addition, a partially imidized polyimide precursor is prepared by previously charging and stirring these dehydrating cyclization reagents in a polyimide precursor solution composition, and casting and drying it on a substrate. It is also possible to obtain a polyimide / substrate laminate or a polyimide film by further heat-treating it as described above.
ここで、前記ポリイミド/基板積層体を用いた積層体の製造方法の一例を説明すると、ポリイミド前駆体溶液組成物を、ガラス基板、セラミック基板、金属基板、或いは耐熱性プラスチック基板へ塗布し、真空中、窒素もしくは空気中で、200〜500℃まで加熱してイミド化し、ポリイミド/基板積層体を製造する工程と、基板よりポリイミドを剥離せずに、得られた積層体のポリイミド表面にセラミック薄膜もしくは金属薄膜を形成させ、薄膜/ポリイミド/基板積層体を製造する工程と、その後必要に応じて、基板よりポリイミドを剥離する工程を具備してなる。基板よりポリイミドを剥離せずに、ポリイミド/基板積層体の状態で、スパッタ蒸着などによって前記薄膜を形成するなどの、その後の加工に用いることで、経済的であり、搬送性が良好であり、寸法安定性や加工時の高い寸法精度を得ることができる。 Here, an example of a method for producing a laminate using the polyimide / substrate laminate will be described. A polyimide precursor solution composition is applied to a glass substrate, a ceramic substrate, a metal substrate, or a heat-resistant plastic substrate, and a vacuum is applied. A process for producing a polyimide / substrate laminate by heating to 200 to 500 ° C. in nitrogen or air, and a ceramic thin film on the polyimide surface of the resulting laminate without peeling the polyimide from the substrate Alternatively, it comprises a step of forming a metal thin film to produce a thin film / polyimide / substrate laminate, and then a step of peeling the polyimide from the substrate, if necessary. By using it for subsequent processing, such as forming the thin film by sputtering deposition, etc., in the state of polyimide / substrate laminate without peeling the polyimide from the substrate, it is economical and has good transportability, Dimensional stability and high dimensional accuracy during processing can be obtained.
本発明のポリイミドは、膜厚10μmのフィルムにしたとき、400nmにおける光透過率が75%以上、好ましくは80%以上、より好ましくは85%以上、特に好ましくは90%以上である。 When the polyimide of the present invention is formed into a film having a thickness of 10 μm, the light transmittance at 400 nm is 75% or more, preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more.
本発明のポリイミドは特に限定されないが、フィルム厚み方向の複屈折率が好ましくは0.01以下、より好ましくは0.005以下、特に好ましくは0.003以下である。複屈折率が低いことで画像のぼやけがなくなり、高精細な画像を表示することができる。 The polyimide of the present invention is not particularly limited, but the birefringence in the film thickness direction is preferably 0.01 or less, more preferably 0.005 or less, and particularly preferably 0.003 or less. Since the birefringence is low, the image is not blurred and a high-definition image can be displayed.
本発明のポリイミドからなるフィルムは、用途にもよるが、フィルムの厚みとしては1μm〜200μm程度が好ましく、さらには1μm〜100μm程度が好ましい。 The film made of the polyimide of the present invention depends on the use, but the thickness of the film is preferably about 1 μm to 200 μm, more preferably about 1 μm to 100 μm.
本発明のポリイミドは、特に限定されないが、優れた透明性を有する、またさらに低複屈折率を有する特性から、このポリイミドを主たる基材としたディスプレイ用透明基板、又はタッチパネル用透明基板、太陽電池用基板として好適に用いることができる。 Although the polyimide of this invention is not specifically limited, From the characteristic which has the outstanding transparency and also a low birefringence, the transparent substrate for displays which used this polyimide as the main base material, or the transparent substrate for touch panels, a solar cell It can be suitably used as a substrate for use.
以下、実施例及び比較例によって本発明を更に説明する。尚、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example.
以下の各例において評価は次の方法で行った。 In each of the following examples, evaluation was performed by the following method.
