JPS6230979B2 - - Google Patents
Info
- Publication number
- JPS6230979B2 JPS6230979B2 JP9871385A JP9871385A JPS6230979B2 JP S6230979 B2 JPS6230979 B2 JP S6230979B2 JP 9871385 A JP9871385 A JP 9871385A JP 9871385 A JP9871385 A JP 9871385A JP S6230979 B2 JPS6230979 B2 JP S6230979B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- low polymer
- formula
- light
- general formula
- 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
- 229920000642 polymer Polymers 0.000 claims description 21
- 230000001186 cumulative effect Effects 0.000 claims description 14
- AAFXQFIGKBLKMC-KQQUZDAGSA-N (e)-3-[4-[(e)-2-carboxyethenyl]phenyl]prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=C(\C=C\C(O)=O)C=C1 AAFXQFIGKBLKMC-KQQUZDAGSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000010408 film Substances 0.000 description 34
- 238000010521 absorption reaction Methods 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid group Chemical group C(C=CC1=CC=CC=C1)(=O)O WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 238000001393 microlithography Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DXNVDDCCNNZXEO-UHFFFAOYSA-N 3-[4-(3-dodecoxy-3-oxoprop-1-enyl)phenyl]prop-2-enoic acid Chemical compound CCCCCCCCCCCCOC(=O)C=CC1=CC=C(C=CC(O)=O)C=C1 DXNVDDCCNNZXEO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WGXGKXTZIQFQFO-CMDGGOBGSA-N ethenyl (e)-3-phenylprop-2-enoate Chemical compound C=COC(=O)\C=C\C1=CC=CC=C1 WGXGKXTZIQFQFO-CMDGGOBGSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
産業上の利用分野
本発明は新規な低重合体及びその製造方法に関
するものである。さらに詳しくいえば、本発明
は、架橋剤や感光性材料などとして有用であり、
またその単量体の累積膜から得られた重合体薄膜
は、各種の電子デバイス作製用や、ミクロリソグ
ラフイーにおける電子線レジスト材料などとして
利用可能な、シクロブタン環とケイ皮酸残基を有
する低重合体、及びこのものを前記薄膜状に容易
に製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel low polymer and a method for producing the same. More specifically, the present invention is useful as a crosslinking agent, a photosensitive material, etc.
In addition, the polymer thin film obtained from the cumulative film of the monomer is a low polymer film containing a cyclobutane ring and cinnamic acid residue that can be used for manufacturing various electronic devices and as an electron beam resist material in microlithography. The present invention relates to a polymer and a method for easily producing the same in the form of a thin film.
従来の技術
従来、構造式
を有するポリケイ皮酸ビニルは、単量体のケイ皮
酸ビニルを重合することによつて得られ、感光性
材料として、例えば印刷製版用、プリント基板
用、ケミカルミーリング用などに広く用いられて
いる。Conventional technology Conventional, structural formula Polyvinyl cinnamate, which has a .
ところで、このようなケイ皮酸残基を有する重
合体において、その単量体の累積膜から得られた
重合体薄膜は、該薄膜がもつ光学的、電気的特性
を活かして各種の電子デバイス作製用や、ミクロ
リソグラフイーにおける電子線レジスト材料など
としての利用が期待されている。 By the way, in polymers having such cinnamic acid residues, polymer thin films obtained from cumulative films of the monomers can be used to fabricate various electronic devices by taking advantage of the optical and electrical properties of the thin films. It is expected to be used as an electron beam resist material in microlithography.
しかしながら、前記のケイ皮酸ビニルは、単分
子膜形成能を有していないため、これを累積膜の
形で反応させて、重合物を得ることができない。 However, since vinyl cinnamate does not have the ability to form a monomolecular film, it is not possible to obtain a polymer by reacting it in the form of a cumulative film.
