JPH0259975B2 - - Google Patents
Info
- Publication number
- JPH0259975B2 JPH0259975B2 JP7072683A JP7072683A JPH0259975B2 JP H0259975 B2 JPH0259975 B2 JP H0259975B2 JP 7072683 A JP7072683 A JP 7072683A JP 7072683 A JP7072683 A JP 7072683A JP H0259975 B2 JPH0259975 B2 JP H0259975B2
- Authority
- JP
- Japan
- Prior art keywords
- methoxyacetophenone
- azidobenzal
- photosensitive composition
- aqueous solution
- photosensitive
- 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
Links
- 239000000203 mixture Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 17
- OPWOGDUGZVCUJS-UHFFFAOYSA-N N(=[N+]=[N-])C1=CC=C(C=C1)C(C(OC)=CC1=CC=CC=C1)=O Chemical compound N(=[N+]=[N-])C1=CC=C(C=C1)C(C(OC)=CC1=CC=CC=C1)=O OPWOGDUGZVCUJS-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- -1 azide compounds Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- YRNDGUSDBCARGC-UHFFFAOYSA-N 2-methoxyacetophenone Chemical compound COCC(=O)C1=CC=CC=C1 YRNDGUSDBCARGC-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SDJOUGYEUFYPLL-UHFFFAOYSA-N 4-azidobenzaldehyde Chemical compound [N-]=[N+]=NC1=CC=C(C=O)C=C1 SDJOUGYEUFYPLL-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- G03F7/008—Azides
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、写真工業、印刷工業、電子工業等に
用いられる感光性組成物に関し、さらに詳しく述
べるならば、本発明は、溶剤に対する溶解性を改
良した感光性化合物とそれによつて光化学的に硬
化あるいは希アルカリ水溶液に不溶化し得るアル
カリ可溶性高分子を含有し、特に経日の粘度変化
が改良された感光性組成物に関する。
アジド化合物を感光性化合物として使用するこ
とは公知であり、しかもフイルム形成用ポリマー
にアルカリ可溶性高分子を用いることも公知であ
る。これらは特公昭45―22082号公報、特公昭44
―26048号公報、特公昭53―34902号公報、特公昭
49―4481号公報等に開示されている。
写真工業、印刷工業、電子工業等の種々の用途
において感光性組成物を適用する場合、そこに使
用するアジド化合物の溶剤への溶解性は大きいこ
とが望まれる。
上記のアジド類化合物についても、溶剤への溶
解性を高める種々の方法がとり入れられている。
たとえば特公昭53―34902号公報においては、モ
ノアジド化合物を使用することにより、溶剤への
溶解性を高めている。
一方、電子工業などの精密分野においては、感
光性組成物の品質に対する要望がきびしく粘度な
どの経日変化はしばしば半導体の製造工程等にお
いてトラブルを起こすもととなる。
本発明は溶解性の改善された新規な4′―アジド
ベンザル―２―メトキシアセトフエノンを用いる
ことにより、経日の粘度変化が改良され、光硬化
性の速い感光性組成物を提供することを目的とす
るものである。
本発明は、
The present invention relates to a photosensitive composition used in the photographic industry, the printing industry, the electronic industry, etc. More specifically, the present invention relates to a photosensitive compound having improved solubility in a solvent and photochemically curing using the same. Alternatively, the present invention relates to a photosensitive composition that contains an alkali-soluble polymer that can be insolubilized in a dilute aqueous alkali solution, and in particular has improved viscosity change over time. It is known to use azide compounds as photosensitive compounds, and it is also known to use alkali-soluble polymers as film-forming polymers. These are Special Publication No. 1972-22082 and Special Publication No. 22082, Special Publication No. 44
-26048 Publication, Special Publication No. 53-34902, Special Publication Sho
It is disclosed in Publication No. 49-4481, etc. When a photosensitive composition is used in various applications such as the photographic industry, the printing industry, and the electronic industry, it is desired that the azide compound used therein has high solubility in a solvent. Various methods have also been adopted for the above azide compounds to increase their solubility in solvents.
