JPS6328442B2 - - Google Patents
Info
- Publication number
- JPS6328442B2 JPS6328442B2 JP14589083A JP14589083A JPS6328442B2 JP S6328442 B2 JPS6328442 B2 JP S6328442B2 JP 14589083 A JP14589083 A JP 14589083A JP 14589083 A JP14589083 A JP 14589083A JP S6328442 B2 JPS6328442 B2 JP S6328442B2
- Authority
- JP
- Japan
- Prior art keywords
- chalcone
- carboxychalcone
- photosensitive resin
- investigated
- ethanol
- 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
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical group C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- 238000010521 absorption reaction Methods 0.000 description 15
- 238000000862 absorption spectrum Methods 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- -1 polyethylene Polymers 0.000 description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000007127 saponification reaction Methods 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- GVSPXQVUXHMUMA-MDWZMJQESA-N (e)-3-(3,5-ditert-butyl-4-hydroxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GVSPXQVUXHMUMA-MDWZMJQESA-N 0.000 description 3
- BFLGEZGYYCQWRT-UHFFFAOYSA-N 4-(3-oxo-3-phenylprop-1-enyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC(=O)C1=CC=CC=C1 BFLGEZGYYCQWRT-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KJHHAPASNNVTSN-KPKJPENVSA-N 4'-Methoxychalcone Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC=CC=C1 KJHHAPASNNVTSN-KPKJPENVSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000005513 chalcones Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WOGITNXCNOTRLK-VOTSOKGWSA-N (e)-3-phenylprop-2-enoyl chloride Chemical compound ClC(=O)\C=C\C1=CC=CC=C1 WOGITNXCNOTRLK-VOTSOKGWSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- VNOJQYPHLMLHGQ-UHFFFAOYSA-N 2,4-dichloro-1,3,5-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1Cl VNOJQYPHLMLHGQ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- XXFQFMHIIWSQAL-UHFFFAOYSA-N 4-(3-phenylprop-2-enoyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(=O)C=CC1=CC=CC=C1 XXFQFMHIIWSQAL-UHFFFAOYSA-N 0.000 description 1
- LOYDPLGHYGKNBM-UHFFFAOYSA-N 4-[3-(4-chlorophenyl)-3-oxoprop-1-enyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC(=O)C1=CC=C(Cl)C=C1 LOYDPLGHYGKNBM-UHFFFAOYSA-N 0.000 description 1
- BIGSVSGNGXWVCJ-UHFFFAOYSA-N 4-[3-(4-cyanophenyl)-3-oxoprop-1-enyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC(=O)C1=CC=C(C#N)C=C1 BIGSVSGNGXWVCJ-UHFFFAOYSA-N 0.000 description 1
- YKIGMBQDQYYDAH-UHFFFAOYSA-N 4-[3-(4-nitrophenyl)-3-oxoprop-1-enyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C=CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YKIGMBQDQYYDAH-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001788 chalcone derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は感光性樹脂の製法に関するものであ
る。さらに詳しくいえば本発明は、光架橋性基と
してカルコン基またはその誘導体基を持つ感光性
樹脂の製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a photosensitive resin. More specifically, the present invention relates to a method for producing a photosensitive resin having a chalcone group or a derivative group thereof as a photocrosslinkable group.
これまで、カルコンまたはその誘導体基を有す
る感光性樹脂の合成はポリベンザルアセトフエノ
ンにアルデヒドを反応させる方法、ポリスチレン
に桂皮酸クロライドをフリーデル・クラフト反応
させる方法などが知られている。これらの方法で
は光架橋性基の高い置換率の感光性樹脂は得られ
ずこれに帰因して感度が低い。更に従来の合成法
では反応時間を長く必要とし、ゲル化を生じるな
どの問題点がある。 Hitherto, known methods for synthesizing photosensitive resins having chalcone or derivative groups thereof include a method in which polybenzalacetophenone is reacted with an aldehyde, and a method in which polystyrene is reacted with cinnamic acid chloride in a Friedel-Crafts reaction. With these methods, a photosensitive resin with a high substitution rate of photocrosslinkable groups cannot be obtained, resulting in low sensitivity. Further, conventional synthesis methods require a long reaction time and have problems such as gelation.
本発明者らは、このような従来の感光性樹脂の
製法のもつ欠点を克服すべく鋭意研究を重ねた結
果、一般式(1)で表わされるカルコンまたはその誘
導体を２，４，６−トリニトロクロルベンゼンの
存在下でアルコール性水酸基をもつ重合体または
共重合体に直接反応させることに成巧し、本発明
をなすに至つた。 The present inventors have conducted extensive research to overcome the drawbacks of conventional photosensitive resin manufacturing methods, and as a result, the chalcone represented by the general formula (1) or its derivatives has been developed to produce 2,4,6-tricone. The present invention was achieved by successfully reacting a polymer or copolymer having an alcoholic hydroxyl group directly in the presence of nitrochlorobenzene.
すなわち本発明はアルコール性水酸基をもつ重
合体または共重合体に
一般式
（式中のR1、R2、R3は前記と同じ意味を示す）
で表わされるカルコン誘導体を有効量の２，４，
６−トリニトロクロルベンゼンの存在下で反応さ
せることを特徴とする。 That is, the present invention provides a polymer or copolymer having an alcoholic hydroxyl group with the general formula (R 1 , R 2 and R 3 in the formula have the same meanings as above)
An effective amount of the chalcone derivative represented by 2, 4,
It is characterized in that the reaction is carried out in the presence of 6-trinitrochlorobenzene.
一般式
（式中のR1、R2、R3は前記と同じ意味を示す）
で表わされる基を有する感光性樹脂の製造を提供
するものである。 general formula (In the formula, R 1 , R 2 , and R 3 have the same meanings as above.) The present invention provides the production of a photosensitive resin having a group represented by the following formula.
本発明に於て用いられるアルコール性水酸基を
もつ重合体または共重合体としてはポリビニルア
ルコール、ポリヒドロキシエチルアクレート、ヒ
ドロキシエチルアクリレート−スチレン共重合
体、ヒドロキシエチルメタクリレート−メチルメ
タクリレート共重合体、ポリ−２−ヒドロキシプ
ロピルメタクリレート、ポリエチレンとポリビニ
ルアルコールの共重合体などを挙げることが出来
る。また一般式(1)で表わされるカルコン誘導体と
しては４−カルボキシカルコン、4′−カルボキシ
カルコン、4′−シアノ−４−カルボキシカルコ
ン、4′nプロピル−３−カルボキシカルコン、
4′−クロロ−２−カルボキシカルコン、4′−ニト
ロ−４−カルボキシカルコン、3′−メチル−２−
カルボキシカルコン、4′−メトキシカルコン、
3′−メトキシカルボニル−４−カルボキシカルコ
ンなどを挙げることが出来る。また本発明に使用
される有機塩基としてはピリジン、トリエチルア
ミン、４−ジメチルアミノピリジン、１，４−ジ
アザビシクロ〔2.2.2〕オクタンなどを挙げるこ
とが出来る。反応溶媒の例としてはＮ，Ｎ−ジメ
チルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミ
ド、ジメチルスルホキシド、ヘキサメチルホスホ
リツクトリアミドなどを挙げることができる。反
応温度は20℃から100℃の範囲が望ましいがこれ
に限定されるものではない。この際のカルコン誘
導体と２，４，６−トリニトロクロルクロルベン
ゼンのモル比は１：１から１：1.5の範囲で選ば
れる。しかしこれに限定されるものではない。ま
た必要に応じて使用される有機塩基とカルコン誘
導体のモル比は２：１から５：１の範囲が望まし
いがそれ以外であつてもよい。反応生成物は反応
混合液を水に注加することにより得られる。 Polymers or copolymers with alcoholic hydroxyl groups used in the present invention include polyvinyl alcohol, polyhydroxyethyl acrylate, hydroxyethyl acrylate-styrene copolymer, hydroxyethyl methacrylate-methyl methacrylate copolymer, poly- Examples include 2-hydroxypropyl methacrylate and a copolymer of polyethylene and polyvinyl alcohol. In addition, as chalcone derivatives represented by general formula (1), 4-carboxychalcone, 4'-carboxychalcone, 4'-cyano-4-carboxychalcone, 4'n propyl-3-carboxychalcone,
4'-chloro-2-carboxychalcone, 4'-nitro-4-carboxychalcone, 3'-methyl-2-
Carboxychalcone, 4′-methoxychalcone,
Examples include 3'-methoxycarbonyl-4-carboxychalcone. Examples of the organic base used in the present invention include pyridine, triethylamine, 4-dimethylaminopyridine, and 1,4-diazabicyclo[2.2.2]octane. Examples of the reaction solvent include N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, and the like. The reaction temperature is preferably in the range of 20°C to 100°C, but is not limited thereto. The molar ratio of the chalcone derivative and 2,4,6-trinitrochlorochlorobenzene is selected in the range of 1:1 to 1:1.5. However, it is not limited to this. Further, the molar ratio of the organic base and the chalcone derivative used as necessary is preferably in the range of 2:1 to 5:1, but may be other than that. The reaction product is obtained by pouring the reaction mixture into water.