発明が解決しようとする問題点
本発明の目的は、感光性材料などとして有用
で、また各種の電子デバイス作製用や、ミクロリ
ソグラフイーにおける電子線レジスト材料などと
して利用可能な、薄膜状の新規なケイ皮酸残基を
有する低重合体を提供することにある。Problems to be Solved by the Invention The object of the present invention is to provide a novel thin film that is useful as a photosensitive material and can also be used as an electron beam resist material for manufacturing various electronic devices and in microlithography. An object of the present invention is to provide a low polymer having a cinnamic acid residue.
問題点を解決するための手段
一般に、有機化合物が単分膜形成能を有するた
めには、分子内に親水性部位と長鎖アルキル基な
どの疎水性部位を有することが必要とされてい
る。Means for Solving the Problems Generally, in order for an organic compound to have the ability to form a monolayer, it is required to have a hydrophilic site and a hydrophobic site such as a long-chain alkyl group in the molecule.
本発明者らは鋭意研究を重ねた結果、一般式
（式中のＲは炭素数７〜22の飽和アルキル基で
ある）
で表わされるケイ皮酸誘導体のｐ―フエニレンジ
アクリル酸モノアルキルエステルは、親水性基と
してカルボキシル基を、疎水性基として長鎖アル
キル基を有するため、単分子膜形成能に優れ、分
子のオーダーで膜厚を制御しうる累積膜を得るこ
とができる。これらは光照射によつて容易に新規
な低重合体を与えることから、単量体としてこの
ものを用いることにより、前記目的を達成しうる
ことを見出し、この知見に基づいて本発明を完成
するに至つた。 As a result of extensive research, the inventors found that the general formula The p-phenylene diacrylic acid monoalkyl ester of the cinnamic acid derivative represented by (R in the formula is a saturated alkyl group having 7 to 22 carbon atoms) has a carboxyl group as a hydrophilic group and a carboxyl group as a hydrophobic group. Since it has a long-chain alkyl group, it has excellent ability to form a monomolecular film, and it is possible to obtain a cumulative film whose thickness can be controlled on the order of molecules. Since these can easily give new low polymers by light irradiation, it has been discovered that the above object can be achieved by using these as monomers, and based on this knowledge, the present invention has been completed. It came to this.
すなわち、本発明は、一般式
（式中のＲは炭素数７〜22の飽和アルキル基、
ｎは２〜５の整数である）
で表わされる低重合体、及びこのものを、前記一
般式（）で表わされるｐ―フエニレンジアクリ
ル酸モノアルキルエステルの累積膜に光を照射す
ることによつて製造する方法を提供するものであ
る。 That is, the present invention provides the general formula (R in the formula is a saturated alkyl group having 7 to 22 carbon atoms,
n is an integer of 2 to 5), and the cumulative film of p-phenylene diacrylic acid monoalkyl ester represented by the general formula () is irradiated with light. Accordingly, a method for manufacturing the same is provided.
本発明において単量体として用いるｐ―フエニ
レンジアクリル酸モノアルキルエステルは、次の
一般式（）
で示される構造を有し、式中のＲは炭素数７〜22
の飽和アルキル基である。このものは、親水性基
としてカルボキシル基を、疎水性基として長鎖ア
ルキル基を有し、水面上や塩化カドミウム水溶液
などの液面上で、安定した単分子膜を形成する。
この単分子膜の形成は、表面圧―占有面積曲線か
ら容易に確認することができる。 The p-phenylene diacrylic acid monoalkyl ester used as a monomer in the present invention has the following general formula () It has a structure shown in the formula, and R has 7 to 22 carbon atoms.
is a saturated alkyl group. This material has a carboxyl group as a hydrophilic group and a long-chain alkyl group as a hydrophobic group, and forms a stable monomolecular film on the surface of water or a liquid such as a cadmium chloride aqueous solution.
Formation of this monomolecular film can be easily confirmed from the surface pressure-occupied area curve.