ポリイミド前駆体の評価
[固形分濃度]
アルミシャーレにポリイミド前駆体組成物1gを量り取り、200℃の熱風循環オーブン中で2時間加熱して固形分以外を除去し、その残分の質量より固形分濃度(質量%)を求めた。
[対数粘度]
0.5g/dL ポリイミド前駆体のN,N−ジメチルアセトアミド溶液を、ウベローデ粘度計を用いて、30℃で測定し、対数粘度を求めた。
Evaluation of polyimide precursors
[Solid content]
1 g of the polyimide precursor composition was weighed in an aluminum petri dish, heated for 2 hours in a hot air circulating oven at 200 ° C. to remove the solid content, and the solid content concentration (mass%) was determined from the mass of the residue.
[Logarithmic viscosity]
An N, N-dimethylacetamide solution of 0.5 g / dL polyimide precursor was measured at 30 ° C. using an Ubbelohde viscometer to determine the logarithmic viscosity.
ポリイミドフィルムの評価
[光透過率]
大塚電子製MCPD−300を用いて、膜厚約10μmのポリイミドフィルムの400nmにおける光透過率を測定した。
[弾性率、破断伸度、破断強度]
ポリイミドフィルムをIEC450規格のダンベル形状に打ち抜いて試験片とし、ORIENTEC社製TENSILONを用いて、チャック間 30mm、引張速度 2mm/minで、初期の弾性率、破断伸度、破断強度を測定した。
[屈折率]
ATAGO製DR−M2を用いて、D線(589nm)でポリイミドフィルムの屈折率を測定した。なお、測定は、23℃、50%RHで行った。
[複屈折率]
王子計測機器製KOBRA−WRを用いて、波長590nmにおけるポリイミドフィルムの面内屈折率(nTE)、面外屈折率(nTM)を測定し、nTE − nTM
を複屈折率とした。なお、測定は、23℃、50%RHで行った。
Evaluation of polyimide film
[Light transmittance]
The light transmittance at 400 nm of a polyimide film having a thickness of about 10 μm was measured using MCPD-300 manufactured by Otsuka Electronics.
[Elastic modulus, elongation at break, strength at break]
The polyimide film was punched into an IEC450 standard dumbbell shape to form a test piece, and the initial elastic modulus, breaking elongation, and breaking strength were measured using a TENSILON manufactured by ORIENTEC Co., Ltd., with a chuck distance of 30 mm and a tensile speed of 2 mm / min.
[Refractive index]
Using ATAGO DR-M2, the refractive index of the polyimide film was measured at D line (589 nm). The measurement was performed at 23 ° C. and 50% RH.
[Birefringence]
Using KOBRA-WR manufactured by Oji Scientific Instruments, the in-plane refractive index (n TE ) and out-of-plane refractive index (n TM ) of the polyimide film at a wavelength of 590 nm were measured, and n TE -n TM
Was the birefringence. The measurement was performed at 23 ° C. and 50% RH.
表1に実施例、比較例で使用したテトラカルボン酸成分、ジアミン成分の構造式を示す。 Table 1 shows the structural formulas of the tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples.
〔実施例1〕
反応容器中にトランス−1,4−ジアミノシクロヘキサン(以下、t−DACHと略記することもある)1.20g(0.0105モル)を入れ、モレキュラーシーブを用いて脱水したN,N−ジメチルアセトアミド(以下、DMAcと略記することもある)27.8gに溶解した。この溶液に4,4’−(ジメチルシランジイル)ジフタル酸二無水物(以下、DPSDAと略記することもある)3.70g(0.0105モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
[Example 1]
1.20 g (0.0105 mol) of trans-1,4-diaminocyclohexane (hereinafter sometimes abbreviated as t-DACH) was put in a reaction vessel, and dehydrated using molecular sieve, N, N-dimethylacetamide Dissolved in 27.8 g (hereinafter sometimes abbreviated as DMAc). To this solution, 3.70 g (0.0105 mol) of 4,4 ′-(dimethylsilanediyl) diphthalic dianhydride (hereinafter sometimes abbreviated as DPSDA) was gradually added and stirred at 25 ° C. for 24 hours. . A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例2〕
反応容器中にt−DACH 1.00g(0.009モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 30.5gに溶解した。この溶液にDPSDA 2.86g(0.0081モル)と2,2’,3,3’−ビフェニルテトラカルボン酸二無水物(以下、i−BPDAと略記することもある)0.27g(0.0009モル)とを徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
[Example 2]
In a reaction vessel, 1.00 g (0.009 mol) of t-DACH was put and dissolved in 30.5 g of DMAc dehydrated using a molecular sieve. In this solution, 2.86 g (0.0081 mol) of DPSDA and 0.27 g (0.001 mol) of 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as i-BPDA) (0. 0009 mol) was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例3〕
ジアミン成分、カルボン酸成分を表1に記載したモル量、以外は、実施例3と同様にして、ポリイミド前駆体溶液、ポリイミドフィルムを得た。このポリイミド前駆体溶液、ポリイミドフィルムの特性を測定した結果を表2に示す。
Example 3
A polyimide precursor solution and a polyimide film were obtained in the same manner as in Example 3 except that the molar amount of the diamine component and the carboxylic acid component described in Table 1 were used. Table 2 shows the results of measuring the properties of the polyimide precursor solution and the polyimide film.
