JPH0437423B2 - - Google Patents
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- Publication number
- JPH0437423B2 JPH0437423B2 JP28815285A JP28815285A JPH0437423B2 JP H0437423 B2 JPH0437423 B2 JP H0437423B2 JP 28815285 A JP28815285 A JP 28815285A JP 28815285 A JP28815285 A JP 28815285A JP H0437423 B2 JPH0437423 B2 JP H0437423B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- formula
- polymer
- organic group
- resistant material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229920000642 polymer Polymers 0.000 claims description 24
- 239000003779 heat-resistant material Substances 0.000 claims description 12
- 125000000962 organic group Chemical group 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920005575 poly(amic acid) Polymers 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
- 239000002253 acid Substances 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- -1 α-Methyl-2-nitrobenzyl Chemical group 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical class OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BWRBVBFLFQKBPT-UHFFFAOYSA-N (2-nitrophenyl)methanol Chemical compound OCC1=CC=CC=C1[N+]([O-])=O BWRBVBFLFQKBPT-UHFFFAOYSA-N 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 1
- OPWQHYSPLFFRMU-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-amine Chemical compound CCC(N)[Si](OC)(OC)OC OPWQHYSPLFFRMU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- GPXCORHXFPYJEH-UHFFFAOYSA-N 3-[[3-aminopropyl(dimethyl)silyl]oxy-dimethylsilyl]propan-1-amine Chemical compound NCCC[Si](C)(C)O[Si](C)(C)CCCN GPXCORHXFPYJEH-UHFFFAOYSA-N 0.000 description 1
- BUJUURFYPIPOJV-UHFFFAOYSA-N 3-phenyl-3H-indene-1,2-diamine Chemical compound NC1=C(C(C2=CC=CC=C12)C1=CC=CC=C1)N BUJUURFYPIPOJV-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- CNODSORTHKVDEM-UHFFFAOYSA-N 4-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)C1=CC=C(N)C=C1 CNODSORTHKVDEM-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VZUHQRBBQSLSHS-SSZFMOIBSA-N Isoimide Chemical group C1=CC(Br)=CC=C1\N=C/1C(CCCC2)=C2C(=O)O\1 VZUHQRBBQSLSHS-SSZFMOIBSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ZTCFKBWDKVMLMM-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 ZTCFKBWDKVMLMM-UHFFFAOYSA-N 0.000 description 1
- WMTLVUCMBWBYSO-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1OC1=CC=CC=C1 WMTLVUCMBWBYSO-UHFFFAOYSA-N 0.000 description 1
- AXCSBFRIHQXBSG-UHFFFAOYSA-N N=C=O.N=C=O.C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 Chemical compound N=C=O.N=C=O.C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 AXCSBFRIHQXBSG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- PBMIETCUUSQZCG-UHFFFAOYSA-N n'-cyclohexylmethanediimine Chemical compound N=C=NC1CCCCC1 PBMIETCUUSQZCG-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
〔産業上の利用分野〕
この発明は新規なポジ型の感光特性を有するポ
ジ型感光性耐熱材料に関するものである。
〔従来の技術〕