For example, in Japanese Patent Publication No. 53-34902, the solubility in solvents is increased by using a monoazide compound. On the other hand, in precision fields such as the electronics industry, there are strict demands on the quality of photosensitive compositions, and changes in viscosity and the like over time often cause problems in semiconductor manufacturing processes and the like. The present invention aims to provide a photosensitive composition with improved viscosity change over time and rapid photocurability by using a novel 4'-azidobenzal-2-methoxyacetophenone with improved solubility. This is the purpose. The present invention
【式】で表わ
される4′―アジドベンザル―２―メトキシアセト
フエノン及びこの化合物により光化学的に硬化
し、アルカリ水溶液に不溶化し得るアルカリ水溶
液可溶性高分子を含有してなる感光性組成物に関
する。
4′―アジドベンザル―４―メトキシアセトフエ
ノンとアルカリ可溶性高分子が感光性組成物とし
て有用であることは特公昭53―34902号公報に開
示されているが、4′―アジドベンザル―４―メト
キシアセトフエノンは、分子の構造が直線的なた
めと思われるが、３の位置あるいは２の位置にメ
トキシ基が置換した化合物に比べて溶剤への溶解
性が小さい。
本発明は使用するメトキシ基の置換基の位置
を、従来の置換基の位置と変えることにより、溶
剤への溶解性の改良された感光性アジド化合物を
用いるものである。
4′―アジドベンザル―２―メトキシアセトフエ
ノンは、例えばｐ―アジドベンズアルデヒドと２
―メトキシアセトフエノンとをアルカリ性化合物
を触媒として反応させて合成できる。
本発明に使用する上記のアルカリ水溶液可溶性
高分子は、水酸基あるいはカルボキシル基を有す
る化合物である。これらの例として、ノボラツク
樹脂、ポリヒドロキシスチレン樹脂、アクリル残
酸またはメタアクリル酸の重合体などがあげられ
る。
これらは、ホモ縮合体もしくは共縮合体、ホモ
重合体もしくは共重合体の形で用いることが可能
である。また、これらは単独であるいは二種以上
の混合物の形で用いられる。
これらの樹脂は市販品としても求めることがで
きる。例えばノボラツク樹脂としては、フエノー
ルノボラツク樹脂、クレゾールノボラツク樹脂、
フエノール・クレゾールノボラツク樹脂などがあ
る。またポリヒドロキシスチレン樹脂としては、
ポリパラビニルフエノール、ポリパラビニルフエ
ノールの臭素化物などがある。アクリル酸または
メタアクリル酸の重合体としては、アクリル酸ま
たはメタアクリル酸ポリマー，アクリル酸または
メタアクリル酸とアクリル酸エステルまたはメタ
クリル酸エステルとの共重合体、アクリル酸また
はメタアクリル酸とスチレンとの共重合体などが
ある。
用いるアルカリ水溶液可溶性高分子としては、
脱溶剤後成膜できることが必要であり、そのため
には数平均分子量は500以上が好ましく、さらに
感光性組成物としての耐熱性を考慮すると、数平
均分子量は1000以上が好ましい。
本発明におけるアルカリ水溶液可溶性高分子
は、光化学的に硬化し、アルカリ水溶液に不溶化
とされる。光化学的な硬化は水銀灯などを用いて
公知の手段で行なわれる。 この硬化によつてア
ルカリ水溶液可溶性高分子はアルカリ水溶液に不
溶性となり、アルカリ水溶液によつて現像可能と
なる。
アルカリ水溶液としては、例えば水酸化ナトリ
ウム、水酸化カリウム、テトラメチルアンモニウ
ム等の例えば５重量％以下の水溶液が用いられ
る。
本発明の感光性組成物はさらに溶剤を含んでも
よい。本発明の感光性組成物は溶剤に溶解した状
態でシリコン、アルミ等の基板表面に塗布され
る。使用できる溶剤としては、アセトン、メチル
エチルケトン、メチルイソブチルケトン、シクロ
ヘキサノン等のケトン系溶剤、メチルセロソル
ブ、メチルセロソルブアセテート、エチルセロソ
ルブアセテート等のセロソルブ系溶剤、酢酸エチ
ル、酢酸ブチル、酢酸イソアミル等のエステル系
溶剤などがある。各溶剤を単独で用いても２種以
上の混合溶剤として用いてもよい。
上記の4′―アジドベンザル―２―メトキシアセ
トフエノンとアルカリ可溶性高分子との混合割合
は、4′―アジドベンザル―２―メトキシアセトフ
エノンがアルカリ可溶性高分子に対し５〜100重
量％の範囲とすることが好ましく、10〜50重量％
の範囲とすることがさらに好ましい。
公知である化合物、たとえば4′―アジドベンザ
ル―３―メトキシアセトフエノンや4′―アジドベ
ンザル―４―メトキシアセトフエノンと前記のア
ルカリ可溶性高分子を含有してなる感光性組成物
は、20℃に溶液の状態で放置しておくと、約３か
月経過すると徐々に増粘が見られ、６か月以上放
置すると、10％以上の増粘が見られる。粘度変化
に対する具体的な許容幅は明確でないが、少なけ
れば少ないほどよい。
本発明になる感光組成物は、上記の感光性化合
物を用い、アルカリ可溶性高分子を含有してなる
感光性組成物に比べて、経日での粘度変化が小さ
いものである。
本発明になる感光性組成物は、その目的に応じ
て、更に副次的な成分を含有してもさしつかえな
い。これらの例としては、貯蔵安定性をはかるた
めの熱重合防止剤、基板からのハレーシヨンを防
止するためのハレーシヨン防止剤、基板との密着
性を向上させるための密着性向上剤などがあげら
れる。
以下、実施例により本発明を説明する。
実施例 １
(1) 4′―アジドベンザル―２―メトキシアセトフ
エノンの合成
500mlのフラスコに、２―メトキシアセトフ
エノン（アルドリツチ製：純度99％）15g、ｐ
―アジドベンズアルデヒド（関東化学製）
15g、10％水酸化ナトリウム50gおよびメタノ
