JPH04328127A - Photo-sensitive wholly fluorinated polyimide precursor and its production - Google Patents
Photo-sensitive wholly fluorinated polyimide precursor and its productionInfo
- Publication number
- JPH04328127A JPH04328127A JP3122946A JP12294691A JPH04328127A JP H04328127 A JPH04328127 A JP H04328127A JP 3122946 A JP3122946 A JP 3122946A JP 12294691 A JP12294691 A JP 12294691A JP H04328127 A JPH04328127 A JP H04328127A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- chemical formula
- photosensitive
- chemical
- polyimide precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 26
- 229920001721 polyimide Polymers 0.000 title claims description 49
- 239000004642 Polyimide Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000126 substance Substances 0.000 claims abstract description 33
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000000962 organic group Chemical group 0.000 claims abstract description 3
- 150000004820 halides Chemical class 0.000 claims abstract 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 125000006551 perfluoro alkylene group Chemical group 0.000 claims description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 claims 1
- 230000036211 photosensitivity Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000005693 optoelectronics Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 22
- 230000003287 optical effect Effects 0.000 description 20
- 239000000463 material Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- -1 dicarboxylic acid diester Chemical class 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- WNMRFYNFVYCNDL-UHFFFAOYSA-N 4,8-difluorofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound FC1=C2C(=O)OC(=O)C2=C(F)C2=C1C(=O)OC2=O WNMRFYNFVYCNDL-UHFFFAOYSA-N 0.000 description 3
- DXPDSWSYCBNHTO-UHFFFAOYSA-N 4-[4-(3,4-dicarboxy-2,5,6-trifluorophenoxy)-2,3,5,6-tetrafluorophenoxy]-3,5,6-trifluorophthalic acid Chemical compound FC1=C(C(O)=O)C(C(=O)O)=C(F)C(F)=C1OC(C(=C1F)F)=C(F)C(F)=C1OC1=C(F)C(F)=C(C(O)=O)C(C(O)=O)=C1F DXPDSWSYCBNHTO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FXGQUGCFZKMIJW-UHFFFAOYSA-N 2,4,5,6-tetrafluorobenzene-1,3-diamine Chemical compound NC1=C(F)C(N)=C(F)C(F)=C1F FXGQUGCFZKMIJW-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- SKQMJTLFJLUFHC-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenoxy)-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1OC1=C(F)C(F)=C(N)C(F)=C1F SKQMJTLFJLUFHC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- MWZVAPQMAYLMST-UHFFFAOYSA-N 3,4,6-trifluoro-5-(1,1,1,3,3,3-hexafluoropropan-2-yl)phthalic acid Chemical compound C(=O)(O)C=1C(=C(C(=C(C=1C(=O)O)F)F)C(C(F)(F)F)C(F)(F)F)F MWZVAPQMAYLMST-UHFFFAOYSA-N 0.000 description 1
- DUEXNLBVFZOZLO-UHFFFAOYSA-N 4-(3,4-dicarboxy-2,5,6-trifluorophenyl)-3,5,6-trifluorophthalic acid Chemical compound FC1=C(C(O)=O)C(C(=O)O)=C(F)C(F)=C1C1=C(F)C(F)=C(C(O)=O)C(C(O)=O)=C1F DUEXNLBVFZOZLO-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group 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
- JDVKYLFCIUDDIA-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)sulfanyl-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1SC1=C(F)C(F)=C(N)C(F)=C1F JDVKYLFCIUDDIA-UHFFFAOYSA-N 0.000 description 1
- CQVODJYUBCNNFG-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)sulfonyl-2,3,5,6-tetrafluoroaniline Chemical compound FC1=C(F)C(N)=C(F)C(F)=C1S(=O)(=O)C1=C(F)C(F)=C(N)C(F)=C1F CQVODJYUBCNNFG-UHFFFAOYSA-N 0.000 description 1
- CMMNSASDJHKAOD-UHFFFAOYSA-N 4-[2-(3,4-dicarboxy-2,5,6-trifluorophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-3,5,6-trifluorophthalic acid Chemical compound FC1=C(C(O)=O)C(C(=O)O)=C(F)C(F)=C1C(C(F)(F)F)(C(F)(F)F)C1=C(F)C(F)=C(C(O)=O)C(C(O)=O)=C1F CMMNSASDJHKAOD-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- YKXPTMWKFSBTJQ-UHFFFAOYSA-N 4-[4-amino-2,3,5-trifluoro-6-(trifluoromethyl)phenyl]-2,3,6-trifluoro-5-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1C(F)(F)F YKXPTMWKFSBTJQ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、フォトマスクを通して
光照射することにより、照射部が適当な溶媒に不溶化し
、光未照射部をその溶媒によって除去した後、加熱によ
り硬化させることにより、Ｃ−Ｈ結合を有しない全フッ
素化ポリイミドのレリーフ構造を形成する感光性全フッ
素化ポリイミド前駆体に関し、特に光電子集積回路（Ｏ
ＥＩＣ）における光導波路として使用可能な低光損失率
ポリイミドレリーフ構造を形成する感光性全フッ素化ポ
リイミド前駆体に関する。[Industrial Application Field] The present invention is characterized in that by irradiating light through a photomask, the irradiated area is insolubilized in a suitable solvent, and after the non-irradiated area is removed with the solvent, it is cured by heating. Regarding photosensitive perfluorinated polyimide precursors forming relief structures of perfluorinated polyimide having no -H bonds, in particular optoelectronic integrated circuits (O
The present invention relates to a photosensitive perfluorinated polyimide precursor that forms a low optical loss rate polyimide relief structure that can be used as an optical waveguide in EIC).
