JPS6348310A - Photosensitive heat-resistant resin composition - Google Patents
Photosensitive heat-resistant resin compositionInfo
- Publication number
- JPS6348310A JPS6348310A JP19189086A JP19189086A JPS6348310A JP S6348310 A JPS6348310 A JP S6348310A JP 19189086 A JP19189086 A JP 19189086A JP 19189086 A JP19189086 A JP 19189086A JP S6348310 A JPS6348310 A JP S6348310A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- photosensitive
- formula
- resin composition
- polyimide resin
- 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.)
- Pending
Links
- 229920006015 heat resistant resin Polymers 0.000 title claims abstract description 17
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 229920001721 polyimide Polymers 0.000 claims abstract description 34
- 239000009719 polyimide resin Substances 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 12
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 5
- 230000036211 photosensitivity Effects 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000003504 photosensitizing agent Substances 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007261 regionalization Effects 0.000 description 5
- 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 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- -1 diamine compound Chemical class 0.000 description 1
- NOMRCDXYHTWTNR-UHFFFAOYSA-N diphenylmethanediamine;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 NOMRCDXYHTWTNR-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical group NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 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
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-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
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0387—Polyamides or polyimides
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【発明の詳細な説明】 〔技術分野〕 この発明は、感光性耐熱樹脂組成物に関する。[Detailed description of the invention] 〔Technical field〕 The present invention relates to a photosensitive heat-resistant resin composition.
半導体の保護膜や、層間絶縁膜として、感光性を有し、
かつ、耐熱性に優れた感光性ポリイミド樹脂組成物や感
光性ポリイミド樹脂前駆体が、開発、上市されている。It has photosensitivity and can be used as a protective film for semiconductors or as an interlayer insulating film.
In addition, photosensitive polyimide resin compositions and photosensitive polyimide resin precursors having excellent heat resistance have been developed and put on the market.
そのような感光性ポリイミド樹脂組成物や感光性ポリイ
ミド樹脂前駆体としては、たとえば、■ ポリアミド酸
のカルボン酸部分に、光重合可能な炭素−炭素二重結合
を持つ化合物をエステル結合によって結合させたもの（
米国特許第３゜９５７．５１２号等）、
■ ポリアミド酸にアミノ基またはその四級塩を含む感
光性モノマーを添加したもの（特開昭５４−１４５７９
４号公報、特開昭５７−１０２９２６号公報、特開昭５
８−１６０３２０号公報等）、
■ 溶剤可溶性ポリイミドのアミン成分として、エチレ
ン性不飽和基を含むジアミン化合物を用いるもの（特開
昭５９−２２０７３０号公報等）等がある。Such photosensitive polyimide resin compositions and photosensitive polyimide resin precursors include, for example: thing(
U.S. Pat.
Publication No. 4, JP-A-57-102926, JP-A-5
8-160320, etc.); (2) A diamine compound containing an ethylenically unsaturated group is used as the amine component of the solvent-soluble polyimide (Japanese Patent Application Laid-Open No. 59-220730, etc.).
これらの感光性ポリイミド樹脂組成物や感光性ポリイミ
ド樹脂前駆体は、たとえば、極性溶媒に溶解した状態で
供給されている。そして、この溶液をスピンナー等を用
いて基板に塗布し、７０〜８０℃に加熱して溶媒を除去
したあと、フォトマスクを用いて露光し、溶媒で現像し
てレリーフパターンを得る、等の方法で使用される。These photosensitive polyimide resin compositions and photosensitive polyimide resin precursors are supplied, for example, in a state dissolved in a polar solvent. Then, this solution is applied to a substrate using a spinner or the like, heated to 70 to 80°C to remove the solvent, exposed using a photomask, and developed with a solvent to obtain a relief pattern. used in
ところが、以上のような感光性ポリイミド樹脂組成物や
感光性ポリイミド樹脂前駆体のうち、上記■および■の
ものでは、ポリイミド樹脂本来の耐熱性を損なわないた
めに、パターン形成後、４００℃程度の高温でベータし
て、耐熱性が低い感光基の部分を熱分解し、除去してや
る必要がある。このため、この■や■のものでは、ベー
タ後の膜減りが著しく、ぼやけが発生して所望のパター
ンを得ることが難しい。However, among the above-mentioned photosensitive polyimide resin compositions and photosensitive polyimide resin precursors, the above-mentioned ones (1) and (2) are heated to about 400°C after pattern formation in order not to impair the inherent heat resistance of the polyimide resin. It is necessary to betatize at a high temperature to thermally decompose and remove the photosensitive groups that have low heat resistance. For this reason, in the case of these ■ and ■, the film decreases significantly after beta, blurring occurs, and it is difficult to obtain a desired pattern.