〔実施例4〕
反応容器中にt−DACH 1.05g(0.0092モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 30.70gに溶解した。この溶液に DPSDA 2.93g(0.0083モル)を徐々に加え、25℃で72時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。この溶液にピロメリット酸二無水物(以下、PMDAと略記することもある)0.20g(0.0009モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
Example 4
The reaction vessel was charged with 1.05 g (0.0092 mol) of t-DACH and dissolved in 30.70 g of DMAc dehydrated using a molecular sieve. To this solution, 2.93 g (0.0083 mol) of DPSDA was gradually added and stirred at 25 ° C. for 72 hours. A uniform and viscous polyimide precursor solution composition was obtained. To this solution, 0.20 g (0.0009 mol) of pyromellitic dianhydride (hereinafter sometimes abbreviated as PMDA) was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例5〕
反応容器中に、4,4‘−ビス(トリフルオロメチル)ベンジジン(以下、TFMBと略記することもある)3.20g (0.01モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 26.9gに溶解した。この溶液にDPSDA 3.52g(0.01モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
Example 5
DMAc which dehydrated using molecular sieve 3.20g (0.01 mol) of 4,4'-bis (trifluoromethyl) benzidine (henceforth abbreviated as TFMB) was put in reaction container. Dissolved in 9 g. To this solution, 3.52 g (0.01 mol) of DPSDA was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例6〕
反応容器中に、t−DACH 0.57g(0.005モル)と TFMB 1.60g(0.005モル) を入れ、モレキュラーシーブを用いて脱水したDMAc 22.8gに溶解した。この溶液にDPSDA 3.52g(0.01モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
Example 6
In a reaction vessel, 0.57 g (0.005 mol) of t-DACH and 1.60 g (0.005 mol) of TFMB were put and dissolved in 22.8 g of DMAc dehydrated using a molecular sieve. To this solution, 3.52 g (0.01 mol) of DPSDA was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例7〕
反応容器中に、4, 4’‐(9‐ フルオレンジイル)ジアミン(以下、FDAと略記することもある) 1.74g(0.005モル)と TFMB 1.60g(0.005モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 20.6gに溶解した。この溶液にDPSDA 3.52g(0.01モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
Example 7
In a reaction vessel, 1.74 g (0.005 mol) and 4,60 '(0.005 mol) of TFMB were added to 4,4 ′-(9-fluorenediyl) diamine (hereinafter sometimes abbreviated as FDA). And dissolved in 20.6 g of DMAc dehydrated using molecular sieves. To this solution, 3.52 g (0.01 mol) of DPSDA was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔実施例8〕
反応容器中に、FDA 1.05g(0.005モル)と TFMB 2.24g(0.007モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 27.2gに溶解した。この溶液にDPSDA 3.52g(0.01モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
Example 8
In a reaction vessel, 1.05 g (0.005 mol) of FDA and 2.24 g (0.007 mol) of TFMB were put and dissolved in 27.2 g of DMAc dehydrated using a molecular sieve. To this solution, 3.52 g (0.01 mol) of DPSDA was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔比較例1〕
反応容器中にt−DACH 7.00g(0.0613モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 183.57gに溶解した後、この溶液に3,3’,4,4’−ビフェニルテトラカルボン酸二無水物(以下、s−BPDAと略記することもある) 18.03g(0.0613モル)を徐々に加え、120℃まで加熱し、5分程度で塩が溶解し始めたのを確認した後、25℃まで急冷し、そのまま25℃で8時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
[Comparative Example 1]
In a reaction vessel, 7.00 g (0.0613 mol) of t-DACH was placed, dissolved in 183.57 g of DMAc dehydrated using molecular sieves, and then 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride (hereinafter sometimes abbreviated as s-BPDA) 18.03 g (0.0613 mol) was gradually added, heated to 120 ° C., and the salt began to dissolve in about 5 minutes. After confirmation, it was rapidly cooled to 25 ° C. and stirred at 25 ° C. for 8 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
〔比較例2〕
反応容器中に4,4‘−ジアミノジフェニルエーテル(以下、ODAと略記することもある)1.20g(0.0060モル)を入れ、モレキュラーシーブを用いて脱水したDMAc 18.77gに溶解した後、この溶液にDPSDA 2.11g(0.0060モル)を徐々に加え、25℃で24時間撹拌した。均一で粘稠なポリイミド前駆体溶液組成物を得た。
[Comparative Example 2]
After putting 1.20 g (0.0060 mol) of 4,4′-diaminodiphenyl ether (hereinafter sometimes abbreviated as ODA) into the reaction vessel and dissolving in 18.77 g of DMAc dehydrated using molecular sieve, To this solution, 2.11 g (0.0060 mol) of DPSDA was gradually added and stirred at 25 ° C. for 24 hours. A uniform and viscous polyimide precursor solution composition was obtained.