【０００２】0002
【従来の技術】プラスチック材料は、無機系の材料に比
べて軽量であり、耐衝撃性、加工性に優れ、取扱いが容
易であるなどの優れた特徴を有しているため、これまで
も光ファイバーや光ディスク用基板、光学用レンズなど
様々な光学用途に用いられてきた。中でもプラスチック
をＯＥＩＣにおける光導波路など、近赤外域（波長＝０
．８〜２．５μｍ）での光学材料として用いる場合、無
機系の材料と比較してまず問題となるのは大きな光損失
である。プラスチックにおける損失原因には大きく分け
て光の散乱と光の吸収の２つがあるが、光通信に用いら
れる波長が今後、長波長域へ移る（０．８５μｍから１
．３μｍ〜１．５μｍへ）に従って、後者の原因、つま
り分子構造に本質的な振動吸収による損失が支配的とな
り、プラスチック光学材料の光導波特性に大きな制約を
もたらすものと考えられる。特にＰＭＭＡやＰＳのよう
に、分子鎖内に炭素−水素結合（Ｃ−Ｈ結合）を有する
ものは高調波の吸収強度が減衰しにくいこともあって、
近赤外域での光損失は大きなものとなっている。このＣ
−Ｈ結合に起因する高調波を小さくしかつ長波長側へシ
フトさせるためには、分子鎖内の水素を重水素（Ｄ）あ
るいはフッ素（Ｆ）で置換することが提案されており、
ＰＭＭＡやＰＳ中の水素を重水素あるいはフッ素で置換
した材料については具体的な検討が既になされている〔
例えば戒能俊邦、アプライド フィジクス レター
ズ（ Ａｐｐｌ． Ｐｈｙｓ． Ｌｅｔｔ． ）第４８
巻、第７５７頁（１９８６年）参照〕。しかし、これら
のプラスチック光学材料は、例えば基板上でのＯＥＩＣ
作製に必要な耐熱性（２６０℃）を持たないため、光電
子集積回路等に適用するには工程上の種々の工夫が必要
である。一方、ポリイミド樹脂はプラスチックの中で最
も耐熱性の優れたものの一つとして知られており、光学
材料への適用も最近検討（ＩＢＭ、ハネウェル、ＮＴＴ
）され始めている。しかしこれまでに検討されたすべて
のポリイミドは分子鎖中にフェニル基のＣ−Ｈ結合を有
するため、Ｃ−Ｈ結合の伸縮振動の高調波あるいはＣ−
Ｈ結合の伸縮振動の高調波と変角振動の結合音が表れ、
近赤外域にはなお大きな吸収損失が存在している。これ
まで全フッ素化ポリイミドは明らかにされていない。更
に、ルブナー（ Ｒｕｂｎｅｒ ） 等の著書「光反応
性重合体前駆物質からの高耐熱性フィルムパターンの製
造」（ Ｐｒｏｄｕｃｔｉｏｎ ｏｆ Ｈｉｇｈｌｙ−
Ｈｅａｔ Ｒｅｓｉｓｔａｎｔ Ｆｉｌｍ Ｐａｔｔｅ
ｒｎｓ ｆｒｏｍ Ｐｈｏｔｏｒｅａｃｔｉｖｅ Ｐｏ
ｌｙｍｅｒ Ｐｒｅｃｕｒｓｏｒｓ ）（１９７６）に
記載されているように、ポリイミドレリーフ構造を形成
する感光性ポリイミド前駆体が知られているが、形成さ
れたポリイミドレリーフ構造がポリイミド分子中にフェ
ニル基のＣ−Ｈ結合を有するため、Ｃ−Ｈ結合の伸縮振
動の高調波あるいはＣ−Ｈ結合の伸縮振動の高調波と変
角振動の結合音が表れ、近赤外域にはなお大きな吸収損
失が存在している。[Prior Art] Plastic materials have excellent characteristics such as being lighter than inorganic materials, superior in impact resistance, processability, and easy to handle, so plastic materials have been used for optical fibers until now. It has been used in a variety of optical applications, such as optical disc substrates, optical lenses, etc. Among them, plastics are used in the near-infrared region (wavelength = 0), such as optical waveguides in OEIC.
．． When used as an optical material (8 to 2.5 μm), the first problem compared to inorganic materials is large optical loss. There are two main causes of loss in plastics: light scattering and light absorption, but in the future the wavelengths used for optical communications will shift to longer wavelengths (from 0.85 μm to 1 μm).
．． 3 .mu.m to 1.5 .mu.m), the latter cause, that is, loss due to vibrational absorption inherent in the molecular structure, becomes dominant, and it is thought that this brings about major restrictions on the optical waveguide properties of plastic optical materials. In particular, materials with carbon-hydrogen bonds (C-H bonds) in their molecular chains, such as PMMA and PS, have difficulty attenuating the harmonic absorption intensity.
Optical loss in the near-infrared region is large. This C
In order to reduce the harmonics caused by -H bonds and shift them to longer wavelengths, it has been proposed to replace hydrogen in the molecular chain with deuterium (D) or fluorine (F).
Specific studies have already been conducted on materials in which hydrogen in PMMA and PS is replaced with deuterium or fluorine.
For example, Toshikuni Kaino, Applied Physics Letters (Appl. Phys. Lett.) No. 48
vol., p. 757 (1986)]. However, these plastic optical materials are not suitable for e.g. OEIC on substrates.
Since it does not have the heat resistance (260° C.) required for fabrication, various steps must be taken in order to apply it to optoelectronic integrated circuits and the like. On the other hand, polyimide resin is known as one of the most heat-resistant plastics, and its application to optical materials is also being considered recently (IBM, Honeywell, NTT
) is beginning to occur. However, all polyimides studied so far have C-H bonds of phenyl groups in their molecular chains, so harmonics of the stretching vibrations of C-H bonds or C-
The harmonics of the H-bond stretching vibration and the combined sound of the bending vibration appear,
Large absorption losses still exist in the near-infrared region. Until now, perfluorinated polyimide has not been disclosed. In addition, the book "Production of Highly Temperature-Resistant Film Patterns from Photoreactive Polymer Precursors" by Rubner et al.