本発明によつて提供される感光性樹脂はこの有
効量を有機容剤に溶解して溶液となし、アルミニ
ウム板、銅板、亜鉛板、銅張り積層板などの支持
体表面上に、流延、吹付け、塗布などの手段で施
し、乾燥して製膜することができる。このように
して得られる感光性膜は基体とする高分子の物性
を受継ぎ、強靭であり、かつ支持体との密着性が
よい。このようにして得られた塗膜にネガを通し
て光照射を行い、未露光部を溶剤で除去すると陰
画像が得られる。そして感度が極めて高くまた化
学的に安定でいわゆる暗反応が起こらないために
溶液状態および製膜状態での品質維持が容易であ
る。そのためにフオトレジスト、印刷用PS版、
金属エツチングマスクなどの用途に好適である。 The photosensitive resin provided by the present invention is dissolved in an effective amount in an organic medium to form a solution, and cast onto the surface of a support such as an aluminum plate, copper plate, zinc plate, or copper-clad laminate. It can be applied by means such as spraying or coating and dried to form a film. The photosensitive film thus obtained inherits the physical properties of the polymer used as the base, is strong, and has good adhesion to the support. The coating film thus obtained is irradiated with light through a negative, and the unexposed areas are removed with a solvent to obtain a negative image. Furthermore, since it has extremely high sensitivity, is chemically stable, and does not cause so-called dark reactions, it is easy to maintain quality in the solution state and film forming state. For this purpose, photoresists, PS plates for printing,
Suitable for applications such as metal etching masks.
次に本発明を実施例により詳細に説明する。 Next, the present invention will be explained in detail with reference to examples.
実施例 １
重合度1400、ケン化度85％のポリビニルアルコ
ール１ｇをジメチルアセトアミド80mlに溶解しこ
れに４−カルボキシカルコン7.44ｇと２，４，６
−トリニトロクロルベンゼン7.30ｇを加え、さら
にピリジン12ｇを添加し80℃で４時間反応させ
る。次に得られた反応混合物を大過剰の水に注加
して目的とする感光性樹脂を単離する。エタノー
ルで洗浄後、乾燥した。収量は27.1ｇであつた。
このものの紫外線吸収スペクトルを調べたところ
吸収極大は310nmであり、これからカルコン基の
導入率を調べたところ60％であつた。さらに赤外
線吸収スペクトルを調べたところカルコン基に基
づく吸収が1605cm-1、及び1665cm-1に認められ
た。Example 1 1 g of polyvinyl alcohol with a degree of polymerization of 1400 and a degree of saponification of 85% was dissolved in 80 ml of dimethylacetamide, and 7.44 g of 4-carboxychalcone and 2,4,6
- Add 7.30 g of trinitrochlorobenzene, further add 12 g of pyridine, and react at 80°C for 4 hours. Next, the resulting reaction mixture is poured into a large excess of water to isolate the desired photosensitive resin. After washing with ethanol, it was dried. The yield was 27.1g.
An examination of the ultraviolet absorption spectrum of this product revealed that the absorption maximum was at 310 nm, and an examination of the chalcone group introduction rate from this revealed that it was 60%. Furthermore, when the infrared absorption spectrum was examined, absorption based on chalcone groups was observed at 1605 cm -1 and 1665 cm -1 .
実施例 ２
重合度1700、ケン化度85％のポリビニルアルコ
ール0.44ｇをジメチルアセトアミド40mlに溶解し
これに4′−ｎプロピル−４−カルボキシカルコン
3.82ｇと２，４，６−トリニトロクロルベンゼン
3.21ｇを加え、さらにピリジン5.1ｇを添加し85
℃で２時間反応させる。次に得られた反応混合物
を大過剰のエタノールに注加して目的とする感光
性樹脂を単離する。エタノールで洗浄後、乾燥し
た。収量は2.12ｇであつた。このものの紫外線吸
収スペクトルを調べたところ吸収極大は306nmで
あり、これからカルコン基の導入率を調べたとこ
ろ67％であつた。さらに赤外線吸収スペクトルを
調べたところカルコン基に基づく吸収が1600cm
-1、及び1650cm-1に認められた。Example 2 0.44 g of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 85% was dissolved in 40 ml of dimethylacetamide, and 4'-n propyl-4-carboxychalcone was added to the solution.