ール50gを入れて、黄色光下で25℃の温度で24
時間かくはんした。反応終了後、析出した結晶
をろ過により採取した。次に水で洗浄を行ない
乾燥し、エタノールから再結晶した。
２―メトキシアセトフエノンの純度は99％で
あり他の位置に置換した材料はほとんど含まれ
ない。
また、アルカリ性水溶液下における合成にお
いて２―メトキシアセトフエノンのメトキシ基
の位置は、変化しないといえる。
4′―アジドベンザル―２―メトキシアセトフ
エノンを以下に示す分析により確認した。
(A) 質量分析（200°C−50eV）ｍ／ｅ＝279第１
図にスペクトルを示す。
(B) IRスペクトル
第２図にスペクトル（KBr法）を示す。2100
cm-1にアジド基（―N3）の強い吸収が認めら
れた。
(C) NMRスペクトル（1H―NMR）
第３図にスペクトルを示す。合わせてメトキシ
の位置が３のスペクトル（第４図）と４のスペ
クトル（第５図）も示す。
第３図から、―OCH3とThe present invention relates to a photosensitive composition containing 4'-azidobenzal-2-methoxyacetophenone represented by the formula: and an alkaline aqueous solution-soluble polymer that can be photochemically cured by this compound and insolubilized in an alkaline aqueous solution. It is disclosed in Japanese Patent Publication No. 34902/1983 that 4'-azidobenzal-4-methoxyacetophenone and an alkali-soluble polymer are useful as photosensitive compositions, but 4'-azidobenzal-4-methoxyacetophenone is useful as a photosensitive composition. Phenone has a lower solubility in solvents than compounds in which a methoxy group is substituted at the 3-position or the 2-position, probably because the molecular structure is linear. The present invention uses a photosensitive azide compound whose solubility in a solvent is improved by changing the position of the substituent of the methoxy group from the conventional position of the substituent. 4'-azidobenzal-2-methoxyacetophenone is, for example, p-azidobenzaldehyde and 2
- Can be synthesized by reacting methoxyacetophenone with an alkaline compound as a catalyst. The alkali aqueous solution-soluble polymer used in the present invention is a compound having a hydroxyl group or a carboxyl group. Examples of these include novolac resins, polyhydroxystyrene resins, and polymers of acrylic residual acid or methacrylic acid. These can be used in the form of homocondensates or cocondensates, homopolymers or copolymers. Further, these may be used alone or in the form of a mixture of two or more. These resins can also be obtained as commercial products. For example, novolak resins include phenol novolak resin, cresol novolak resin,
Examples include phenolic cresol novolak resin. In addition, as polyhydroxystyrene resin,
Examples include polyparavinylphenol and brominated polyparavinylphenol. Examples of polymers of acrylic acid or methacrylic acid include acrylic acid or methacrylic acid polymers, copolymers of acrylic acid or methacrylic acid and acrylic esters or methacrylic esters, and copolymers of acrylic acid or methacrylic acid and styrene. There are copolymers, etc. The alkaline aqueous solution-soluble polymer used is