また、■のものでは、先の■、■と同様に感光基を熱分
解すると、それにともなってイミド骨格も分解されてし
まう恐れがあるため、感光基を分解することができない
。このため、ポリイミド本来の耐熱性を充分に活かすこ
とができず、パターンの耐熱性が充分得られない、と言
う問題がある〔発明の目的〕
この発明は、以上の事情に鑑みてなされたものであって
、パターン形成後の高温によるベータが不要で、しかも
、耐熱性に優れたパターンを得ることができる感光性耐
熱樹脂組成物を提供することを目的としている。In addition, in the case of (2), when the photosensitive group is thermally decomposed as in the previous cases (2) and (2), the imide skeleton may also be decomposed along with the thermal decomposition, so the photosensitive group cannot be decomposed. For this reason, there is a problem in that the inherent heat resistance of polyimide cannot be fully utilized, and the pattern cannot have sufficient heat resistance. [Object of the Invention] This invention has been made in view of the above circumstances. The object of the present invention is to provide a photosensitive heat-resistant resin composition that does not require beta due to high temperature after pattern formation and can provide a pattern with excellent heat resistance.
以上の目的を達成するため、この発明は、以下の一般式
（Ａ）で表されたポリイミド樹脂骨格を成分中に含んで
いることを特徴とする感光性耐熱樹脂組成物。In order to achieve the above object, the present invention provides a photosensitive heat-resistant resin composition containing a polyimide resin skeleton represented by the following general formula (A) in its components.
・・・（Ａ）
ただし、上記式中Ｒ１は、以下の一般式から選ばれる少
なくとも１つの二価の基をあられし、式中Ｒ１は、以下
の一般式から選ばれる少なくとも１つの四価の基をあら
れし、
式中Ｒｓ 、Ｒａ 、Ｒｓ 、Ｒｈは、それぞれ、水素
、芳香族基およびアルキル基の中から選ばれた少なくと
も１つの一価の基をあられし、ｎは１以上の整数をあら
れしている、
を要旨としている。...(A) However, in the above formula, R1 represents at least one divalent group selected from the following general formula, and in the formula, R1 represents at least one tetravalent group selected from the following general formula. In the formula, Rs, Ra, Rs, and Rh each represent at least one monovalent group selected from hydrogen, an aromatic group, and an alkyl group, and n is an integer of 1 or more. The gist is that there is a hailstorm.
以下に、この発明の詳細な説明する。The present invention will be explained in detail below.
この発明の感光性耐熱樹脂組成物は、以下の一般式（Ａ
）であられされたポリイミド樹脂骨格を成分中に含んで
いることを特徴としている。The photosensitive heat-resistant resin composition of this invention has the following general formula (A
) is characterized by containing a polyimide resin skeleton in its components.
・・・ （Ａ）
以上のようなポリイミド骨格末端のマレイミド基（式中
括弧外の部分）は、熱によって反応するのみならず、紫
外線等の化学線によっても付加反応する、すなわち、感
光性を有していることが一般に知られている。そして、
上記マレイミド基が付加反応してできた硬化物は、従来
のアクリル系、メタクリル系等の官能基が付加反応して
できた硬化物に比べて高い耐熱性を有している。この発
明は、このようなマレイミド基の感光性および耐熱性を
利用したもので、それによってパターン形成後の熱処理
等が不要で、しかも、耐熱性に優れたパターンを得るこ
とができる感光性耐熱樹脂組成物を得ようとするもので
ある。... (A) The maleimide group at the end of the polyimide skeleton (the part outside the parentheses in the formula) not only reacts with heat but also undergoes an addition reaction with actinic radiation such as ultraviolet rays, that is, it increases photosensitivity. It is generally known that it has. and,
The cured product produced by the addition reaction of the maleimide group has higher heat resistance than the conventional cured product produced by the addition reaction of acrylic or methacrylic functional groups. The present invention utilizes the photosensitivity and heat resistance of such maleimide groups, thereby creating a photosensitive heat-resistant resin that does not require heat treatment after pattern formation and can form patterns with excellent heat resistance. The aim is to obtain a composition.