Heat Resistant Film Patte
rns from Photoreactive Po
lymer Precursors) (1976), a photosensitive polyimide precursor that forms a polyimide relief structure is known; Therefore, a harmonic of the stretching vibration of the C-H bond or a combination sound of the harmonic of the stretching vibration of the C-H bond and the bending vibration appears, and a large absorption loss still exists in the near-infrared region.
【０００３】0003
【発明が解決しようとする課題】すなわち近赤外域での
ＯＥＩＣ用光学材料として用いるプラスチック材料には
、耐熱性の不足とＣ−Ｈ結合の存在に基づく大きな光損
失という問題があった。本発明はこのような現状にかん
がみてなされたものであり、その目的は光電子集積回路
を作製するのに十分な耐熱性があり、近赤外域において
光透過損失の極めて少ないポリイミドレリーフ構造を提
供することにある。[Problems to be Solved by the Invention] Plastic materials used as optical materials for OEIC in the near-infrared region have problems of insufficient heat resistance and large optical loss due to the presence of C--H bonds. The present invention was made in view of the current situation, and its purpose is to provide a polyimide relief structure that has sufficient heat resistance for manufacturing optoelectronic integrated circuits and has extremely low light transmission loss in the near-infrared region. There is a particular thing.
【０００４】0004
【課題を解決するための手段】本発明を概説すれば、本
発明の第１の発明は感光性全フッ素化ポリイミド前駆体
に関する発明であって、下記一般式（化１）：[Means for Solving the Problems] To summarize the present invention, the first invention of the present invention relates to a photosensitive perfluorinated polyimide precursor, which has the following general formula (Formula 1):
【化１】
〔ここで式中Ｒ＊ は光反応により化学結合を形成し、
分子間を橋架けする有機基、Ｒ１ は下記式（化２）：
[Chemical formula 1] [In the formula, R* forms a chemical bond by photoreaction,
The organic group bridging between molecules, R1, has the following formula (Chemical formula 2):
【化２】
で表される基のうちのいずれかの基、Ｒ２ は下記式（
化３）：Any group among the groups represented by [Chemical formula 2], R2 is represented by the following formula (
3):
【化３】
で表される基のうちのいずれかの基であり、ここで式中
Ｒｆはフッ素、又はパーフルオロアルキル基、Ｘは下記
式（化４）：[Chemical formula 3], where Rf is fluorine or a perfluoroalkyl group, and X is the following formula (Chemical formula 4):
【化４】
（ここで式中Ｒｆ′はパーフルオロアルキレン基、ｎは
１〜１０の数を示す）で表される基のうちのいずれかの
基である〕で表される繰返し単位を含有することを特徴
とする。また、本発明の第２の発明は、上記第１の発明
の感光性全フッ素化ポリイミド前駆体の製造方法に関す
る発明であって、下記一般式（化５）：Contains a repeating unit represented by [Chemical formula 4] (wherein Rf' is a perfluoroalkylene group and n is a number from 1 to 10) It is characterized by Further, a second invention of the present invention relates to a method for producing the photosensitive perfluorinated polyimide precursor of the first invention, which has the following general formula (Chemical formula 5):
【化５】
〔式中Ｒ１ は一般式（化１）中のＲ１ と同義である
〕で表されるテトラカルボン酸、又はその誘導体と、式
Ｒ＊ ＯＨ〔式中Ｒ＊ は一般式（化１）中のＲ＊ と
同義である〕で表される感光性アルコールとを反応させ
、その後酸ハライド化し、次いで下記一般式（化６）：
[Chemical formula 5] [In the formula, R1 has the same meaning as R1 in the general formula (Chemical formula 1)] A tetracarboxylic acid represented by the formula R* OH [In the formula, R* has the same meaning as the general formula (Chemical formula 1) is reacted with a photosensitive alcohol represented by R
【化６】Ｈ２ Ｎ−Ｒ２ −ＮＨ２ 〔式中Ｒ２ は一
般式（化１）中のＲ２ と同義である〕で表されるジア
ミンと反応させることを特徴とする。It is characterized by reacting with a diamine represented by H2N-R2-NH2 (wherein R2 has the same meaning as R2 in the general formula (Chemical formula 1)).
【０００５】本発明者らは、種々の既存のポリイミド及
びポリイミド光学材料について、その赤外域、近赤外域
の吸収スペクトルを測定し、近赤外域での光損失を算出
するとともに、その原因について鋭意検討した。その結
果、近赤外域で大きな光損失を引起こす原因の第１は、
アルキル基やフェニル環等におけるＣ−Ｈ結合の伸縮振
動の高調波吸収、及びＣ−Ｈ結合の伸縮振動の高調波と
変角振動の結合音による吸収であることが明らかとなっ
た。[0005] The present inventors measured the absorption spectra of various existing polyimides and polyimide optical materials in the infrared region and near-infrared region, calculated the optical loss in the near-infrared region, and diligently investigated the cause of the loss. investigated. As a result, the first cause of large optical loss in the near-infrared region is
It has become clear that this is due to harmonic absorption of stretching vibrations of C--H bonds in alkyl groups, phenyl rings, etc., and absorption due to the combination sound of harmonics of stretching vibrations of C--H bonds and bending vibrations.