It is necessary to be able to form a film after removing the solvent, and for this purpose the number average molecular weight is preferably 500 or more, and furthermore, in consideration of the heat resistance as a photosensitive composition, the number average molecular weight is preferably 1000 or more. The alkaline aqueous solution-soluble polymer in the present invention is photochemically cured and rendered insoluble in the alkaline aqueous solution. Photochemical curing is performed by known means using a mercury lamp or the like. By this curing, the alkaline aqueous solution-soluble polymer becomes insoluble in the alkaline aqueous solution and becomes developable with the alkaline aqueous solution. As the alkaline aqueous solution, for example, an aqueous solution of 5% by weight or less of sodium hydroxide, potassium hydroxide, tetramethylammonium, etc. is used. The photosensitive composition of the present invention may further contain a solvent. The photosensitive composition of the present invention is applied to the surface of a substrate such as silicon or aluminum in a state dissolved in a solvent. Usable solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, cellosolve solvents such as methyl cellosolve, methyl cellosolve acetate, and ethyl cellosolve acetate, and ester solvents such as ethyl acetate, butyl acetate, and isoamyl acetate. and so on. Each solvent may be used alone or as a mixed solvent of two or more. The mixing ratio of the above 4'-azidobenzal-2-methoxyacetophenone and the alkali-soluble polymer is in the range of 5 to 100% by weight of 4'-azidobenzal-2-methoxyacetophenone to the alkali-soluble polymer. Preferably, 10-50% by weight
It is more preferable to set it as the range of. A photosensitive composition containing a known compound such as 4'-azidobenzal-3-methoxyacetophenone or 4'-azidobenzal-4-methoxyacetophenone and the alkali-soluble polymer described above is heated to 20°C. If left as a solution, it will gradually increase in viscosity after about 3 months, and if left in solution for more than 6 months, it will increase in viscosity by more than 10%. Although the specific allowable range for viscosity change is not clear, the smaller the better. The photosensitive composition of the present invention uses the above-mentioned photosensitive compound and has a smaller change in viscosity over time than a photosensitive composition containing an alkali-soluble polymer. The photosensitive composition of the present invention may further contain secondary components depending on its purpose. Examples of these include thermal polymerization inhibitors to measure storage stability, antihalation agents to prevent halation from the substrate, and adhesion improvers to improve adhesion to the substrate. The present invention will be explained below with reference to Examples. Example 1 (1) Synthesis of 4'-azidobenzal-2-methoxyacetophenone In a 500 ml flask, 15 g of 2-methoxyacetophenone (manufactured by Aldrich, purity 99%), p.