本発明の低重合体を製造するには、まずｐ―フ
エニレンジアクリル酸モノアルキルエステルをク
ロロホルムなどの有機溶媒に溶解したのち、この
溶液を蒸留水や塩化カドミウム水溶液などの液面
上に徐々に滴下して、該液面上にｐ―フエニレン
ジアクリル酸モノアルキルエステルの単分子膜を
形成させ、次いでこの単分子膜をガラスなどの基
板上に移しとる操作を繰り返して累積膜を作成し
たのち、これに後記のような光源を用い、光照射
して附加重合させ、薄膜状の低重合体を得る方法
である。この際の累積膜は、結晶状態のように特
定の分子配列構造を有し、光によつて反応する。
例えば、10層以上積層した累積膜は、280〜
340nmの波長域に吸収極大を有しており、キセノ
ンランプなどで光照射することにより、二重結合
間で反応が起こり、この吸収極大の吸光度は減少
する。この光照射した薄膜はゲルパーミエーシヨ
ンクロマトグラフイーで測定した分子量から判断
すると二量体の低重合体であり、赤外吸収スペク
トルなどから、次のようなシクロブタン環を主鎖
に有する構造であることが確認された。 To produce the low polymer of the present invention, first, p-phenylene diacrylic acid monoalkyl ester is dissolved in an organic solvent such as chloroform, and then this solution is gradually poured onto the surface of a liquid such as distilled water or an aqueous cadmium chloride solution. to form a monomolecular film of p-phenylene diacrylic acid monoalkyl ester on the liquid surface, and then transfer this monomolecular film onto a substrate such as glass to create a cumulative film. Thereafter, this is irradiated with light using a light source as described later to cause addition polymerization, thereby obtaining a thin film-like low polymer. The accumulated film at this time has a specific molecular arrangement structure like a crystalline state, and reacts to light.
For example, a cumulative film of 10 or more layers has a thickness of 280~
It has an absorption maximum in the wavelength range of 340 nm, and when irradiated with light from a xenon lamp or the like, a reaction occurs between double bonds and the absorbance at this absorption maximum decreases. Judging from the molecular weight measured by gel permeation chromatography, this light-irradiated thin film is a dimeric low polymer, and from the infrared absorption spectrum, it has the following structure with a cyclobutane ring in the main chain. It was confirmed that there is.
このようにして得られた本発明の低重合体は、
前記一般式（）で示されるように、シクロブタ
ン環と末端にケイ皮酸残基を有する重合度２〜５
の、文献未載の新規化合物であり、クロロホルム
やジメチルホルムアミドなどの有機溶剤に可溶で
ある。 The low polymer of the present invention thus obtained is
As shown in the general formula (), the polymerization degree is 2 to 5, which has a cyclobutane ring and a cinnamic acid residue at the end.
It is a new compound that has not been described in any literature, and is soluble in organic solvents such as chloroform and dimethylformamide.
発明の効果
本発明の低重合体は、単量体としてｐ―フエニ
レンジアクリル酸モノアルキルエステルを用い、
その累積膜に光を照射して得られた、薄膜状のも
のであつて、シクロブタン環と末端にケイ皮酸残
基を有しており、このケイ皮酸残基における二重
結合の光反応性を利用して、架橋剤や感光性材料
などとして用いることができる。特に累積膜から
得られた低重合体薄膜は、その光学的、電気的特
性を活かして各種の電子デバイス作製用や、ミク
ロリソグラフイーにおける電子線レジスト材料な
どとして利用可能である。Effects of the invention The low polymer of the present invention uses p-phenylene diacrylic acid monoalkyl ester as a monomer,
It is a thin film obtained by irradiating the cumulative film with light, and has a cyclobutane ring and a cinnamic acid residue at the end, and the photoreaction of the double bond in this cinnamic acid residue Taking advantage of its properties, it can be used as a crosslinking agent, photosensitive material, etc. In particular, the low polymer thin film obtained from the cumulative film can be used to make various electronic devices by taking advantage of its optical and electrical properties, and as an electron beam resist material in microlithography.