【０００６】本発明の感光性全フッ素化ポリイミド前駆
体は、フォトリソグラフィ工程により形成される全フッ
素化ポリイミドがアルキル基、フェニル環等の炭素に結
合するすべての１価元素をフッ素、又はパーフルオロア
ルキル基とし、繰返し単位内にＣ−Ｈ結合を持たない構
造とすることによって、近赤外域での最大の光損失原因
であるＣ−Ｈ結合に基づく振動吸収を無くし、またイミ
ド結合を主鎖構造に導入してポリイミドとすることによ
って、光電子集積回路を作製する上での十分な耐熱性（
２６０℃以上）を持たせることができる。In the photosensitive perfluorinated polyimide precursor of the present invention, the perfluorinated polyimide formed by a photolithography process replaces all monovalent elements bonded to carbon such as alkyl groups and phenyl rings with fluorine or perfluorinated polyimide. By using an alkyl group and having a structure that does not have a C-H bond in the repeating unit, vibrational absorption based on the C-H bond, which is the largest cause of optical loss in the near-infrared region, is eliminated, and the imide bond is removed from the main chain. By incorporating polyimide into the structure, sufficient heat resistance (
260°C or higher).
【０００７】本発明の感光性全フッ素化ポリイミド前駆
体を製造する時に使用するテトラカルボン酸無水物とし
ては、分子内のアルキル基、フェニル環等の炭素に結合
するすべての１価元素をフッ素、又はパーフルオロアル
キル基としたものであればどのようなものでもよい。テ
トラカルボン酸無水物前駆体のテトラカルボン酸並びに
その誘導体としての酸無水物、酸塩化物、エステル化物
等としては次のようなものが挙げられる：１，４−ジフ
ルオロピロメリット酸、１−トリフルオロメチル−４−
フルオロピロメリット酸、１，４−ジ（トリフルオロメ
チル）ピロメリット酸、１，４−ジ（ペンタフルオロエ
チル）ピロメリット酸、ヘキサフルオロ−３，３′，４
，４′−ビフェニルテトラカルボン酸、ヘキサフルオロ
−３，３′，４，４′−ベンゾフェノンテトラカルボン
酸、２，２−ビス（３，４−ジカルボキシトリフルオロ
フェニル）ヘキサフルオロプロパン、１，３−ビス（３
，４−ジカルボキシトリフルオロフェニル）ヘキサフル
オロプロパン、１，４−ビス（３，４−ジカルボキシト
リフルオロフェノキシ）テトラフルオロベンゼン、ヘキ
サフルオロ−３，３′（又は４，４′）−オキシビスフ
タル酸。酸無水物への転化は、通常の方法で良く、例え
ば１００℃以上に加熱すればよい。この中でピロメリッ
ト酸二無水物のベンゼン環にフルオロアルキル基を導入
した含フッ素酸二無水物である１，４−ジ（トリフルオ
ロメチル）ピロメリット酸二無水物、１，４−ジ（ペン
タフルオロエチル）ピロメリット酸二無水物等の製造方
法は特願昭６３−１６５０５６号明細書に記載されてい
る。The tetracarboxylic acid anhydride used in producing the photosensitive perfluorinated polyimide precursor of the present invention has all the monovalent elements bonded to carbon atoms such as alkyl groups and phenyl rings in the molecule such as fluorine, Alternatively, any perfluoroalkyl group may be used. Tetracarboxylic acids as tetracarboxylic acid anhydride precursors and their derivatives such as acid anhydrides, acid chlorides, esters, etc. include the following: 1,4-difluoropyromellitic acid, 1-trifluoropyromellitic acid, Fluoromethyl-4-
Fluoropyromellitic acid, 1,4-di(trifluoromethyl)pyromellitic acid, 1,4-di(pentafluoroethyl)pyromellitic acid, hexafluoro-3,3',4
, 4'-biphenyltetracarboxylic acid, hexafluoro-3,3',4,4'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxytrifluorophenyl)hexafluoropropane, 1,3 - screw (3
, 4-dicarboxytrifluorophenyl)hexafluoropropane, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene, hexafluoro-3,3' (or 4,4')-oxybis Phthalic acid. Conversion to an acid anhydride may be carried out by a conventional method, for example by heating to 100° C. or higher. Among them, 1,4-di(trifluoromethyl)pyromellitic dianhydride, 1,4-di(trifluoromethyl)pyromellitic dianhydride, which is a fluorine-containing dianhydride with a fluoroalkyl group introduced into the benzene ring of pyromellitic dianhydride, and 1,4-di( A method for producing pyromellitic dianhydride (pentafluoroethyl) is described in Japanese Patent Application No. 165056/1983.
【０００８】上記酸無水物に感光基及び重合反応基とな
る酸ハロゲン化基を導入する方法は、通常の方法で良く
、例えば前記ルブナー等の著書に記載されている方法を
使用できる。例えば、次の方式が挙げられる。まず、２
−ヒドロキシエチルメタクリート（ＨＥＭＡ）と酸無水
物を反応させ、感光基を導入する。次に、得られたジカ
ルボン酸ジエステルが塩化チオニルとの反応によって、
対応する二酸塩化物に転化される。また本発明に用いる
ことのできるジアミンの例としては、分子内のアミノ基
を除くアルキル基、フェニル環等の炭素に結合するすべ
ての１価元素をフッ素、又はパーフルオロアルキル基と
したものであればどのようなものでもよく、３，４，５
，６−テトラフルオロ−１，２−フェニレンジアミン、
２，４，５，６−テトラフルオロ−１，３−フェニレン
ジアミン、２，３，５，６−テトラフルオロ−１，４−
フェニレンジアミン、４，４′−ジアミノオクタフルオ
ロビフェニル、ビス（２，３，５，６−テトラフルオロ
−４−アミノフェニル）エーテル、ビス（２，３，５，
６−テトラフルオロ−４−アミノフェニル）スルホン、
ヘキサフルオロ−２，２′−ビス（トリフルオロメチル
）−４，４′−ジアミノビフェニル等が挙げられる。[0008] The method for introducing the photosensitive group and the acid halogenated group which becomes the polymerization reaction group into the above-mentioned acid anhydride may be any conventional method, for example, the method described in the book by Rubner et al. For example, the following method may be mentioned. First, 2
-Hydroxyethyl methacrylate (HEMA) and acid anhydride are reacted to introduce a photosensitive group. Next, the obtained dicarboxylic acid diester is reacted with thionyl chloride to
It is converted to the corresponding diacid chloride. Examples of diamines that can be used in the present invention include those in which all monovalent elements bonded to carbon, such as alkyl groups other than amino groups and phenyl rings in the molecule, are fluorine or perfluoroalkyl groups. It can be anything like 3, 4, 5.