-Azidebenzaldehyde (manufactured by Kanto Kagaku)
15g, 50g of 10% sodium hydroxide and 50g of methanol and heated at a temperature of 25℃ under yellow light for 24 hours.
I stirred for hours. After the reaction was completed, the precipitated crystals were collected by filtration. Next, it was washed with water, dried, and recrystallized from ethanol. The purity of 2-methoxyacetophenone is 99%, and it contains almost no materials substituted at other positions. Furthermore, it can be said that the position of the methoxy group in 2-methoxyacetophenone does not change during synthesis under an alkaline aqueous solution. 4'-azidobenzal-2-methoxyacetophenone was confirmed by the analysis shown below. (A) Mass spectrometry (200°C-50eV) m/e=279 1st
The spectrum is shown in the figure. (B) IR spectrum Figure 2 shows the spectrum (KBr method). 2100
Strong absorption of azide group (-N 3 ) was observed at cm -1 . (C) NMR spectrum ( 1 H-NMR) The spectrum is shown in Figure 3. Also shown are spectra with methoxy at position 3 (Fig. 4) and 4 (Fig. 5). From Figure 3, -OCH 3 and
【式】が確認さ
れた。
比較例である第４図，第５図と比較して２―メ
トキシ基の存在が確認される。6.8ppmから
8.1ppmのスペクトルが、芳香核のメトキシの置
換基の位置によつて相違している。
(D) 結晶色
黄色。
(E) 紫外線吸収スペクトルの吸収極大330nm（エ
タノール溶媒）。
(F) 融点
90℃。
(2) 感光性組成物の製造
4′―アジドベンザル―２―メトキシアセトフ
エノン１重量部をポリ―ｐ―ビニルフエノール
（丸善石油製商品名レジンＭ）５重量部と共に
シクロヘキサノン25重量部に溶かし、感光性組
成物を作製した。この組成物をアルミ板上に
3000rpmで30秒間回転塗布し、乾燥して約1μm
の感光膜を形成した。
つづいてこの基板を250Wの水銀灯を用いて
10mW／cm2（365nmで測定）の強度の光で10秒
間露光した。露光層を１重量％のテトラメチル
アンモニウム水溶液に20℃の温度で５分間浸漬
したが膜は溶解しなかつた。なお未露光の場合
は、同一の現像液を使用すると１〜２分で溶解
し、本材料は感光性組成物として使用できるこ
とがわかつた。
実施例 ２
4′―アジドベンザル―２―メトキシアセトフエ
ノン１重量部とクレゾールノボラツク樹脂（群栄
化学製商品名PSF―2807）４重量部をエチルセロ
ソルブアセテート25重量部に溶かし感光性組成物
を作製した。
この組成物をシリコンウエーハ上に3000rpmで
30秒間回転塗布し、乾燥して約1μmの感光膜を形
成した。
実施例１と同一の水銀灯を用いて、クロムマス
クを介して、３秒間露光した。未露光層を２重量
％のテトラメチルアンモニウム水溶液で現像し、
未露光部の感光膜を溶解除去したところ2μm幅の
ラインと2μm幅のスペースの繰り返しパターンが
形成された。
実施例 ３
4′―アジドベンザル―２―メトキシアセトフエ
ノン１重量部にメタアクリル酸とメタアクリル酸
ブチルエステルとの共重合比がメタアクリル酸：
メタアクリル酸ブチルエステルが３：７である樹
脂４重量部をメチルセロソルブアセテート40重量
部に溶かし、感光性組成物を作製した。
この組成物をシリコーンウエーハ上に3000rpm
で30秒間回転塗布し、乾燥して約1.5μmの感光膜
を形成した。つづいて、この基板を実施例１と同
一の水銀灯を用いて、クロムマスクを介して５秒
間露光した。未露光層を２重量％のテトラメチル
アンモニウム水溶液で現像し、未露光部の感光膜
を溶解除去したところ1.5μm幅のラインと1.5μm
幅のスペースの繰り返しパターンが形成された。
4′―アジドベンザル―２―メトキシアセトフエ
ノンの溶解性を4′―アジドベンザル―４―メトキ
シアセトフエノンと比較した。[Formula] was confirmed. The presence of a 2-methoxy group is confirmed by comparison with FIGS. 4 and 5, which are comparative examples. From 6.8ppm
The spectrum at 8.1 ppm differs depending on the position of the methoxy substituent on the aromatic nucleus. (D) Crystal color: yellow. (E) Maximum absorption of ultraviolet absorption spectrum at 330 nm (ethanol solvent). (F) Melting point 90℃. (2) Production of photosensitive composition 1 part by weight of 4'-azidobenzal-2-methoxyacetophenone was dissolved in 25 parts by weight of cyclohexanone along with 5 parts by weight of poly-p-vinylphenol (trade name: Resin M manufactured by Maruzen Oil Co., Ltd.). A photosensitive composition was prepared. This composition is placed on an aluminum plate.