上記マレイミド基の間を繋ぐポリイミド骨格（式中括弧
内の部分）は、閉環した構造を有しており、そのままで
は溶媒に溶けにくいものとなる恐れがある。そこで、こ
の発明では、上記ポリイミド骨格中のＲ３およびＲ２を
、以下の一般式であられされた非対称形のもの（構造が
直線的でないもの）に特定することで、その溶媒への溶
解性を向上させる必要がある。The polyimide skeleton (the part in parentheses in the formula) that connects the maleimide groups has a closed ring structure, and there is a possibility that it will be difficult to dissolve in a solvent if left as is. Therefore, in this invention, by specifying R3 and R2 in the polyimide skeleton to be asymmetric (non-linear structure) represented by the following general formula, the solubility in the solvent is improved. It is necessary to do so.
すなわち、Ｒ１は、以下の一般式から選ばれた少な（と
も１つの二価の基である必要がある。That is, R1 must be at least one divalent group selected from the following general formula.
また、Ｒ２は、以下の一般式から選ばれた少なくとも１
つの四価の基である必要がある。Furthermore, R2 is at least one selected from the following general formulas.
It must be one tetravalent group.
なお、上記式（Ａ）中Ｒ１〜Ｒｂは、同一か、または、
異なることができ、水素、芳香族基およびアルキル基の
中から選ばれた少なくとも１つの一価の基をあられして
おり、ｎは１以上の整数をあられしている。In addition, R1 to Rb in the above formula (A) are the same or,
and at least one monovalent group selected from hydrogen, an aromatic group, and an alkyl group, and n is an integer of 1 or more.
ｎを１以上の整数とするのは、ｎがＯでは分子量が小さ
過ぎて充分な物性を持ったパターンを形成することがで
きないからである。また、このｎは、この発明では、２
〜１００の範囲内であることが好ましい。ｎが１００以
内であることが好ましいのは、ｎが１００を超えたもの
では、１分子中の感光基（マレイミド基）の濃度が低く
なり過ぎて、良好な感度を得ることができない傾向かあ
るからである。The reason why n is an integer of 1 or more is because when n is O, the molecular weight is too small to form a pattern with sufficient physical properties. In addition, in this invention, this n is 2
It is preferably within the range of 100 to 100. The reason why n is preferably within 100 is that if n exceeds 100, the concentration of photosensitive groups (maleimide groups) in one molecule tends to be too low, making it impossible to obtain good sensitivity. It is from.
この発明の感光性耐熱樹脂組成物は、以上のような式（
Ａ）であられされたポリイミド樹脂骨格のみからなって
いてもよいし、上記式（Ａ）のポリイミド樹脂骨格と、
それ以外の樹脂との混合物であってもよい、また、壱の
感光性を調整するために、必要に応じて、増感剤、光重
合開始剤および感光性モノマーのうちの少なくとも１つ
が配合され）ようであってもかまわない。The photosensitive heat-resistant resin composition of this invention has the above formula (
It may consist only of the polyimide resin skeleton formed by A), or the polyimide resin skeleton of the above formula (A),
It may be a mixture with other resins, and if necessary, at least one of a sensitizer, a photoinitiator, and a photosensitive monomer may be blended to adjust the photosensitivity. ) It doesn't matter if it looks like this.
増感剤、光重合開始剤および感光性モノマーの種類は、
この発明では特に限定されず、通常使用されているもの
を用いることができる。そのような増感剤、光重合開始
剤および感光性モノマーとしては、たとえば、ベンゾイ
ンメチルエーテル。The types of sensitizer, photoinitiator and photosensitive monomer are as follows:
This invention is not particularly limited, and commonly used materials can be used. Examples of such sensitizers, photoinitiators and photosensitive monomers include benzoin methyl ether.
ベンゾインエチルエーテル、ベンゾインジメチルエーテ
ル等のベンゾイン類、チオキサントン、クロルチオキサ
ントン、アルキルチオキサントン等のチオキサントン類
、キサントン、ミヒラーケトン、２−エチルアントラキ
ノン、ベンゾフェノン類等が挙げられる。Examples include benzoins such as benzoin ethyl ether and benzoin dimethyl ether, thioxanthones such as thioxanthone, chlorothioxanthone, and alkylthioxanthone, xanthone, Michler's ketone, 2-ethylanthraquinone, and benzophenones.
上記一般式（Ａ）のポリイミド樹脂骨格を得る方法も、
この発明では特に限定されないが、たとえば、以下のよ
うにして製造される。The method for obtaining the polyimide resin skeleton of the above general formula (A) also includes:
Although not particularly limited in the present invention, it can be manufactured, for example, as follows.