, 6-tetrafluoro-1,2-phenylenediamine,
2,4,5,6-tetrafluoro-1,3-phenylenediamine, 2,3,5,6-tetrafluoro-1,4-
Phenyl diamine, 4,4'-diaminooctafluorobiphenyl, bis(2,3,5,6-tetrafluoro-4-aminophenyl) ether, bis(2,3,5,
6-tetrafluoro-4-aminophenyl) sulfone,
Examples include hexafluoro-2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl.
【０００９】感光性全フッ素化ポリイミド前駆体の製造
方法は、通常の感光性全フッ素化ポリイミド前駆体の製
造条件と同じでよく、一般的にはＮ−メチル−２−ピロ
リドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメ
チルホルムアミドなどの極性有機溶媒中で反応させる。
本発明においてはジアミンまた感光性テトラカルボン酸
二塩化物とも単一化合物で用いるばかりではなく、複数
のジアミン、感光性テトラカルボン酸二塩化物を混合し
て用いる場合がある。その場合は、複数又は単一のジア
ミンのモル数の合計と複数又は単一の感光性テトラカル
ボン酸二塩化物のモル数の合計が等しいかほぼ等しくな
るようにする。得られた感光性全フッ素化ポリイミド前
駆体溶液は、水中に注ぎ沈殿させる。更に再沈殿法等に
より精製した後、適当な溶媒に溶解してキャスト溶液と
する。得られた前述の感光性全フッ素化ポリイミド前駆
体溶液において、その溶液の濃度は５〜４０重量％（１
０〜２５重量％であることが好ましい）、また前記ポリ
マー溶液の回転粘度（２５℃）は、５０〜５０００ポア
ズであることが好適である。The method for producing the photosensitive perfluorinated polyimide precursor may be the same as the production conditions for ordinary photosensitive perfluorinated polyimide precursors, and generally N-methyl-2-pyrrolidone, N,N- The reaction is carried out in a polar organic solvent such as dimethylacetamide or N,N-dimethylformamide. In the present invention, both the diamine and the photosensitive tetracarboxylic acid dichloride are not only used as a single compound, but also a plurality of diamines and photosensitive tetracarboxylic acid dichloride may be used as a mixture. In that case, the total number of moles of a plurality of diamines or a single diamine and the total number of moles of a plurality of photosensitive tetracarboxylic acid dichlorides are made to be equal or approximately equal. The resulting photosensitive perfluorinated polyimide precursor solution is poured into water and allowed to precipitate. After further purification by a reprecipitation method or the like, it is dissolved in an appropriate solvent to obtain a cast solution. In the photosensitive perfluorinated polyimide precursor solution obtained above, the concentration of the solution is 5 to 40% by weight (1
(preferably from 0 to 25% by weight), and the rotational viscosity (25° C.) of the polymer solution is preferably from 50 to 5000 poise.
【００１０】本発明の感光性全フッ素化ポリイミド前駆
体からレリーフ構造を得る方法には、通常の方法が使用
できる。例えば感光性全フッ素化ポリイミド前駆体溶液
を、基板上にスピンコートし、窒素雰囲気下で７０〜８
０℃で乾燥させて得られる。このフィルムに、フォトマ
スクを介して高圧水銀灯等で、紫外線を照射する。適当
な溶媒で未照射部を除去した後、加熱して、残された溶
媒、感光基を除去すると共にイミド化を行い、ポリイミ
ドレリーフ構造を得る。加熱は、３００℃以上まで段階
的に行うのが一般的である。Conventional methods can be used to obtain a relief structure from the photosensitive perfluorinated polyimide precursor of the present invention. For example, a photosensitive perfluorinated polyimide precursor solution is spin-coated onto a substrate and heated to 70-80% under nitrogen atmosphere.
Obtained by drying at 0°C. This film is irradiated with ultraviolet light using a high-pressure mercury lamp or the like through a photomask. After removing the unirradiated area with an appropriate solvent, it is heated to remove the remaining solvent and photosensitive groups and to imidize to obtain a polyimide relief structure. Heating is generally performed in stages up to 300°C or higher.
【００１１】[0011]
【実施例】以下、本発明を実施例により更に具体的に説
明するが、本発明はこれら実施例に限定されない。[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.
【００１２】実施例１
滴下管、窒素導入管を有する容器中で、以下の構造式（
化７）を持つ１，４−ビス（３，４−ジカルボキシトリ
フルオロフェノキシ）テトラフルオロベンゼン酸二無水
物：Example 1 In a container having a dropping tube and a nitrogen introduction tube, the following structural formula (
1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzenic dianhydride having chemical formula 7):
【化７】
１１．６４４ｇ（２０．０ｍｍｏｌ）を８０ｇのヘキサ
メチルりん酸トリアミド（ＨＭＰＴＡ）に溶解した後、
窒素雰囲気を保ちながら５℃に冷却した。次に、温度が
上がらないように注意しながら、ＨＥＭＡ５．２０４ｇ
（４０ｍｍｏｌ）を滴下した後、室温で１０日間かくは
んした。
温度を−１０℃に下げて、塩化チオニル４．７５９ｇを
少しずつ加えた。添加終了後、冷却を止めて３時間反応
させた。次に１０℃まで温度を下げ、３０ｇのＮ，Ｎ−
ジメチルアセトアミド（ＤＭＡｃ）８６ｇに溶解した以
外の構造式（化８）を持つ２，４，５，６−テトラフル
オロ−１，３−フェニレンジアミン：embedded image After dissolving 11.644 g (20.0 mmol) in 80 g of hexamethylphosphate triamide (HMPTA),
The mixture was cooled to 5° C. while maintaining a nitrogen atmosphere. Next, while being careful not to raise the temperature, add 5.204g of HEMA.