3.82g and 2,4,6-trinitrochlorobenzene
Add 3.21g and then add 5.1g of pyridine to
Incubate at ℃ for 2 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried. The yield was 2.12g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was found to be 306 nm, and when the chalcone group introduction rate was examined from this, it was 67%. Furthermore, we investigated the infrared absorption spectrum and found that the absorption based on chalcone groups was 1600 cm
-1 , and 1650 cm -1 .
実施列 ３
重合度2000、ケン化度85％のポリビニルアルコ
ール0.44ｇをジメチルアセトアミド40mlに溶解し
これに4′−クロロ−４−カルボキシカルコン3.72
ｇと２，４，６−トリニトロクロルベンゼン3.21
ｇを加え、さらにピリジン5.1ｇを添加し80℃で
23時間反応させる。次に得られた反応混合物を大
過剰のエタノールに注加して目的とする感光性樹
脂を単離する。エタノールで洗浄後、乾燥した。
収量は2.55ｇであつた。このものの紫外線吸収ス
ペクトルを調べたところ吸収極大は315nmであ
り、これからカルコン基の導入率を調べたところ
76％であつた。さらに赤外線吸収スペクトルを調
べたところカルコン基に基づく吸収が1600cm-1、
及び1665cm-1に認められた。Example 3: Dissolve 0.44 g of polyvinyl alcohol with a degree of polymerization of 2000 and a degree of saponification of 85% in 40 ml of dimethylacetamide, and add 3.72 g of 4'-chloro-4-carboxychalcone to this solution.
g and 2,4,6-trinitrochlorobenzene 3.21
Then add 5.1g of pyridine and heat at 80℃.
Incubate for 23 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried.
The yield was 2.55g. When we investigated the ultraviolet absorption spectrum of this product, we found that the maximum absorption was at 315 nm, and from this we investigated the introduction rate of chalcone groups.
It was 76%. Furthermore, we investigated the infrared absorption spectrum and found that the absorption based on chalcone groups was 1600 cm -1 .
and 1665 cm -1 .
実施例 ４
重合度1700、ケン化度90％のポリビニルアルコ
ール0.25ｇをジメチルアセトアミド20mlに溶解し
これに4′−メチル−３−カルボキシカルコン1.97
ｇと２，４，６−トリニトロクロルベンゼン1.83
ｇを加え、さらにピリジン3.2ｇを添加し85℃で
４時間反応させる。次に得られた反応混合物を大
過剰のエタノールに注加して目的とする感光性樹
脂を単離する。エタノールで洗浄後、乾燥した。
収量は0.92ｇであつた。このものの紫外線吸収ス
ペクトルを調べたところ吸収極大は316nmであ
り、これからカルコン基の導入率を調べたところ
59％であつた。さらに赤外線吸収スペクトルを調
べたところカルコン基に基づく吸収が1605cm-1、
及び1660cm-1に認められた。Example 4 0.25 g of polyvinyl alcohol with a degree of polymerization of 1700 and a degree of saponification of 90% was dissolved in 20 ml of dimethylacetamide, and 1.97 g of 4'-methyl-3-carboxychalcone was dissolved in it.
g and 2,4,6-trinitrochlorobenzene 1.83
Then, 3.2 g of pyridine was added and the mixture was reacted at 85°C for 4 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried.
The yield was 0.92g. When we investigated the ultraviolet absorption spectrum of this product, the absorption maximum was found to be 316 nm, and from this we investigated the introduction rate of chalcone groups.
It was 59%. Furthermore, we investigated the infrared absorption spectrum and found that the absorption based on chalcone groups was 1605 cm -1 .
and 1660 cm -1 .