Spin coating at 3000 rpm for 30 seconds and dry to approximately 1 μm.
A photoresist film was formed. Next, this board was heated using a 250W mercury lamp.
Exposure was performed for 10 seconds with a light intensity of 10 mW/cm 2 (measured at 365 nm). The exposed layer was immersed in a 1% by weight aqueous tetramethylammonium solution at 20° C. for 5 minutes, but the film did not dissolve. It was found that when unexposed, the material was dissolved in 1 to 2 minutes using the same developing solution, and the present material could be used as a photosensitive composition. Example 2 A photosensitive composition was prepared by dissolving 1 part by weight of 4'-azidobenzal-2-methoxyacetophenone and 4 parts by weight of cresol novolac resin (product name PSF-2807 manufactured by Gunei Chemical Co., Ltd.) in 25 parts by weight of ethyl cellosolve acetate. Created. This composition was applied onto a silicon wafer at 3000 rpm.
It was spin-coated for 30 seconds and dried to form a photoresist film with a thickness of about 1 μm. Using the same mercury lamp as in Example 1, exposure was carried out for 3 seconds through a chrome mask. The unexposed layer was developed with a 2% by weight tetramethylammonium aqueous solution,
When the unexposed areas of the photosensitive film were dissolved and removed, a repeating pattern of 2 μm wide lines and 2 μm wide spaces was formed. Example 3 The copolymerization ratio of methacrylic acid and butyl methacrylate to 1 part by weight of 4'-azidobenzal-2-methoxyacetophenone was methacrylic acid:
A photosensitive composition was prepared by dissolving 4 parts by weight of a resin containing 3:7 butyl methacrylate in 40 parts by weight of methyl cellosolve acetate. This composition was applied onto a silicone wafer at 3000 rpm.
It was spin-coated for 30 seconds and dried to form a photoresist film with a thickness of about 1.5 μm. Subsequently, this substrate was exposed to light for 5 seconds through a chrome mask using the same mercury lamp as in Example 1. When the unexposed layer was developed with a 2% by weight tetramethylammonium aqueous solution and the photosensitive film in the unexposed area was dissolved and removed, a 1.5 μm wide line and a 1.5 μm wide line were formed.
A repeating pattern of wide spaces was formed. The solubility of 4'-azidobenzal-2-methoxyacetophenone was compared with that of 4'-azidobenzal-4-methoxyacetophenone.