実施例
次に実施例により本発明をさらに詳細に説明す
る。Examples Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
ベンゼンから数回再結晶により精製したｐ―フ
エニレンジアクリル酸モノ―ｎ―ドデシルエステ
ル10mgを、十分に精製されたクロロホルム25mlに
溶解し、この溶液をラウダ社製フイルムバランス
装置を用いて、濃度10-3mol／ｌの塩化カドミウ
ム水溶液（PH5.3）の液面上に徐々に滴下して展
開し、単分子膜を形成させた。この際、ｐ―フエ
ニレンジアクリル酸モノ―ｎ―ドデシルエステル
の表面圧―占有面積曲線から20〜30dyn／cmで液
体凝縮膜の存在が確認されたので、該装置を
25dyn／cmに設定して、単分子膜を形成させた。Example 1 10 mg of p-phenylene diacrylic acid mono-n-dodecyl ester purified by recrystallization several times from benzene was dissolved in 25 ml of sufficiently purified chloroform, and this solution was purified using a Lauda film balance device. Then, it was gradually dropped onto the surface of a cadmium chloride aqueous solution (PH5.3) with a concentration of 10 -3 mol/l and spread to form a monomolecular film. At this time, the presence of a liquid condensation film at 20 to 30 dyn/cm was confirmed from the surface pressure-occupied area curve of p-phenylene diacrylic acid mono-n-dodecyl ester, so the device was
A monomolecular film was formed by setting at 25 dyn/cm.
次に、このようにして形成された単分子膜を、
垂直浸せき法によりガラス板に移しとり、単分子
膜10層から成る累積膜を作成した。この累積膜
は、290nmの波長域にUVスペクトルの吸収極大
を有し、これにキセノンランプを用いて10分間光
照射すると、二重結合間で反応が起り、この吸収
極大の吸光度は減少した。５分間光照射後の累積
膜をテトラフランに溶解しゲルパーミエーシヨン
クロマトグラフイーにより分子量を調べてみると
２〜３量体である。このもののUV吸収スペクト
ルは280nmに吸収極大を持つ。又、赤外吸収スペ
クトルを原料のｐ―フエニレンジアクリル酸モノ
―ｎ―ドデシルエステルのそれと比較するとオレ
フイン二重結合（1640cm-1）の吸収が減少してい
ること、カルボニルの吸収（1720cm-1）が巾広く
なつており高波数側に移動している。これらの事
から、この生成物は二重結合の環化附加反応によ
り形成されたシクロブタン環を有する低重合体で
あると判断した。この生成物はｘ線分析によると
ほとんど無定型であり、したがつて明らかな融点
を示さない。この低重合体に300nm以上の光を更
に長時間照射すると吸収極大は消失し、高分子量
のポリマーとなり一般の有機溶媒に不溶となる。 Next, the monomolecular film formed in this way is
A cumulative film consisting of 10 monomolecular films was prepared by transferring it to a glass plate using the vertical dipping method. This cumulative film has an absorption maximum in the UV spectrum in the wavelength range of 290 nm, and when it was irradiated with light for 10 minutes using a xenon lamp, a reaction occurred between double bonds and the absorbance at this absorption maximum decreased. The accumulated film after 5 minutes of light irradiation was dissolved in tetrafuran and the molecular weight was determined by gel permeation chromatography, and it was found to be a dimer to trimer. The UV absorption spectrum of this substance has an absorption maximum at 280 nm. Furthermore, when comparing the infrared absorption spectrum with that of p-phenylene diacrylic acid mono-n-dodecyl ester as a raw material, it was found that the absorption of olefin double bonds (1640 cm -1 ) decreased and the absorption of carbonyl (1720 cm -1 ) decreased. 1 ) is becoming wider and moving toward higher wavenumbers. From these facts, it was determined that this product was a low polymer having a cyclobutane ring formed by a cyclization addition reaction of a double bond. The product is almost amorphous according to x-ray analysis and therefore exhibits no apparent melting point. When this low polymer is irradiated with light of 300 nm or more for a longer period of time, the absorption maximum disappears, and the polymer becomes a high molecular weight polymer that is insoluble in common organic solvents.