実施例 ５
重合度500、ケン化度85％のポリビニルアルコ
ール0.25ｇをジメチルスルホキシド20mlに溶解し
これに3′−ニトロ−３−カルボキシカルコン2.19
ｇと２，４，６−トリニトロクロルベンゼン1.83
ｇを加え、さらにピリジン3.4ｇを添加し70℃で
25時間反応させる。次に得られた反応混合物を大
過情のエタノールに注加して目的とする感光性樹
脂を単離する。エタノールで洗浄後、乾燥した。
収量は1.35ｇであつた。このものの紫外線吸収ス
ペクトルを調べたところ吸収極大は320nmであ
り、これからカルコン基の導入率を調べたところ
70％であつた。さらに赤外線吸収スペクトルを調
べたところカルコン基に基づく吸収が1600cm-1、
及び1685cm-1に認められた。Example 5 0.25 g of polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 85% was dissolved in 20 ml of dimethyl sulfoxide, and 2.19 g of 3'-nitro-3-carboxychalcone was dissolved in it.
g and 2,4,6-trinitrochlorobenzene 1.83
Then add 3.4g of pyridine and heat at 70℃.
Incubate for 25 hours. Next, the obtained reaction mixture is poured into a large amount of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried.
The yield was 1.35g. When we investigated the ultraviolet absorption spectrum of this product, we found that the absorption maximum was at 320 nm, and from this we investigated the introduction rate of chalcone groups.
It was 70%. Furthermore, we investigated the infrared absorption spectrum and found that the absorption based on chalcone groups was 1600 cm -1 .
and 1685 cm -1 .
実施例 ６
重合度2100、ケン化度87％のポリビニルアルコ
ール0.25ｇをジメチルホルムアミド20mlに溶解し
これに2′−ニトロ−４−カルボキシカルコン2.19
ｇと２，４，６−トリニトロクロルベンゼン1.83
ｇを加え、さらにピリジン3.2ｇを添加し80℃で
24時間反応させる。次に得られた反応混合物を大
過剰のエタノールに注加して目的とする感光性樹
脂を単離する。エタノールで洗浄後、乾燥した。
収量は1.28ｇであつた。このものの紫外線吸収ス
ペクトルを調べたところ吸収極大は319nmであ
り、これからカルコン基の導入率を調べたところ
68％であつた。さらに赤外線吸収スペクトルを調
べたところカルコン基に基ずく吸収が1600cm-1、
及び1685cm-1に認められた。またニトロ基に基ず
く吸収が1560cm-1、1350cm-1に認められた。Example 6 0.25 g of polyvinyl alcohol with a degree of polymerization of 2100 and a degree of saponification of 87% was dissolved in 20 ml of dimethylformamide, and 2.19 g of 2'-nitro-4-carboxychalcone was dissolved in it.
g and 2,4,6-trinitrochlorobenzene 1.83
Then add 3.2g of pyridine and heat at 80℃.
Allow to react for 24 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried.
The yield was 1.28g. When we investigated the ultraviolet absorption spectrum of this product, we found that the absorption maximum was at 319 nm, and from this we investigated the introduction rate of chalcone groups.
It was 68%. Furthermore, we investigated the infrared absorption spectrum and found that the absorption based on chalcone groups was 1600 cm -1 .
and 1685 cm -1 . In addition, absorption based on nitro groups was observed at 1560 cm -1 and 1350 cm -1 .
実施例 ７
分子量45000のポリヒドロキシエチルアクリレ
ート1.15ｇをジメチルホルムアミド80mlに溶解し
これに４−カルボキシカルコン2.52ｇと２，４，
６−トリニトロクロルベンゼン2.53ｇを加え、さ
らにピリジン4.2ｇを添加し40℃で24時間反応さ
せる。次に得られた反応混合物を大過剰のエタノ
ールに注加して目的とする感光性樹脂を単離す
る。エタノールで洗浄後、乾燥した。収量は3.24
ｇであつた。このものの紫外線吸収スペクトルを
調べたところ吸収極大は310nmであり、これから
カルコン基の導入率を調べたところ87％であつ
た。さらに赤外線吸収スペクトルを調べたところ
カルコン基に基づく吸収が1605cm-1、及び1665cm
-1に認められた。Example 7 1.15 g of polyhydroxyethyl acrylate with a molecular weight of 45,000 was dissolved in 80 ml of dimethylformamide, and 2.52 g of 4-carboxychalcone and 2,4,
Add 2.53 g of 6-trinitrochlorobenzene, and further add 4.2 g of pyridine, and react at 40°C for 24 hours. Next, the obtained reaction mixture is poured into a large excess of ethanol to isolate the desired photosensitive resin. After washing with ethanol, it was dried. Yield is 3.24
It was hot at g. When the ultraviolet absorption spectrum of this product was examined, the absorption maximum was found to be 310 nm, and when the chalcone group introduction rate was examined from this, it was 87%. Further investigation of the infrared absorption spectrum revealed absorption based on chalcone groups at 1605 cm -1 and 1665 cm
-1 was recognized.