(40 mmol) was added dropwise, and the mixture was stirred at room temperature for 10 days. The temperature was lowered to -10°C and 4.759 g of thionyl chloride was added in portions. After the addition was completed, cooling was stopped and the reaction was allowed to proceed for 3 hours. Next, the temperature was lowered to 10℃, and 30g of N,N-
2,4,5,6-tetrafluoro-1,3-phenylenediamine having a structural formula (chemical formula 8) other than that dissolved in 86 g of dimethylacetamide (DMAc):
【化８】
を３．６０２ｇ（２０．０ｍｍｏｌ）加えた。この溶液
を窒素雰囲気中、室温で３日間かくはんし、感光性全フ
ッ素化ポリイミド前駆体のＤＭＡｃ溶液を得た。この溶
液を水中にあけ、沈殿させた後、再びＤＭＡｃに溶かし
て、水中に沈殿させる再沈殿精製を２回繰返した。生成
物をＤＭＡｃに溶かし、２０重量％の感光性全フッ素化
ポリイミド前駆体溶液を得た。この溶液に、感光性全フ
ッ素化ポリイミド前駆体に対して１％のミヒラーケトン
を加え、アルミ板上にスピンコーティングし、窒素雰囲
気下で７０℃で２時間乾燥させて、厚さ１０μｍの感光
性フィルムを得た。このフィルムに、幅１０μｍのスリ
ットを持つフォトマスクを介して、３６５ｎｍの波長域
で１０ｍＷ／ｃｍ２ の強度を持つ高圧灯を１０秒間照
射した後、ＤＭＡｃで現像し、未照射部を除去した。こ
のフィルムを１６０℃で１時間、２５０℃で３０分、３
５０℃で１時間加熱したところ、幅１０μｍ、厚さ５μ
ｍのレリーフ構造を得た。また、フォトマスクを使わず
に感光させて、５μｍの全フッ素化ポリイミドフィルム
も作製した。このポリイミドフィルムの赤外吸収スペク
トルを測定するとイミド基に特有の吸収が、１７９０ｃ
ｍ−１に現れ、イミド化が完全に進行したことが確認で
きた。このポリイミドフィルムの波長０．８〜１．７μ
ｍの範囲での光の吸収を測定したところ、図１に示すと
おり、水の吸収以外に光の吸収はなかった。以下に示す
比較例１で作製した従来のポリイミドフィルムに比べて
小さかった。なお、図１において実線は実施例１の全フ
ッ素化ポリイミド、破線は後記比較例１のポリイミドに
おける、それぞれ光の吸光度の波長依存性を示すグラフ
であり、横軸は波長（μｍ）、縦軸は吸光度を表す。3.602 g (20.0 mmol) of embedded image was added. This solution was stirred at room temperature in a nitrogen atmosphere for 3 days to obtain a DMAc solution of a photosensitive perfluorinated polyimide precursor. This solution was poured into water to precipitate it, and then re-dissolved in DMAc and precipitated in water. This reprecipitation purification was repeated twice. The product was dissolved in DMAc to obtain a 20% by weight photosensitive perfluorinated polyimide precursor solution. To this solution, 1% Michler's ketone was added to the photosensitive perfluorinated polyimide precursor, spin-coated onto an aluminum plate, and dried at 70°C for 2 hours in a nitrogen atmosphere to form a photosensitive film with a thickness of 10 μm. I got it. This film was irradiated with a high-pressure lamp having an intensity of 10 mW/cm2 in a wavelength range of 365 nm for 10 seconds through a photomask having slits with a width of 10 μm, and then developed with DMAc to remove the unirradiated portions. This film was heated at 160°C for 1 hour and at 250°C for 30 minutes.
When heated at 50℃ for 1 hour, the width was 10μm and the thickness was 5μm.
A relief structure of m was obtained. A 5 μm perfluorinated polyimide film was also produced by exposing the film to light without using a photomask. When the infrared absorption spectrum of this polyimide film was measured, the absorption characteristic of imide groups was found to be 1790c.
m-1, and it was confirmed that imidization had completely progressed. The wavelength of this polyimide film is 0.8 to 1.7μ
When light absorption was measured in a range of m, as shown in FIG. 1, there was no light absorption other than water absorption. It was smaller than the conventional polyimide film produced in Comparative Example 1 shown below. In addition, in FIG. 1, the solid line is a graph showing the wavelength dependence of light absorbance in the perfluorinated polyimide of Example 1, and the broken line is the polyimide of Comparative Example 1 described later, where the horizontal axis is the wavelength (μm) and the vertical axis is the wavelength dependence. represents absorbance.
【００１３】実施例２
実施例１と同様に、１，４−ビス（３，４−ジカルボキ
シトリフルオロフェノキシ）テトラフルオロベンゼン二
無水物と以下の構造式（化９）で示されるビス（２，３
，５，６−テトラフルオロ−４−アミノフェニル）エー
テル：Example 2 In the same manner as in Example 1, 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene dianhydride and bis(2 ,3
, 5,6-tetrafluoro-4-aminophenyl) ether:
【化９】
から全フッ素化ポリイミドレリーフ構造とフィルムを得
た。このフィルムの吸収スペクトルを測定したところ、
波長０．８〜１．７μｍの範囲で水の吸収以外に吸収ピ
ークは見られなかった。A perfluorinated polyimide relief structure and film were obtained from [Image Omitted]. When we measured the absorption spectrum of this film, we found that
No absorption peak other than water absorption was observed in the wavelength range of 0.8 to 1.7 μm.