従来、感光性を有する耐熱性樹脂として、(1)ポ
リアミド酸と重クロム酸塩の混合物（特公昭49−
17374号公報）(2)ピロメリツト酸誘導体から合成
される感光性ポリアミド（特開昭49−115541号公
報）(3)ポリアミド酸と不飽和アミンの混合物（特
開昭54−145794号公報）(4)ポリアミド酸と不飽和
エポキシの反応物（特開昭55−45746号公報）(5)
ポリアミド酸とアジド基含有アミンの混合物（特
開昭58−67724号公報）など種々の提案がなされ
ている。
〔発明が解決しようとする問題点〕
しかしながら、上記した材料はすべてネガ型の
感光特性を有したものである。ネガ型感光性樹脂
は、溶解性の樹脂を光架橋させて不溶化させ、未
露光部との溶解差を利用して現像を行ない、パタ
ーニングを行なうものである。光架橋反応を完全
に起こすことができれば、露光部と未露光部とに
おいて、良好な溶解差を生じさせることが可能で
あるが、通常、この反応は完全には起こすことは
難しい。そのため、未露光部を洗い出すための現
像工程で、露光部の架橋不十分な部分が一部洗い
出されるために、表面の膜粗れの原因となる。
さらに、ネガ型感光性樹脂は、現像液に溶解す
る樹脂を、光架橋反応を起こさせて不溶化するこ
とにより、画像を形成させるものであり、この現
像の工程で、架橋部（露光部）の現像液による膨
潤はさけることが出来ない。そのため、これを原
因としたパターンの乱れや、剥離等が発生して、
画像形成の信頼性が乏しくなるばかりでなく、高
解像度の画像形成を行なう上で、非常に不利とな
る。
この発明は、かかる問題点を解決するためにな
されたもので、直接光および電子線でパターニン
グが可能で、パターンの乱れが無く、高耐熱性で
高解像度のポジ型感光性耐熱材料を得ることを目
的とする。
〔問題点を解決するための手段〕
この発明のポジ型感光性耐熱材料は、一般式
（式中、R1は２価の有機基、R2は４価の有機基、
R3はオルト位にニトロ基を有するベンジル誘導
体残基を示し、ｎは任意の正の整数を示す。）
で示される重合体および一般式
（式中、R4は２価の有機基、R5は４価の有機基、
ｍは任意の正の整数を示す。）
で示される重合体を含有するものである。
〔作用〕
この発明の感光性耐熱材料は、ポジ型であるた
め、現像液による膨潤などが無く高解像度とな
り、硬化時の重量変化が低減するためパターンの
乱れが無く、さらに加熱によるイミド化により高
耐熱性となる。
〔実施例〕
この発明の実施例のポジ型感光性耐熱材料が、
一般式(1)で示される重合体20〜90重量部および一
般式(2)で示される重合体10〜80重量部含有するこ
とは好ましい。
この発明に係わる一般式(1)で示される重合体の
合成は種々可能であるが、典型的な方法を述べる
と、一般式(3)で示されるジカルボン酸クロライド
H2N−R1−NH2 (4)
（式中、R1、R2、R3は一般式(1)と同様）
と一般式(4)で示されるジアミンとの重縮合により
行なう方法、および一般式(5)で示されるジカルボ
ン酸と一般式(6)で示されるジイソシアネートとの
OCN−R1−NCO (6)
（式中、R1、R2、R3は一般式(1)と同様）
反応により行なう方法などを挙げることができ
る。
また、この発明に係わる一般式(2)で示される重
合体は、種々の方法により合成が可能であるが、
通常、下記構造の一般式(7)、(8)
H2N−R4−NH2 (7)
（式中、R4、R5は一般式(2)と同様）
の化合物の付加縮合により得られるポリアミド酸
を、シクロヘキシルカルボジイミド（高分子論文
集第34巻第577頁1977年刊行）、チオニルクロライ
ド｛雑誌（European Polymer Journal第15巻第
409頁1979年刊行）｝、三塩化リン｛雑誌（Journal
of Applied Polymer Science第11巻第609頁
1967年刊行）｝、無水トリフルオロ酢酸｛雑誌
（Vysokomol soyed第A17巻第1764頁1975年刊
行）｝などの脱水剤を用いて閉環させることによ
り合成することが可能である。
一般式(1)で示される重合体の合成に際して使用
される一般式(3)および(5)の化合物は以下のように
して合成することが可能である。即ち、ベンジル
アルコール誘導体とテトラカルボン酸二無水物と
の反応により、一般式(5)のジカルボン酸が合成さ
れ、さらに酸ハロゲン化を行なうことにより一般
式(3)のジカルボン酸クロライドが合成される。
テトラカルボン酸二無水物としては、例えばピ
ロメリツト酸二無水物、３，3′，４，4′−テトラ
カルボン酸二無水物、３，3′，４，4′−ビフエニ
ルテトラカルボン酸二無水物、１，２，５，６−
ナフタレンテトラカルボン酸二無水物、２，２−
ビス（ジカルボキシフエニル）ヘキサフルオロプ
ロパン二酸無水物、１，２，３，４−ブタンテト
ラカルボン酸二無水物および１，２，３，４−シ
クロペンタンテトラカルボン酸二無水物などをあ
げることができる。また、ベンジルアルコール誘
導体としては、２−ニトロベンジルアルコール、
α−メチル−２−ニトロベンジルアルコール、α
−エチル−２−ニトロベンジルアルコール、２，
４−ジニトロベンジルアルコールおよびα−メチ
ル−２，４−ジニトロベンジルアルコールなどを
あげることができる。
さらに、一般式(4)および(7)で示されるジアミン
としては、例えば、エチレンジアミン、トリメチ
レンジアミン、ヘキサメチレンジアミン、ジアミ
ノジシクロヘキシルジアミン、キシリレンジアミ
ン、ジアミノジフエニルエーテル、ジアミノジフ
エニルメタン、ジアミノジフエニルスルホン、ジ
アミノベンゾフエノン、ビス（γ−アミノプロピ
ル）テトラメチルジシロキサン、ジアミノフエニ
ルインデン、ベンジシン、Ｏ−トリジンおよび
１，３−ジ（Ｐ−アミノフエニル）テトラメチル
ジシクロサンなどを挙げることができる。
また、一般式(6)で示されるジイソシアネートと
しては、ジフエニルメタンジイソシアネート、ト
ルエンジイソシアネート、ジフエニルエーテルジ
イソシアネート、ベンゾフエノンジイソシアネー
ト、ジフエニルスルホンジイソシアネート、およ
びナフタレンジイソシアネートなどを挙げること
ができる。
この発明の一実施例のポジ型感光性耐熱材料は
有機溶媒の10〜50重量％の濃度の溶液として使用
されるのが好ましく、その濃度は作業上の条件に
合せて任意の選択が可能である。この有機溶媒と
しては、一般式(1)および(2)の重合体に不活性であ
り、良溶媒であるものならばどのようなものでも