まず、上記式中Ｒ３をその骨格中に含むジアミンと、Ｒ
８をその骨格中に含む二数無水物と、無水マレイン酸と
を用意する。用意したこれらの化合物を、たとえば、ジ
メチルホルムアミド、ジメチルスルホキシド、２−メチ
ルピロリドン等の極性溶媒に溶解し、室温付近の温度で
一定時間かく拌すると、ポリアミド酸が得られる。そし
て、得られたポリアミド酸を脱水閉環してやれば、上記
式（Ａ）のポリイミド樹脂骨格が得られるのである。First, a diamine containing R3 in the above formula in its skeleton, and R
A dianhydride containing 8 in its skeleton and maleic anhydride are prepared. When these prepared compounds are dissolved in a polar solvent such as dimethylformamide, dimethylsulfoxide, 2-methylpyrrolidone, etc. and stirred for a certain period of time at a temperature around room temperature, a polyamic acid is obtained. Then, by dehydrating and ring-closing the obtained polyamic acid, the polyimide resin skeleton of the above formula (A) can be obtained.
なお、この発明においては、この脱水閉環を加熱によっ
て行うと、ポリアミド酸中にシス型で存在する末端のマ
レイン酸モノアミド基が、ポリマーの物性に悪影響を与
えるマレイン酸のトランス体となってしまう恐れがある
。このため、この発明においては、上記脱水閉環を、化
学的に行ってやることが好ましい。そのような化学的閉
環法としては、たとえば、無水酢酸等の閉環剤を用いて
室温程度の温度で閉環する方法等がある。In addition, in this invention, if this dehydration ring closure is performed by heating, there is a risk that the terminal maleic acid monoamide group, which exists in the cis form in the polyamic acid, will become the trans form of maleic acid, which has an adverse effect on the physical properties of the polymer. There is. Therefore, in the present invention, it is preferable to carry out the dehydration ring closure chemically. Examples of such a chemical ring-closing method include a method of ring-closing using a ring-closing agent such as acetic anhydride at a temperature around room temperature.
以上のような、この発明の感光性耐熱樹脂組成物は、従
来のフォトレジストと同様にしてパターン形成に使用す
ることができる。The photosensitive heat-resistant resin composition of the present invention as described above can be used for pattern formation in the same manner as conventional photoresists.
すなわち、上記式（Ａ）のポリイミド樹脂骨格を含むこ
の発明の感光性耐熱樹脂組成物をジメチルホルムアミド
、２−メチルピロリドン等の極性溶媒に溶解したあと、
さらに、必要に応じて、前記増感剤、光重合開始剤およ
び感光性モノマーのうちの少なくとも１つをも配合し、
それを基板上に、スピンナー等を用いて均一に塗布する
。That is, after dissolving the photosensitive heat-resistant resin composition of the present invention containing the polyimide resin skeleton of the above formula (A) in a polar solvent such as dimethylformamide or 2-methylpyrrolidone,
Furthermore, if necessary, at least one of the sensitizer, photopolymerization initiator and photosensitive monomer is also blended,
It is uniformly applied onto the substrate using a spinner or the like.
溶液の濃度は、この発明では特に限定されないが、１〜
３０重量％（以下、「％」と記す）であることが好まし
い。なぜなら、溶液の濃度が１％未満では、濃度が低す
ぎて充分な膜厚を持った塗膜を形成することができず膜
としての機能が期待できない恐れがあり、逆に、３０％
を超えると、溶媒への溶解性が悪化する恐れがあるから
であるつぎに、基板を加熱、乾燥して、塗布された溶液
から溶媒を除去したあと、その上にフォトマスクを置い
て紫外線等の化学線を照射、露光する。The concentration of the solution is not particularly limited in this invention, but is 1 to 1.
It is preferably 30% by weight (hereinafter referred to as "%"). This is because if the concentration of the solution is less than 1%, the concentration is too low and it may not be possible to form a coating film with sufficient thickness and the function as a film cannot be expected.
This is because if the temperature exceeds 100%, the solubility in the solvent may deteriorate.Next, after heating and drying the substrate to remove the solvent from the applied solution, a photomask is placed on top of it and exposed to ultraviolet rays, etc. irradiate and expose to actinic radiation.
そして、溶媒等で現像すれば、レリーフパターンが得ら
れる。Then, by developing with a solvent or the like, a relief pattern is obtained.