【００１４】実施例３
１，４−ビス（３，４−ジカルボキシトリフルオロフェ
ノキシ）テトラフルオロベンゼン二無水物と以下の式（
化１０）の構造を持つビス（２，３，５，６−テトラフ
ルオロ−４−アミノフェニル）スルフィド：Example 3 1,4-bis(3,4-dicarboxytrifluorophenoxy)tetrafluorobenzene dianhydride and the following formula (
Bis(2,3,5,6-tetrafluoro-4-aminophenyl) sulfide having the structure shown in Chemical formula 10:
【化１０】
から、実施例１と同様の方法で、全フッ素化ポリイミド
レリーフ構造とフィルムを得た。このフィルムの吸収ス
ペクトルを測定したところ、波長０．８〜１．７μｍの
範囲で水の吸収以外に吸収ピークは見られなかった。A perfluorinated polyimide relief structure and film were obtained from ##STR10## in the same manner as in Example 1. When the absorption spectrum of this film was measured, no absorption peak other than water absorption was observed in the wavelength range of 0.8 to 1.7 μm.
【００１５】実施例４
以下の構造式（化１１）を持つ１，４−ジフルオロピロ
メリット酸二無水物：Example 4 1,4-difluoropyromellitic dianhydride having the following structural formula (Formula 11):
【化１１】
と２，４，５，６−テトラフルオロ−１，３−フェニレ
ンジアミンから実施例１と同様の方法で、全フッ素化ポ
リイミドレリーフ構造とフィルムを得た。このフィルム
の吸収スペクトルを測定したところ、波長０．８〜１．
７μｍの範囲で水の吸収以外に吸収ピークは見られなか
った。A perfluorinated polyimide relief structure and film were obtained from [Chemical Formula 11] and 2,4,5,6-tetrafluoro-1,3-phenylenediamine in the same manner as in Example 1. When the absorption spectrum of this film was measured, the wavelength ranged from 0.8 to 1.
No absorption peak other than water absorption was observed in the 7 μm range.
【００１６】実施例５
１，４−ジフルオロピロメリット酸二無水物とビス（２
，３，５，６−テトラフルオロ−４−アミノフェニル）
エーテルから実施例１と同様の方法で全フッ素化レリー
フ構造とポリイミドフィルムを得た。このフィルムの吸
収スペクトルを測定したところ、波長０．８〜１．７μ
ｍの範囲で水の吸収以外に吸収ピークは見られなかった
。Example 5 1,4-difluoropyromellitic dianhydride and bis(2
,3,5,6-tetrafluoro-4-aminophenyl)
A perfluorinated relief structure and a polyimide film were obtained from ether in the same manner as in Example 1. When the absorption spectrum of this film was measured, the wavelength was 0.8 to 1.7μ.
No absorption peak other than water absorption was observed in the m range.
【００１７】実施例６
１，４−ジフルオロピロメリット酸二無水物とビス（２
，３，５，６−テトラフルオロ−４−アミノフェニル）
スルフィドから、実施例１と同様の方法で全フッ素化ポ
リイミド前駆体とフィルムを得た。このフィルムの吸収
スペクトルを測定したところ、波長０．８〜１．７μｍ
の範囲で水の吸収以外に吸収ピークは見られなかった。Example 6 1,4-difluoropyromellitic dianhydride and bis(2
,3,5,6-tetrafluoro-4-aminophenyl)
A perfluorinated polyimide precursor and a film were obtained from sulfide in the same manner as in Example 1. When the absorption spectrum of this film was measured, the wavelength was 0.8 to 1.7 μm.
No absorption peak other than water absorption was observed in the range of .
【００１８】比較例１
以下の構造式（化１２）を持つ２，２−ビス（３，４−
ジカルボキシフェニル）ヘキサフルオロプロパン二無水
物：Comparative Example 1 2,2-bis(3,4-
Dicarboxyphenyl)hexafluoropropane dianhydride:
【化１２】
と以下の構造式（化１３）で示される２，２′−ビス（
トリフルオロメチル）−４，４′−ジアミノビフェニル
：[Chemical formula 12] and 2,2'-bis(
trifluoromethyl)-4,4'-diaminobiphenyl:
【化１３】
から、実施例１と同様の方法でポリイミドレリーフ構造
とフィルムを得た。このポリイミドフィルムの波長０．
８〜１．７μｍの範囲での光の吸収を測定したところ、
図１の破線で示すとおり、１．１μｍ付近にＣ−Ｈ結合
の伸縮振動の３倍音による吸収が、また１．４μｍ付近
にはＣ−Ｈ結合の伸縮振動の高調波と変角振動の結合音
による吸収が、また１．６５μｍ付近ではＣ−Ｈ結合の
伸縮振動の２倍音による吸収が現れた。A polyimide relief structure and film were obtained from [Image Omitted] in the same manner as in Example 1. The wavelength of this polyimide film is 0.
When light absorption was measured in the range of 8 to 1.7 μm,
As shown by the broken line in Figure 1, there is absorption by the third harmonic of the stretching vibration of the C-H bond near 1.1 μm, and a combination of the harmonic of the stretching vibration of the C-H bond and the bending vibration near 1.4 μm. Absorption by sound and absorption by the second harmonic of the stretching vibration of the C--H bond appeared near 1.65 μm.
【００１９】[0019]
【発明の効果】これらの結果から、本発明の感光性前駆
体から得られる全フッ素化ポリイミドは従来のものと比
較して、近赤外領域での光透過損失率が極めて小さいこ
とが明らかとなった。[Effects of the Invention] From these results, it is clear that the perfluorinated polyimide obtained from the photosensitive precursor of the present invention has an extremely small light transmission loss rate in the near-infrared region compared to conventional polyimides. became.