Claims (1)
合体に 一般式 （式中のR1、R2どちらか一つはオキソメチレン
結合であり、他は単なる結合、R3は水素原子、
アルキル基、シアノ基、ニトロ基、アルコキシ
基、アルコキシカルボニル基、ハロゲン原子であ
る）で表わされるカルコン誘導体を有効量の２，
４，６−トリニトロクロルベンゼンの存在下で反
応させることを特徴とする、 一般式 （式中のR1、R2、R3は前記と同じ意味を示す） で表わされる基を有する感光性樹脂の製法。[Claims] 1. General formula for a polymer or copolymer having an alcoholic hydroxyl group (Either R 1 or R 2 in the formula is an oxomethylene bond, the others are simple bonds, R 3 is a hydrogen atom,
An effective amount of 2,
The general formula is characterized in that the reaction is carried out in the presence of 4,6-trinitrochlorobenzene. (In the formula, R 1 , R 2 , and R 3 have the same meanings as above.) A method for producing a photosensitive resin having a group represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14589083A JPS6036504A (en) | 1983-08-10 | 1983-08-10 | Production of photo-sensitive resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14589083A JPS6036504A (en) | 1983-08-10 | 1983-08-10 | Production of photo-sensitive resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6036504A JPS6036504A (en) | 1985-02-25 |
| JPS6328442B2 true JPS6328442B2 (en) | 1988-06-08 |
Family
ID=15395413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14589083A Granted JPS6036504A (en) | 1983-08-10 | 1983-08-10 | Production of photo-sensitive resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6036504A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100574482B1 (en) * | 1999-09-07 | 2006-04-27 | 주식회사 하이닉스반도체 | Organic diffuse reflection prevention film composition and preparation method thereof |
-
1983
- 1983-08-10 JP JP14589083A patent/JPS6036504A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6036504A (en) | 1985-02-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4540650A (en) | Photoresists suitable for forming relief structures of highly heat-resistant polymers | |
| JP2001049231A (en) | Antireflection organic polymer and its production | |
| Merrill et al. | Photosensitive azide polymers | |
| JPH0225378B2 (en) | ||
| US4451613A (en) | Ethylenically-unsaturated dextrin oligomers | |
| EP0033721A1 (en) | Polymers cross-linkable by light with pending thioxanthone and imidyl groups, and process for preparing same | |
| JP2022133300A (en) | Method for producing polyimide precursor, method for producing photosensitive resin composition, method for producing pattern cured product, method for producing interlayer insulating film, cover coat layer or surface protective film, and method for producing electronic component | |
| KR940001555B1 (en) | Visible radiation photosensitive composition | |
| US5240811A (en) | Photogenerated polycarbodiimides from poly(tetrazole-5-thiones) and use in the preparation of coatings and deep-UV photoresists | |
| JPH0336215B2 (en) | ||
| JPS6328442B2 (en) | ||
| JPS6210104A (en) | Production of novel photopolymer | |
| JPH0651510A (en) | Method used for forming mixture, which can be bridged with radiation, and relief structure, which is stable at high temperature | |
| JPH06122713A (en) | Polyvinyl acetal resin and photosensitive resin composition containing the same | |
| JPH0424694B2 (en) | ||
| JPH0356243B2 (en) | ||
| JPS5939441B2 (en) | Method for producing photo-insolubilizable polyvinyl alcohol derivative | |
| JPH11140186A (en) | Photoreactive solvent soluble polyimide | |
| JP3478094B2 (en) | Method for dehydration ring closure of heat-resistant polymer precursor | |
| JPH0311350A (en) | Negative photosensitive coating material | |
| JPS62192404A (en) | Photopolymer and its production | |
| JP3004948B2 (en) | Method for preparing polyhydroxystyrene derivative | |
| JPS6221773B2 (en) | ||
| JPS5910721B2 (en) | Method for producing photo-insolubilizable polyvinyl alcohol derivative | |
| JPS59521B2 (en) | Method for producing photoinsolubilizable photosensitive material |