なお、ここで、溶媒除去のための加熱温度が１００℃を
超えると、マレイミド基が分解されて耐熱性が悪くなる
恐れがある。したがって、溶媒除去のための加熱は１０
０℃以下で行うことが好ましい。Note that if the heating temperature for removing the solvent exceeds 100° C., the maleimide group may be decomposed and the heat resistance may deteriorate. Therefore, the heating for solvent removal is 10
Preferably, the temperature is 0°C or lower.
また、現像に、ポリマーの良溶媒である前記極性溶媒と
、アルコール等の貧溶媒とを混合したものを用いれば、
良い結果が得られる。In addition, if a mixture of the polar solvent, which is a good solvent for the polymer, and a poor solvent such as alcohol is used for development,
Good results can be obtained.
以上のようにして得られたレリーフパターンは、そのま
までも充分に耐熱性に富んだものであるが、耐熱性をさ
らに高めるため、現像後２００〜３００℃程度の温度で
熱処理してやることもできる。The relief pattern obtained as described above has sufficient heat resistance as it is, but in order to further increase the heat resistance, it can be heat-treated at a temperature of about 200 to 300° C. after development.
以上のような、この発明の感光性耐熱樹脂組成物は、現
像後、高温でベータする必要がないため膜減りの発生す
る恐れがなく、シがも、ポリイミド樹脂を骨格とするも
のであるため、耐熱性に優れたパターンを形成すること
ができるようになるつぎに、この発明の実施例について
説明する。As described above, the photosensitive heat-resistant resin composition of the present invention does not need to be betatized at a high temperature after development, so there is no risk of film thinning, and since it has a polyimide resin skeleton, Next, embodiments of the present invention will be described.
（実施例１）
Ｒ，をその骨格中に含むジアミンである３、３′−ジア
ミノジフェニルスルホン（ＤＤＳ）１６．８ｇをジメチ
ルホルムアミド５９ｇとともに、２００ｍ７三つロフラ
スコに入れ、かく拌して溶解させた。この溶液に、Ｒ２
をその骨格中に含む二数無水物であるベンゾフェノンテ
トラカルボン酸二無水物（ＢＴＤＡ）１５．１ ｇと無
水マレイン酸（ＭＡ）５．５ｇとを、溶液の温度が３０
℃以上に上昇しないよう気をつけながら、交互に少しず
つ加えていき、約２時間で、上記ＢＴＤＡとＭＡの全量
を溶液に添加した。添加後、この溶液を室温で２４時間
かく拌して反応させ反応液を得た。得られた反応液を、
酢酸ナトリウムＬｏｇを溶かした無水酢酸１００ａＺ中
に投入し、室温で約１時間かく拌して、上記反応液中の
反応物を閉環させたあと、この溶液をＩＩ！の精製水中
に投入して沈澱を発生させ、それを減圧ろ過し、水洗を
５回行って、ポリイミド樹脂２８ｇを得た。(Example 1) 16.8 g of 3,3'-diaminodiphenylsulfone (DDS), which is a diamine containing R in its skeleton, was placed in a 200 m7 three-bottle flask together with 59 g of dimethylformamide, and dissolved by stirring. . In this solution, R2
15.1 g of benzophenone tetracarboxylic dianhydride (BTDA), which is a dianhydride containing in its skeleton, and 5.5 g of maleic anhydride (MA) were added at a temperature of 30
While being careful not to raise the temperature above .degree. C., they were added little by little alternately, and the entire amount of BTDA and MA was added to the solution in about 2 hours. After the addition, the solution was stirred at room temperature for 24 hours to react, and a reaction solution was obtained. The obtained reaction solution was
After pouring sodium acetate Log into 100aZ of acetic anhydride and stirring at room temperature for about 1 hour to ring-close the reactants in the reaction solution, this solution was mixed with II! The mixture was poured into purified water to generate a precipitate, which was filtered under reduced pressure and washed with water five times to obtain 28 g of polyimide resin.
得られたポリイミド樹脂の構造をＩＲならびにＮＭＲを
用いて測定したところ、一般式（Ａ）であられされた、
閉環したものであることがわかった。When the structure of the obtained polyimide resin was measured using IR and NMR, it was found to have the general formula (A),
It was found that the ring was closed.
このポリイミド樹脂１．５ｇを溶媒であるＮ−メチル−
２ピロリドン８．５ｇに溶解し、０．０７５ｇのミヒラ
ーケトンを増感剤として添加してポリマー溶液を作成し
、それを、５ ｃｍ Ｘ ５ ｃｒａのアルミナ基板に
スピンナーを用いて塗布したあと、８０℃、３０分間の
乾燥を行って、厚み約５１ｒｍの塗膜を形成した。1.5 g of this polyimide resin was mixed with N-methyl-
A polymer solution was prepared by dissolving 2-pyrrolidone in 8.5 g and adding 0.075 g of Michler's ketone as a sensitizer. After coating it on a 5 cm x 5 cra alumina substrate using a spinner, it was heated at 80°C. After drying for 30 minutes, a coating film with a thickness of about 51 rm was formed.
塗膜が形成されたアルミナ基板表面に、所定のパターン
が描かれたフォトマスクを密着させ、１５ｃｍの距離か
ら５００Ｗ超高圧水銀灯（ウシオ電気０菊製、ＵＳＨ−
５０００）によって紫外線を１０分間照射した。そのあ
と、この基板を、ジメチルホルムアミド５重量部（以下
「部」と記す）とイソプロピルアルコール４部との混合
液で現像シ、２５０℃、６０分間の熱処理を行うことに
より、レリーフパターンを得た。A photomask with a predetermined pattern drawn on it was brought into close contact with the surface of the alumina substrate on which the coating film was formed, and a 500W ultra-high pressure mercury lamp (manufactured by Ushio Electric Kiku, USH-
5000) for 10 minutes. Thereafter, this substrate was developed with a mixture of 5 parts by weight of dimethylformamide (hereinafter referred to as "parts") and 4 parts of isopropyl alcohol, and heat treated at 250°C for 60 minutes to obtain a relief pattern. .
得られたレリーフパターンは、高温によるベータをして
いないため膜減りがなく、しかも、耐熱性に優れたもの
であった。The obtained relief pattern had no film loss because it was not exposed to beta due to high temperatures, and had excellent heat resistance.
（実施例２）
上記実施例１で得られたポリイミド樹脂１ｇを、を８媒
であるＮ−メチル−２ピロリドン８．５ｇに溶解し、０
．０７５ ｇのベンゾインジメチルエーテルを増感剤と
して添加してポリマー溶液を作成した以外は、実施例１
と同様にしてレリーフパターンを得た。(Example 2) 1 g of the polyimide resin obtained in Example 1 above was dissolved in 8.5 g of N-methyl-2-pyrrolidone, which was an 8-solvent.
．． Example 1 except that 0.75 g of benzoin dimethyl ether was added as a sensitizer to make the polymer solution.
A relief pattern was obtained in the same manner.
得られたレリーフパターンは、上記実施例１と同様、高
温によるベータをしていないため膜減りがなく、しかも
、耐熱性に優れたものであった。As in Example 1, the obtained relief pattern did not suffer from beta damage due to high temperatures, so there was no film loss, and it had excellent heat resistance.
（実施例３）
Ｒ１をその骨格中に含むジアミンとして、３゜３′−ジ
アミノジフェニルスルホンのかわりに、３．３′−ジア
ミノジフヱニルメタン（Ｄ Ｄ Ｍ） １４゜９ｇを
使用した以外は、実施例１と同様にしてレリーフパター
ンを得た。(Example 3) As the diamine containing R1 in its skeleton, 14.9 g of 3.3'-diaminodiphenylmethane (D D M) was used instead of 3.3'-diaminodiphenylsulfone. A relief pattern was obtained in the same manner as in Example 1.
得られたレリーフパターンは、上記実施例１と同様、高
温によるベータをしていないため膜減りがなく、しかも
、耐熱性に優れたものであった。As in Example 1, the obtained relief pattern did not suffer from beta damage due to high temperatures, so there was no film loss, and it had excellent heat resistance.
（実施例４）
上記実施例１で得られたポリイミド樹脂２ｇを、溶媒で
あるジメチルホルムアミド６．０ｇに溶解したことと、
厚み１．０−の塗膜を形成したこと以外は、実施例１と
同様にしてレリーフパターンを得た。(Example 4) 2 g of the polyimide resin obtained in Example 1 above was dissolved in 6.0 g of dimethylformamide as a solvent,
A relief pattern was obtained in the same manner as in Example 1, except that a coating film having a thickness of 1.0- was formed.
得られたレリーフパターンは、上記実施例１と同様、高
温によるベータをしていないため膜減りがなく、しかも
、耐熱性に優れたものであった。As in Example 1, the obtained relief pattern did not suffer from beta damage due to high temperatures, so there was no film loss, and it had excellent heat resistance.