【図１】実線は実施例１の全フッ素化ポリイミド、破線
は比較例１のポリイミドにおける、それぞれ光の吸光度
の波長依存性を示すグラフである。FIG. 1 is a graph showing the wavelength dependence of the light absorbance of the perfluorinated polyimide of Example 1 as a solid line and the polyimide of Comparative Example 1 as the broken line.
Claims (2)
分子間を橋架けする有機基、Ｒ１ は下記式（化２）：
【化２】 で表される基のうちのいずれかの基、Ｒ２ は下記式（
化３）： 【化３】 で表される基のうちのいずれかの基であり、ここで式中
Ｒｆはフッ素、又はパーフルオロアルキル基、Ｘは下記
式（化４）： 【化４】 （ここで式中Ｒｆ′はパーフルオロアルキレン基、ｎは
１〜１０の数を示す）で表される基のうちのいずれかの
基である〕で表される繰返し単位を含有することを特徴
とする感光性全フッ素化ポリイミド前駆体。[Claim 1] The following general formula (Chemical formula 1): [Chemical formula 1] [In the formula, R* forms a chemical bond by photoreaction,
The organic group bridging between molecules, R1, has the following formula (Chemical formula 2):
Any group among the groups represented by [Chemical formula 2], R2 is represented by the following formula (
Chemical formula 3): Any of the groups represented by the following formula (Chemical formula 3), where Rf is fluorine or a perfluoroalkyl group, and X is the following formula (Chemical formula 4): [Chemical 4] (wherein Rf' is a perfluoroalkylene group, and n is a number from 1 to 10). A photosensitive perfluorinated polyimide precursor.
〕で表されるテトラカルボン酸、又はその誘導体と、式
Ｒ＊ ＯＨ〔式中Ｒ＊ は一般式（化１）中のＲ＊ と
同義である〕で表される感光性アルコールとを反応させ
、その後酸ハライド化し、次いで下記一般式（化６）：
【化６】Ｈ２ Ｎ−Ｒ２ −ＮＨ２ 〔式中Ｒ２ は一
般式（化１）中のＲ２ と同義である〕で表されるジア
ミンと反応させることを特徴とする請求項１に記載の感
光性全フッ素化ポリイミド前駆体の製造方法。[Claim 2] A tetracarboxylic acid represented by the following general formula (Chemical formula 5): [Chemical formula 5] [In the formula, R1 has the same meaning as R1 in the general formula (Chemical formula 1)], or a derivative thereof; R* OH [in the formula, R* has the same meaning as R* in the general formula (Chemical formula 1)] is reacted with a photosensitive alcohol, and then converted into an acid halide, and then the following general formula (Chemical formula 6):
The photosensitivity according to claim 1, characterized in that it is reacted with a diamine represented by H2N-R2-NH2 [wherein R2 has the same meaning as R2 in the general formula (Chemical formula 1)] A method for producing a perfluorinated polyimide precursor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3122946A JP2920887B2 (en) | 1991-04-26 | 1991-04-26 | Photosensitive perfluorinated polyimide precursor and methods for producing them |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3122946A JP2920887B2 (en) | 1991-04-26 | 1991-04-26 | Photosensitive perfluorinated polyimide precursor and methods for producing them |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04328127A true JPH04328127A (en) | 1992-11-17 |
| JP2920887B2 JP2920887B2 (en) | 1999-07-19 |
Family
ID=14848534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3122946A Expired - Lifetime JP2920887B2 (en) | 1991-04-26 | 1991-04-26 | Photosensitive perfluorinated polyimide precursor and methods for producing them |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920887B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994014874A1 (en) * | 1992-12-22 | 1994-07-07 | Amoco Corporation | Photodefinable optical waveguides |
| EP0720030A1 (en) | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Waveguide device and method for production thereof |
| JP2002037885A (en) * | 2000-07-27 | 2002-02-06 | Kanegafuchi Chem Ind Co Ltd | Positive type fluorine containing polyimide precursor and positive type photosensitive fluorine containing polyimide precursor composition |
| JP2002047252A (en) * | 2000-07-26 | 2002-02-12 | Kanegafuchi Chem Ind Co Ltd | Ester compound |
| CN115044040A (en) * | 2021-03-09 | 2022-09-13 | 信越化学工业株式会社 | Polyimide-containing polymer, positive photosensitive resin composition, negative photosensitive resin composition, and pattern formation method |
-
1991
- 1991-04-26 JP JP3122946A patent/JP2920887B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994014874A1 (en) * | 1992-12-22 | 1994-07-07 | Amoco Corporation | Photodefinable optical waveguides |
| EP0720030A1 (en) | 1994-12-28 | 1996-07-03 | Hoechst Aktiengesellschaft | Waveguide device and method for production thereof |
| JP2002047252A (en) * | 2000-07-26 | 2002-02-12 | Kanegafuchi Chem Ind Co Ltd | Ester compound |
| JP2002037885A (en) * | 2000-07-27 | 2002-02-06 | Kanegafuchi Chem Ind Co Ltd | Positive type fluorine containing polyimide precursor and positive type photosensitive fluorine containing polyimide precursor composition |
| CN115044040A (en) * | 2021-03-09 | 2022-09-13 | 信越化学工业株式会社 | Polyimide-containing polymer, positive photosensitive resin composition, negative photosensitive resin composition, and pattern formation method |
| EP4056627A1 (en) * | 2021-03-09 | 2022-09-14 | Shin-Etsu Chemical Co., Ltd. | Polyimide-based polymer, positive photosensitive resin composition, negative photosensitive resin compostion, patterning method, method for forming cured film, interlayer insulating film, surface protective film, and electronic component |
| TWI820625B (en) * | 2021-03-09 | 2023-11-01 | 日商信越化學工業股份有限公司 | Polyimide-based polymer, positive photosensitive resin composition, negative photosensitive resin composition, patterning method, method for forming cured film, interlayer insulating film, surface protective film, and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2920887B2 (en) | 1999-07-19 |
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