【表】
溶剤に対する4′―アジドベンザル―４―メトキ
シアセトフエノンの溶解量を１として4′―アジド
ベンザル―２―メトキシアセトフエノンの溶解量
を示した。
比較例
4′―アジドベンザル―２―メトキシアセトフエ
ノンを用いた感光性組成物と、メトキシの位置が
異なる他の感光性化合物を用いた感光性組成物と
の経日の粘度変化の比較を行なつた。[Table] The amount of 4'-azidobenzal-2-methoxyacetophenone dissolved is shown, with the amount of 4'-azidobenzal-4-methoxyacetophenone dissolved in the solvent as 1. Comparative Example A comparison was made of the change in viscosity over time between a photosensitive composition using 4'-azidobenzal-2-methoxyacetophenone and a photosensitive composition using another photosensitive compound with a different methoxy position. Summer.
【表】
粘度変化の測定条件：実施例１の感光性組成物
の4′―アジドベンザル―２―メトキシアセトフエ
ノンを4′―アジドベンザル―３―メトキシアセト
フエノンまたは4′―アジドベンザル―４―メトキ
シアセトフエノンに変えて500nm以下の光をカツ
トした容器の中に保存し、40℃に１か月放置し、
20℃に１か月間放置した組成物との粘度変化を比
較した。
本発明になる溶剤に対する溶解性の改良された
感光性化合物を含有する本発明になる感光性組成
物は、光硬化性にすぐれ、経日の粘度変化が従来
の組成物の1/2であることが示される。[Table] Measurement conditions for viscosity change: 4'-azidobenzal-2-methoxyacetophenone of the photosensitive composition of Example 1 was replaced with 4'-azidobenzal-3-methoxyacetophenone or 4'-azidobenzal-4-methoxy Change it to acetophenone, store it in a container that blocks light below 500 nm, and leave it at 40℃ for one month.
The viscosity change was compared with a composition that had been left at 20°C for one month. The photosensitive composition of the present invention containing a photosensitive compound with improved solubility in a solvent has excellent photocurability, and the viscosity change over time is 1/2 that of conventional compositions. It is shown that
第１図は本発明に用いる化合物の質量分析スペ
クトルの分子イオンピーク、第２図はその赤外線
吸収スペクトル、第３図はそのNMRスペクト
ル、第４図及び第５図は類似化合物のNMRスペ
クトルである。
Figure 1 shows the molecular ion peak of the mass spectrometry spectrum of the compound used in the present invention, Figure 2 shows its infrared absorption spectrum, Figure 3 shows its NMR spectrum, and Figures 4 and 5 show NMR spectra of similar compounds. .
Claims (1)
セトフエノン及びこの化合物により光化学的に硬
化し、アルカリ水溶液に不溶化し得るアルカリ水
溶液可溶性高分子を含有してなる感光性組成物。[Scope of Claims] 1 Comprising 4'-azidobenzal-2-methoxyacetophenone represented by the formula and an alkaline aqueous solution-soluble polymer that can be photochemically cured by this compound and insolubilized in an alkaline aqueous solution. Photosensitive composition.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7072683A JPS59195640A (en) | 1983-04-21 | 1983-04-21 | Photosensitive composition |
| DE3415033A DE3415033C2 (en) | 1983-04-20 | 1984-04-19 | 4'-Azidobenzal-2-methoxyacetophenone, process for its preparation and photosensitive composition containing it |
| US06/886,353 US4698291A (en) | 1983-04-20 | 1986-07-17 | Photosensitive composition with 4-azido-2'-methoxychalcone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7072683A JPS59195640A (en) | 1983-04-21 | 1983-04-21 | Photosensitive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59195640A JPS59195640A (en) | 1984-11-06 |
| JPH0259975B2 true JPH0259975B2 (en) | 1990-12-14 |
Family
ID=13439832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7072683A Granted JPS59195640A (en) | 1983-04-20 | 1983-04-21 | Photosensitive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59195640A (en) |
-
1983
- 1983-04-21 JP JP7072683A patent/JPS59195640A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59195640A (en) | 1984-11-06 |
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