（実施例５）
上記実施例１で得られたポリイミド樹脂１．５ｇを、ジ
アミノジフェニルメタンビスマレイミド０゜２ｇと混合
してから８．５ｇのＮ−メチル−２ピロリドンに溶解し
た以外は、実施例１と同様にしてレリーフパターンを得
た。(Example 5) Example 5 except that 1.5 g of the polyimide resin obtained in Example 1 above was mixed with 0.2 g of diaminodiphenylmethane bismaleimide and then dissolved in 8.5 g of N-methyl-2-pyrrolidone. A relief pattern was obtained in the same manner as in 1.
得られたレリーフパターンは、上記実施例１と同様、高
温によるベークをしていないため膜減りがなく、しかも
、耐熱性に優れたものであった。As in Example 1, the obtained relief pattern had no film loss because it was not baked at high temperatures, and had excellent heat resistance.
この発明の感光性耐熱樹脂組成物は、以上のように構成
されており、前記一般式（Ａ）で表されたポリイミド樹
脂骨格を成分中に含んでいるため、パターン形成後の高
温によるベークが不要で、しかも、耐熱性に優れたパタ
ーンを得ることができるようになる。The photosensitive heat-resistant resin composition of the present invention has the above-mentioned structure, and since it contains the polyimide resin skeleton represented by the general formula (A) in its components, it can be baked at high temperatures after pattern formation. It becomes possible to obtain a pattern that is unnecessary and has excellent heat resistance.
代理人 弁理士 松 本 武 彦
用巨糸六ネ甫正書く自発
昭和６１年１２月 ５日
昭和６１年特ＨＭＩＩ、１９１８９０号３．１鉦をする
者
事件との酪系 特許出願人
件 所 大阪府門真市大字門真１０４８番地
名 称 （５８３）松下電工株式会社
代表者 イ懐嘘役 藤 井 貞 夫
４、代理人
６゜補正の対象
明細書
７、補正の内容
■ 明細書の特許請求の範囲量の全文を下記のとおりに
訂正する。Agent: Takehiko Matsumoto, Patent Attorney: Written by Rokune Hosho Kyoto, December 5, 1985, Special HMII, No. 191890, 3.1 Case related to person who makes a gong Patent applicant: Osaka Prefecture 1048 Oaza Kadoma, Kadoma City Name (583) Matsushita Electric Works Co., Ltd. Representative Ikai Uso Sadao Fujii 4, Agent 6゜Specification subject to amendment 7, Contents of amendment■ Amount of claims in the specification The entire text is corrected as follows.
一記一
「（１） 以下の一般式（Ａ）で表されたポリイミド
樹脂骨格を成分中に含んでいることを特徴とする感光性
耐熱樹脂組成物。1. (1) A photosensitive heat-resistant resin composition characterized by containing a polyimide resin skeleton represented by the following general formula (A) in its components.
・・・（Ａ）
ただし、上記式中Ｒ５は、以下の一般式から選ばれる少
なくとも１つの二価の基をあられし、式中Ｒ２は、以下
の一般式から選ばれる少なくとも１つの四価の基をあら
れし、
式中Ｒ，，Ｒ４，Ｒ，，Ｒ，は、それぞれ、水素、芳香
族基およびアルキル基の中から選ばれた少なくとも１つ
の一価の基をあられし、ｎは１以上の整数をあられして
いる。...(A) However, in the above formula, R5 represents at least one divalent group selected from the following general formula, and R2 represents at least one tetravalent group selected from the following general formula. In the formula, R,,R4,R,,R, each represent at least one monovalent group selected from hydrogen, an aromatic group, and an alkyl group, and n is 1 or more. It is raining integers.
（２）必要に応じて、増感剤および光重合開始剤少うち
の少なくともｆが配合されている特許請求の範囲第１項
記載の感光性耐熱樹脂組成物。」■ 明細書第１０頁第
５行ないし同頁第６行に［増感剤、光重合開始剤および
感光性モヅマーのうちの少なくとも１つが」とあるを、
「増感剤および光重合開始剤のうちの少なくとも一方が
」と訂正する。(2) The photosensitive heat-resistant resin composition according to claim 1, which contains at least f of a sensitizer and a photopolymerization initiator, if necessary. ” ■ On page 10 of the specification, line 5 to line 6 of the same page, it says “at least one of a sensitizer, a photopolymerization initiator, and a photosensitive modulum”,
The sentence is corrected to "at least one of a sensitizer and a photopolymerization initiator."
■ 明細書第１０頁第８行および同頁第１１行に、それ
ぞれ、「および感光性モノマー」とあるを削除する。■ The words "and photosensitive monomer" are deleted from line 8 and line 11 of page 10 of the specification, respectively.