使用可能であるが、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
メチルスルホキシドｍ−クレゾールおよびＮ，Ｎ
−ジメチルホルムアミドなどは好ましい溶媒であ
る。
この発明のポジ型感光性耐熱材料をガラス板あ
るいはシリコンウエハー上に回転塗布したのち、
50〜90℃でブレキユアーして膜を形成することが
できる。この際、α−アミノプロピルトリメトキ
シシランおよび４−アミノフエニルトリメトキシ
シランなどのカツプリング剤を処理した基板を用
いることにより、さらにすぐれた接着性を与える
ことができる。
上述の膜上に所定のパターンを有するマスクを
装着し、光または電子線を照射し、アルカリ水溶
液で現像することにより、露光部が洗い出されて
端面のシヤープなレリーフパターンが得られる。
この際、使用される現像液はアルカリ水溶液であ
ればどよのうなものでも良く、苛性カリウム、テ
トラメチルアンモニウムヒドロキサイド、エタノ
ールアミンおよびＮ，Ｎ−ジメチルエタノールア
ミンなどの水溶液を例としてあげることができ
る。
以下、この発明を実施例により具体的に説明す
るが、これよりこの発明が限定されない。
実施例 １
33.46ｇ（0.22モル）のＯ−ニトロベンジルア
ルコールと800mlの乾燥したトルエンとを加え、
均一に溶解し、この中に、ピロメリツト酸二無水
物の21.8ｇ（0.1モル）を加えて、５時間リフラ
ツクスさせた。析出した結晶を回収し、元素分
析、赤外線吸収スペクトルの測定から、ピロメリ
ツト酸ジ（Ｏ−ニトロベンジルエステル）である
ことが確認できた。
得られた酸を、チオニルクロライド中で、リフ
ラツクスさせ、酸ハロゲン化させた。反応後、一
部のチオニルクロライドを留去し、結晶を析出さ
せた。元素分析および、赤外線吸収スペクトルの
測定から、酸ハロゲンの確認ができた。また、こ
の物質は70％の収率で得られた。
４，4′−ジアミノジフエニルエーテル１ｇ
（0.005モル）と無水炭酸ナトリウム0.63ｇ（0.006
モル）と、蒸留水100ml、アセトン200mlとを１
のビーカに加え、完全に溶解させたのち、氷浴で
冷却させた。一方、上記で得られた酸クロライド
の2.805ｇ（0.005モル）を乾燥したクロロホルム
100ｇに溶解させた。
これらの二液を、高速ミキサーで、低温で混合
した。反応後、エタノールを加えて、ポリマーを
析出させ、十分水洗後、回収し、乾燥させ一般式
(1)の重合体を得た。
[Industrial Application Field] The present invention relates to a positive photosensitive heat-resistant material having novel positive photosensitive characteristics. [Prior art] Conventionally, as a photosensitive heat-resistant resin, (1) a mixture of polyamic acid and dichromate (Japanese Patent Publication No. 1973-
17374) (2) Photosensitive polyamide synthesized from pyromellitic acid derivatives (Japanese Patent Application Laid-open No. 115541/1982) (3) Mixture of polyamic acid and unsaturated amine (Japanese Patent Application Laid-open No. 145794/1989) (4) ) Reaction product of polyamic acid and unsaturated epoxy (JP-A-55-45746) (5)
Various proposals have been made, such as a mixture of polyamic acid and an amine containing an azide group (Japanese Unexamined Patent Publication No. 58-67724). [Problems to be Solved by the Invention] However, all of the above-mentioned materials have negative photosensitive characteristics. Negative photosensitive resins are those in which a soluble resin is photo-crosslinked to become insolubilized, and developed and patterned using the difference in solubility between the resin and the unexposed area. If the photocrosslinking reaction can occur completely, it is possible to create a good solubility difference between the exposed and unexposed areas, but it is usually difficult to cause this reaction to occur completely. Therefore, in the development process for washing out the unexposed areas, the insufficiently crosslinked parts of the exposed areas are partially washed out, which causes film roughening on the surface. Furthermore, negative photosensitive resins form images by causing a photocrosslinking reaction to insolubilize the resin that dissolves in the developer, and in this development process, the crosslinked areas (exposed areas) are removed. Swelling caused by the developer cannot be avoided. As a result, pattern disturbances and peeling may occur due to this.