得られたポリイミド前駆体溶液組成物をガラス基板に塗布し、窒素雰囲気下で120℃で1時間、150℃で30分、200℃で30分、次いで最終的に350℃まで昇温して熱的にイミド化を行なって、無色透明な膜厚が約10μmのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表2に示す。 The obtained polyimide precursor solution composition was applied to a glass substrate, and heated in a nitrogen atmosphere at 120 ° C. for 1 hour, 150 ° C. for 30 minutes, 200 ° C. for 30 minutes, and finally heated to 350 ° C. Imidization was performed to obtain a polyimide film having a colorless and transparent film thickness of about 10 μm. The results of measuring the properties of this film are shown in Table 2.
表2に示した結果から分かるとおり、本発明のポリイミドは比較例1、2に比べて優れた光透過性を有している。また、実施例1、5〜8については高い透明性だけでなく、低い複屈折率をも有している。 As can be seen from the results shown in Table 2, the polyimide of the present invention has superior light transmittance as compared with Comparative Examples 1 and 2. Examples 1 and 5 to 8 have not only high transparency but also low birefringence.
本発明によって、優れた透明性、高耐熱性を有するポリイミド、またさらに低複屈折率を有するポリイミドを提供することができる。本発明のポリイミドは、特にフレキシブルなディスプレイやタッチパネルなどの表示装置において透明性基材として好適に用いることができる。 According to the present invention, a polyimide having excellent transparency and high heat resistance, and a polyimide having a low birefringence can be provided. The polyimide of the present invention can be suitably used as a transparent substrate particularly in display devices such as flexible displays and touch panels.
Claims (13)
このポリイミド前駆体から得られるポリイミドが、厚さ10μmのフィルムでの波長400nmの光透過率が75%以上であることを特徴とするポリイミド前駆体。
〔式(2)中、R3〜R9はそれぞれ独立に水素原子、メチル基及びトリフルオロメチル基よりなる群から選択される1種以上を示す。〕 X in the following chemical formula (1) is a polyimide precursor having a unit structure of the following chemical formula (1) selected from the group represented by the following chemical formula (2),
The polyimide obtained from this polyimide precursor has a light transmittance of 75% or more at a wavelength of 400 nm in a 10 μm thick film.
[In Formula (2), R < 3 > -R < 9 > shows 1 or more types selected from the group which consists of a hydrogen atom, a methyl group, and a trifluoromethyl group each independently. ]
〔式(3)中、Zは2価の基を表し、R10、R11はいずれも独立に、水素原子又は、炭素数1〜6のアルキル基、炭素数3〜9のアルキルシリル基であり、Yは下記化学式(4)の構造の4価の基を表す。〕
[In Formula (3), Z represents a divalent group, and R 10 and R 11 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. Yes, Y represents a tetravalent group having the structure of the following chemical formula (4). ]
このポリイミドが、厚さ10μmのフィルムでの波長400nmの光透過率が75%以上であることを特徴とするポリイミド。
The polyimide is characterized in that the light transmittance at a wavelength of 400 nm in a film having a thickness of 10 μm is 75% or more.
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