Claims (2)
格を成分中に含んでいることを特徴とする感光性耐熱樹
脂組成物。 ▲数式、化学式、表等があります▼・・・（Ａ） ただし、上記式中Ｒ＿１は、以下の一般式から選ばれる
少なくとも１つの二価の基をあらわし、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼ ▲数式、化学式、表等があります▼および ▲数式、化学式、表等があります▼ 式中Ｒ＿２は、以下の一般式から選ばれる少なくとも１
つの四価の基をあらわし、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ 式中Ｒ＿３、Ｒ＿４、Ｒ＿５、Ｒ＿６は、それぞれ、水
素、芳香族基およびアルキル基の中から選ばれた少なく
とも１つの一価の基をあらわし、ｎは１以上の整数をあ
らわしている。(1) A photosensitive heat-resistant resin composition characterized by containing a polyimide resin skeleton represented by the following general formula (A) in its components. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(A) However, in the above formula, R_1 represents at least one divalent group selected from the following general formulas, and ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_2 is at least one selected from the following general formulas.
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc.▼ In the formula, R_3, R_4, R_5, and R_6 each represent at least one monovalent group selected from hydrogen, an aromatic group, and an alkyl group, and n represents an integer of 1 or more. ing.
性モノマーのうちの少なくとも１つが配合されている特
許請求の範囲第１項記載の感光性耐熱樹脂組成物。(2) The photosensitive heat-resistant resin composition according to claim 1, which contains at least one of a sensitizer, a photopolymerization initiator, and a photosensitive monomer, if necessary.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19189086A JPS6348310A (en) | 1986-08-15 | 1986-08-15 | Photosensitive heat-resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19189086A JPS6348310A (en) | 1986-08-15 | 1986-08-15 | Photosensitive heat-resistant resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6348310A true JPS6348310A (en) | 1988-03-01 |
Family
ID=16282152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19189086A Pending JPS6348310A (en) | 1986-08-15 | 1986-08-15 | Photosensitive heat-resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6348310A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010053181A1 (en) | 2008-11-07 | 2010-05-14 | 日立化成工業株式会社 | Blood serum or blood plasma separation method |
-
1986
- 1986-08-15 JP JP19189086A patent/JPS6348310A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010053181A1 (en) | 2008-11-07 | 2010-05-14 | 日立化成工業株式会社 | Blood serum or blood plasma separation method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3321548B2 (en) | Photosensitive polyimide precursor composition and pattern forming method using the same | |
| CA1258946A (en) | Polyimides, a process for their preparation and their use | |
| JPH03763A (en) | Positive type photosensitive polyimide composition | |
| JPH0539281A (en) | Di-substituted aromatic dianhydride and polyimide prepared therefrom | |
| JPS63318549A (en) | Heatresistant photosensitive polymer composition | |
| JPS6042425A (en) | Actinic ray-sensitive polymer composition | |
| JPS6348310A (en) | Photosensitive heat-resistant resin composition | |
| JPS59160140A (en) | Polymer composition sensitive to chemical ray | |
| US5851736A (en) | Heat-resistant photoresist composition, photosensitive substrate, and process for forming heat-resistant positive or negative pattern | |
| JP3093055B2 (en) | Heat resistant negative photoresist composition, photosensitive substrate, and negative pattern forming method | |
| JPS62179563A (en) | Photosensitive polymer composition | |
| JPS6348318A (en) | Photosensitive heat-resistant resin composition | |
| JPS5915449A (en) | Photosensitive resin composition | |
| JP2895571B2 (en) | Heat-resistant photosensitive composition | |
| JPH05134406A (en) | Production of semiconductor device | |
| JPH01283554A (en) | Thermoresisting photosensitive polymer composition | |
| JP2693670B2 (en) | Photosensitive resin composition | |
| JPH02154262A (en) | Photosensitive resin composition and photosensitive element using this photosensitive resin composition | |
| JPS6347142A (en) | Cover containing radiation-sensitive polyimide layer having specific diaminodiphenyl methane unit | |
| JPS5813630A (en) | Photo-setting resin composition | |
| JPH01118514A (en) | Photosensitive polymer composition | |
| JPH0337652A (en) | Actinic ray sensitive polymer composition | |
| JPH02305820A (en) | Photosensitive polyimide | |
| JPH0296167A (en) | Photosensitive heat resistant resin composition | |
| JPS63226639A (en) | Photosensitive resin composition |