This not only reduces the reliability of image formation, but is also extremely disadvantageous in forming high-resolution images. This invention was made to solve these problems, and it is an object of the present invention to obtain a positive photosensitive heat-resistant material that can be patterned with direct light and electron beams, has no pattern disturbance, and has high heat resistance and high resolution. With the goal. [Means for solving the problems] The positive photosensitive heat-resistant material of the present invention has the general formula (In the formula, R 1 is a divalent organic group, R 2 is a tetravalent organic group,
R 3 represents a benzyl derivative residue having a nitro group at the ortho position, and n represents any positive integer. ) Polymer and general formula represented by (In the formula, R 4 is a divalent organic group, R 5 is a tetravalent organic group,
m represents any positive integer. ) Contains the polymer shown below. [Function] Since the photosensitive heat-resistant material of the present invention is a positive type, it does not swell due to developer and has high resolution. Weight change during curing is reduced, so there is no pattern disturbance, and furthermore, it can be imidized by heating. High heat resistance. [Example] The positive photosensitive heat-resistant material of the example of this invention is
It is preferable to contain 20 to 90 parts by weight of the polymer represented by general formula (1) and 10 to 80 parts by weight of the polymer represented by general formula (2). The polymer represented by the general formula (1) according to this invention can be synthesized in various ways, but a typical method is to synthesize a dicarboxylic acid chloride represented by the general formula (3). A method carried out by polycondensation of H 2 N−R 1 −NH 2 (4) (wherein R 1 , R 2 , and R 3 are the same as in general formula (1)) and a diamine represented by general formula (4). , and a dicarboxylic acid represented by the general formula (5) and a diisocyanate represented by the general formula (6). OCN-R 1 -NCO (6) (In the formula, R 1 , R 2 and R 3 are the same as in general formula (1)) A method of carrying out the reaction can be mentioned. Furthermore, the polymer represented by the general formula (2) according to this invention can be synthesized by various methods, but
Usually, the following general formulas (7) and (8) H 2 N−R 4 −NH 2 (7) (In the formula, R 4 and R 5 are the same as the general formula (2).) A polyamic acid obtained by addition condensation of the compound of the formula {Magazine (European Polymer Journal Vol. 15 No.
409 pages, published in 1979)}, phosphorus trichloride {Journal
of Applied Polymer Science Vol. 11, p. 609
It can be synthesized by ring-closing using a dehydrating agent such as trifluoroacetic anhydride (Vysokomol soyed Vol. A17, p. 1764, published in 1975). The compounds of general formulas (3) and (5) used in the synthesis of the polymer represented by general formula (1) can be synthesized as follows. That is, the dicarboxylic acid of the general formula (5) is synthesized by the reaction of the benzyl alcohol derivative and the tetracarboxylic dianhydride, and the dicarboxylic acid chloride of the general formula (3) is synthesized by further acid halogenation. . Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-tetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. thing, 1, 2, 5, 6-
naphthalenetetracarboxylic dianhydride, 2,2-
Examples include bis(dicarboxyphenyl)hexafluoropropanedioic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. be able to. In addition, as benzyl alcohol derivatives, 2-nitrobenzyl alcohol,
α-Methyl-2-nitrobenzyl alcohol, α
-ethyl-2-nitrobenzyl alcohol, 2,
Examples include 4-dinitrobenzyl alcohol and α-methyl-2,4-dinitrobenzyl alcohol. Furthermore, examples of diamines represented by general formulas (4) and (7) include ethylenediamine, trimethylenediamine, hexamethylenediamine, diaminodicyclohexyldiamine, xylylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, and diaminodiphenyl diamine. Enylsulfone, diaminobenzophenone, bis(γ-aminopropyl)tetramethyldisiloxane, diaminophenylindene, benzicine, O-tolidine and 1,3-di(P-aminophenyl)tetramethyldisiloxane, etc. I can do it. Further, examples of the diisocyanate represented by the general formula (6) include diphenylmethane diisocyanate, toluene diisocyanate, diphenyl ether diisocyanate, benzophenone diisocyanate, diphenylsulfone diisocyanate, and naphthalene diisocyanate. The positive photosensitive heat-resistant material of one embodiment of the present invention is preferably used as a solution of an organic solvent at a concentration of 10 to 50% by weight, and the concentration can be arbitrarily selected depending on the working conditions. be. As this organic solvent, any solvent can be used as long as it is inert to the polymers of general formulas (1) and (2) and is a good solvent, but N-methyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylsulfoxide m-cresol and N,N
-Dimethylformamide and the like are preferred solvents. After spin-coating the positive photosensitive heat-resistant material of this invention onto a glass plate or silicon wafer,
A film can be formed by breaking at 50-90°C. In this case, even better adhesion can be provided by using a substrate treated with a coupling agent such as α-aminopropyltrimethoxysilane and 4-aminophenyltrimethoxysilane. A mask having a predetermined pattern is placed on the above film, irradiated with light or electron beams, and developed with an alkaline aqueous solution, whereby exposed areas are washed out and a sharp relief pattern on the end face is obtained.
At this time, the developer used may be any alkaline aqueous solution, and examples include aqueous solutions of caustic potassium, tetramethylammonium hydroxide, ethanolamine, and N,N-dimethylethanolamine. can. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. Example 1 Add 33.46 g (0.22 mol) of O-nitrobenzyl alcohol and 800 ml of dry toluene,
The mixture was uniformly dissolved, 21.8 g (0.1 mol) of pyromellitic dianhydride was added thereto, and the mixture was refluxed for 5 hours. The precipitated crystals were collected, and elemental analysis and infrared absorption spectrum measurements confirmed that they were pyromellitic acid di(O-nitrobenzyl ester). The resulting acid was refluxed in thionyl chloride for acid halogenation. After the reaction, a part of thionyl chloride was distilled off to precipitate crystals. An acid halogen was confirmed through elemental analysis and infrared absorption spectrum measurement. Also, this material was obtained in 70% yield. 4,4'-diaminodiphenyl ether 1g
(0.005 mol) and anhydrous sodium carbonate 0.63 g (0.006
1 mole), 100 ml of distilled water, and 200 ml of acetone.
After completely dissolving the mixture, it was cooled in an ice bath. On the other hand, 2.805 g (0.005 mol) of the acid chloride obtained above was dried in chloroform.
It was dissolved in 100g. These two liquids were mixed at low temperature using a high speed mixer. After the reaction, ethanol is added to precipitate the polymer, which is thoroughly washed with water, collected, and dried to give the general formula
The polymer (1) was obtained.
【表】【table】
【表】
撹拌機、温度計、チツ素導入管、塩化カルシウ
ム管を備えた500mlの４つ口フラスコに、４，
4′−ジアミノジフエニルエーテル20ｇ（0.1モル）
と乾燥したＮ−メチル−２−ピロリドン350ｇを
加え、均一に溶解させた。３，3′，４，4′−ベン
ゾフエノンテトラカルボン酸無水物の32.2ｇ
（0.1モル）を反応温度が30℃を越えないように、
数回に分けて添加させる。添加後、８時間反応を
続けてポリアミド酸を得た。次いで、この溶液を
０〜５℃に冷却させ、シクロヘキシルカルボジイ
ミド41.3ｇ（0.2モル）を数回に分けて添加し、
十分撹拌した。添加後、４時間反応を続けたの
ち、室温にもどした。
反応後、析出した尿素誘導体を加圧ろ加して除
き、メタノール中に再沈して、十分、アルコール
洗浄し、尿素誘導体を除いて一般式(2)の重合体を
得た。
得られた重合体の赤外線吸収スペクトルにおい
て、1800cm-1、1710cm-1にカルボニル基による吸
収が、930cm-1にラクトンのＣ−Ｏにより吸収が
認められることから、一般式(2)のイソイミド構造
を有することが明らかとなつた。[Table] 4,
4′-diaminodiphenyl ether 20g (0.1mol)
and 350 g of dried N-methyl-2-pyrrolidone were added and uniformly dissolved. 32.2 g of 3,3',4,4'-benzophenonetetracarboxylic acid anhydride
(0.1 mol) so that the reaction temperature does not exceed 30℃.
Add in several portions. After the addition, the reaction was continued for 8 hours to obtain polyamic acid. Next, this solution was cooled to 0 to 5°C, and 41.3 g (0.2 mol) of cyclohexylcarbodiimide was added in several portions.
Stir thoroughly. After the addition, the reaction was continued for 4 hours, and then the temperature was returned to room temperature. After the reaction, the precipitated urea derivative was removed by pressure filtration, reprecipitated in methanol, thoroughly washed with alcohol, and the urea derivative was removed to obtain a polymer of general formula (2). In the infrared absorption spectrum of the obtained polymer, absorption due to carbonyl group is observed at 1800 cm -1 and 1710 cm -1 and absorption due to C-O of lactone is observed at 930 cm -1 , indicating that the isoimide structure of general formula (2) is observed. It has become clear that there is a
【表】【table】
【表】
上記のようにして得た一般式(1)で示される重合
体４ｇ、および一般式(2)で示される重合体６ｇを
Ｎ−メチル−２−ピロリドンに混合し樹脂液と
し、この発明の一実施例のポジ型感光性耐熱材料
を得た。
得られた樹脂液をガラス板に塗布し、80℃30分
間加熱乾燥させることにより膜を得た。この膜
に、所定のマスクを通して、紫外線（Hg−Xeラ
ンプ500W）を30秒間照射した。照射後、テトラ
メチルアンモニウムヒドロキサイドの５％水溶液
により現像を行なうことにより、良好なパターン
が得られた。このパターンを、200℃30分、350℃
30分チツ素中で加熱を行なつたが、パターンの乱
れは、ほとんど起らず、良好なパターンが得られ
た。
加熱処理を行なつた膜の、熱重量減少を測定し
た結果を、表３に合せて示した。なお、条件は、
10℃／分、チツ素気流下で測定した。その結果、
耐熱性に優れていることが解る。
実施例 ２〜８
表１のアミンを用いる他は上記と同様の方法に
より一般式(1)の重合体を合成し、表２のジアミン
と酸二無水物を用いる他は上記と同様の方法によ
り一般式(2)の重合体を合成した。
表３に示した一般式(1)で示される重合体、一般
式(2)で示される重合体および溶媒を用いる他は実
施例１と同様にしてこの発明の他の実施例のポジ
型感光性耐熱材料を得、その特性を実施例１と同
様に検討した結果を合せて表３に示し、実施例１
と同様の優れた特性を得た。
〔発明の効果〕[Table] 4 g of the polymer represented by the general formula (1) obtained as above and 6 g of the polymer represented by the general formula (2) are mixed with N-methyl-2-pyrrolidone to make a resin liquid. A positive photosensitive heat-resistant material according to an example of the invention was obtained. The obtained resin liquid was applied to a glass plate and dried by heating at 80° C. for 30 minutes to obtain a film. This film was irradiated with ultraviolet light (Hg-Xe lamp 500W) for 30 seconds through a predetermined mask. After irradiation, a good pattern was obtained by developing with a 5% aqueous solution of tetramethylammonium hydroxide. Repeat this pattern at 200℃ for 30 minutes, then at 350℃.
Heating was carried out in a nitrogen atmosphere for 30 minutes, but the pattern was hardly disturbed and a good pattern was obtained. Table 3 also shows the results of measuring the thermal weight loss of the heat-treated film. In addition, the conditions are:
Measurement was carried out at 10°C/min under a nitrogen gas flow. the result,
It can be seen that it has excellent heat resistance. Examples 2 to 8 A polymer of general formula (1) was synthesized by the same method as above except for using the amine in Table 1, and a polymer of general formula (1) was synthesized by the same method as above except for using the diamine and acid dianhydride in Table 2. A polymer of general formula (2) was synthesized. A positive photosensitive photosensitive material according to another example of the present invention was prepared in the same manner as in Example 1 except that the polymer represented by the general formula (1) shown in Table 3, the polymer represented by the general formula (2), and the solvent were used. The properties of the heat-resistant material were investigated in the same manner as in Example 1, and the results are shown in Table 3.
The same excellent properties were obtained. 〔Effect of the invention〕
【表】【table】
【表】
以上説明したとおり、この発明は、一般式
（式中、R1は２価の有機基、R2は４価の有機基、
R3はオルト位にニトロ基を有するベンジル誘導
体残基、ｎは任意の正の整数を示す。）
で示される重合体、および一般式
（式中、R4は２価の有機基、R5は４価の有機基、
ｍは任意の正の整数を示す。）
で示される重合体を含有するものを用いることに
より、直接光および電子線でパターニングが可能
で、パターンの乱れが無く、高耐熱性で高解像度
のポジ型感光性耐熱材料を得ることができる。[Table] As explained above, the present invention is based on the general formula (In the formula, R 1 is a divalent organic group, R 2 is a tetravalent organic group,
R 3 is a benzyl derivative residue having a nitro group at the ortho position, and n is any positive integer. ) and the general formula (In the formula, R 4 is a divalent organic group, R 5 is a tetravalent organic group,
m represents any positive integer. ) By using a polymer containing the polymer shown in (1), it is possible to pattern with direct light and electron beam, and it is possible to obtain a positive photosensitive heat-resistant material with high heat resistance and high resolution without pattern disturbance. .
Claims (1)
R3はオルト位にニトロ基を有するベンジル誘導
体残基、ｎは任意の正の整数を示す。） で示される重合体、および 一般式 （式中、R4は２価の有機基、R5は４価の有機基、
ｍは任意の正の整数を示す。） で示される重合体を含有するポジ型感光性耐熱材
料。 ２ R3が 【式】【式】 【式】および 【式】 のうち何れか一種である特許請求の範囲第１項記
載のポジ型感光性耐熱材料。[Claims] 1. General formula (In the formula, R 1 is a divalent organic group, R 2 is a tetravalent organic group,
R 3 is a benzyl derivative residue having a nitro group at the ortho position, and n is any positive integer. ) and the general formula (In the formula, R 4 is a divalent organic group, R 5 is a tetravalent organic group,
m represents any positive integer. ) A positive photosensitive heat-resistant material containing a polymer represented by: 2. The positive-working photosensitive heat-resistant material according to claim 1, wherein R 3 is any one of [Formula] [Formula] [Formula] and [Formula].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28815285A JPS62145239A (en) | 1985-12-19 | 1985-12-19 | Positive type photosensitive heat resistant material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28815285A JPS62145239A (en) | 1985-12-19 | 1985-12-19 | Positive type photosensitive heat resistant material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62145239A JPS62145239A (en) | 1987-06-29 |
| JPH0437423B2 true JPH0437423B2 (en) | 1992-06-19 |
Family
ID=17726474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28815285A Granted JPS62145239A (en) | 1985-12-19 | 1985-12-19 | Positive type photosensitive heat resistant material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62145239A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5614354A (en) * | 1993-02-03 | 1997-03-25 | Toray Industries, Inc. | Method of forming positive polyimide patterns |
| CN101405655B (en) | 2006-03-16 | 2013-02-06 | 旭硝子株式会社 | Negative-type photosensitive fluorinated aromatic resin composition |
| TW202208510A (en) * | 2020-06-23 | 2022-03-01 | 日商富士軟片股份有限公司 | Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermosetting resin |
-
1985
- 1985-12-19 JP JP28815285A patent/JPS62145239A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62145239A (en) | 1987-06-29 |
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