実施例 ２
アセトンから再結晶により精製したｐ―フエニ
レンジアクリル酸モノ―ｎ―ステアリルエステル
３mgを、精製したクロロホルム10mlに溶解し、こ
の溶液をフイルムバランス装置を用いて再蒸留水
の水面上に徐々に滴下して展開し、単分子膜を形
成させた。この際、該化合物の表面圧―占有面積
曲線から20〜30dyn／cmで液体凝縮膜の存在が確
認されたので、該装置を25dyn／cmに設定して、
単分子膜を形成させた。Example 2 3 mg of p-phenylene diacrylic acid mono-n-stearyl ester purified by recrystallization from acetone was dissolved in 10 ml of purified chloroform, and this solution was poured onto the surface of redistilled water using a film balance device. It was gradually dropped and spread to form a monomolecular film. At this time, the presence of a liquid condensation film was confirmed from the surface pressure-occupied area curve of the compound at 20 to 30 dyn/cm, so the device was set at 25 dyn/cm.
A monolayer was formed.
次に、このようにして形成された単分子膜を、
垂直浸せき法により、十分に洗浄した石英ガラス
板に移しとり、単分子膜15層から成る累積膜を作
成した。この累積膜は、320nmの波長域にUVス
ペクトルの吸収極大を有し、これにキセノンラン
プを用いて20分間光照射すると、二重結合間で反
応が起り、この吸収極大の吸光度は減少した。５
〜10分間光照射後の累積膜をテトラヒドロフラン
に溶解し、ゲルパーミエーシヨンクロマトグラフ
イーで分子量を調べてみると、生成物は２量体あ
るいは３量体であることがわかつた。又、赤外吸
収スペクトルは原料のｐ―フエニレンジアクリル
酸モノ―ｎ―ステアリエステルと比較するとオレ
フイン二重結合（1640cm-1）の吸収が減少してい
ること、カルボニルの吸収（1720cm-1）が巾広く
なつており高波数側に移動していることから、こ
の生成物は二重結合の環化附加反応により形成さ
れたシクロブタン環を有する低重合体であると判
断した。この生成物はｘ線分析によるとほとんと
無定型であり、明確な融点を示さない。この低重
合体に300nm以上の光を更に長時間照射すると吸
収極大は消失し、膜は一般の有機溶媒に不溶とな
る。 Next, the monomolecular film formed in this way is
A cumulative film consisting of 15 monomolecular films was prepared by transferring it to a thoroughly cleaned quartz glass plate using the vertical dipping method. This cumulative film had an absorption maximum in the UV spectrum in the 320 nm wavelength range, and when it was irradiated with light for 20 minutes using a xenon lamp, a reaction occurred between double bonds and the absorbance at this absorption maximum decreased. 5
The accumulated film after irradiation with light for ~10 minutes was dissolved in tetrahydrofuran, and the molecular weight was examined by gel permeation chromatography, and it was found that the product was a dimer or trimer. In addition, the infrared absorption spectrum shows that the absorption of olefin double bonds (1640 cm -1 ) is decreased and the absorption of carbonyl (1720 cm -1 ) became wider and moved to the higher wavenumber side, it was determined that this product was a low polymer having a cyclobutane ring formed by a cyclization addition reaction of a double bond. The product is almost amorphous according to x-ray analysis and does not exhibit a definite melting point. When this low polymer is irradiated with light of 300 nm or more for a longer period of time, the absorption maximum disappears and the film becomes insoluble in common organic solvents.
Claims (1)
ｎは２〜５の整数である） で表わされる低重合体。 ２ 一般式 （式中のＲは炭素数７〜22の飽和アルキル基で
ある） で表わされるｐ―フエニレンジアクリル酸モノア
ルキルエステルの累積膜に光を照射することを特
徴とする、一般式 （式中のＲは前記の意味をもち、ｎは２〜５の
整数である） で表わされる低重合体の製造方法。[Claims] 1. General formula (R in the formula is a saturated alkyl group having 7 to 22 carbon atoms,
n is an integer of 2 to 5) A low polymer represented by: 2 General formula (R in the formula is a saturated alkyl group having 7 to 22 carbon atoms) A general formula characterized by irradiating light to a cumulative film of p-phenylene diacrylic acid monoalkyl ester represented by (In the formula, R has the above-mentioned meaning, and n is an integer of 2 to 5.) A method for producing a low polymer represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9871385A JPS61257947A (en) | 1985-05-10 | 1985-05-10 | Novel low polymer and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9871385A JPS61257947A (en) | 1985-05-10 | 1985-05-10 | Novel low polymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61257947A JPS61257947A (en) | 1986-11-15 |
| JPS6230979B2 true JPS6230979B2 (en) | 1987-07-06 |
Family
ID=14227153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9871385A Granted JPS61257947A (en) | 1985-05-10 | 1985-05-10 | Novel low polymer and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61257947A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01139620A (en) * | 1987-11-26 | 1989-06-01 | Agency Of Ind Science & Technol | Production of novel thin filmy polymer |
-
1985
- 1985-05-10 JP JP9871385A patent/JPS61257947A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61257947A (en) | 1986-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2002161117A (en) | Polymer and photoresist compound | |
| JPH11286469A (en) | Monomer, polymer, production of monomer, production of polymer, photoresist, production of photoresist and semiconductor element | |
| US5248734A (en) | Process for preparing a polyphenylene polymer | |
| JP4067251B2 (en) | Photoresist monomer and method for producing the same, photoresist copolymer and method for producing the same, photoresist composition, and method for forming photoresist pattern | |
| US6403281B1 (en) | Cross-linker monomer comprising double bond and photoresist copolymer containing the same | |
| US6200731B1 (en) | Photoresist cross-linking monomers, photoresist polymers and photoresist compositions comprising the same | |
| KR20000015014A (en) | New photoresist monomer, polymer, and photoresist compound | |
| KR910004040B1 (en) | Novel organometallic polymers | |
| FR2782715A1 (en) | NEW PHOTORESIST MONOMER HAVING A HYDROXY GROUP AND A CARBOXY GROUP, ITS COPOLYMER AND PHOTORESIST COMPOSITION USING THE SAME | |
| US6455226B1 (en) | Photoresist polymers and photoresist composition containing the same | |
| US4150989A (en) | Photosensitive article having polyaldehydes and its use in photoimaging | |
| JPS6230979B2 (en) | ||
| US6818376B2 (en) | Cross-linker monomer comprising double bond and photoresist copolymer containing the same | |
| JPH01138236A (en) | Formation of thin layer | |
| KR19980081872A (en) | Acrylic acid or methacrylic acid derivatives and polymers obtained therefrom | |
| JPH01139620A (en) | Production of novel thin filmy polymer | |
| JPH10510865A (en) | Polymerizable composition using acetylene and photopolymerization method of acetylene | |
| KR100520167B1 (en) | Novel photoresist monomers, polymers thereof, and photoresist composition containing the same | |
| JPS63126578A (en) | Composite parts including thin film | |
| JPH03131626A (en) | Photo-sensitive amphipathic polymeric compound and production thereof | |
| JPH02208306A (en) | Production of new photoreactive thin-film polymer | |
| JP2830442B2 (en) | Thermo-sensitive element | |
| JP2717553B2 (en) | Phthalocyanine compounds and Langmuir-Blodgett membranes | |
| JPS63280086A (en) | Dinuclear complex of salt thereof and langmuir-blodgett membrane | |
| JPS6365659B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |