JPH0368044B2 - - Google Patents
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- Publication number
- JPH0368044B2 JPH0368044B2 JP2841889A JP2841889A JPH0368044B2 JP H0368044 B2 JPH0368044 B2 JP H0368044B2 JP 2841889 A JP2841889 A JP 2841889A JP 2841889 A JP2841889 A JP 2841889A JP H0368044 B2 JPH0368044 B2 JP H0368044B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- thin film
- film
- light
- irradiated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229920000642 polymer Polymers 0.000 claims description 35
- 239000010409 thin film Substances 0.000 claims description 32
- 239000010408 film Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 239000010453 quartz Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- -1 olefin compound Chemical class 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000001393 microlithography Methods 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical group 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- NFURDKBDRIUBCV-UHFFFAOYSA-N dodecyl 3-[4-(3-dodecoxy-3-oxoprop-1-enyl)phenyl]prop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C=CC1=CC=C(C=CC(=O)OCCCCCCCCCCCC)C=C1 NFURDKBDRIUBCV-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は新規な光反応性薄膜状重合体の製造方
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、シクロブタン環を有する重合体を
薄膜状に製造する方法に関するものである。本発
明において、薄膜を作製するのに用いられる重合
体は構造式（）で示され、棒状で剛直なある種
のオレフイン化合物の結晶に光照射することによ
り得られる。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel photoreactive thin film polymer. More specifically, the present invention relates to a method for producing a thin film of a polymer having a cyclobutane ring, which can be used for producing various electronic devices and as an electron beam resist material in microlithography. In the present invention, the polymer used to prepare the thin film is represented by the structural formula (), and is obtained by irradiating a rod-shaped, rigid crystal of a certain type of olefin compound with light.
（式中のＲは水素またはシアノ残基R′は炭素
数６〜22の飽和アルキル基を有するエステル残基
または炭素数６〜22の飽和アルキル基を有するシ
アノアクリル酸エステル残基、ｎは２〜200の整
数である。）
この重合体は化学的、物理的特性から感光性材
料、電子デバイス材料として期待されているが、
結晶性が非常に高く、有機溶媒に溶解しにくいた
め粉沫としての取り扱いが一般的であり、上記に
述べたような材料としての利用が困難であつた。
本発明の目的は、感光性材料などとして有用で、
また各種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、主鎖にシクロブタン環を有する新規な
薄膜状重合体を提供することにある。 (In the formula, R is hydrogen or a cyano residue R' is an ester residue having a saturated alkyl group having 6 to 22 carbon atoms or a cyanoacrylic acid ester residue having a saturated alkyl group having 6 to 22 carbon atoms, and n is 2 (It is an integer of ~200.) This polymer is expected to be used as a photosensitive material and electronic device material due to its chemical and physical properties.
Because it has very high crystallinity and is difficult to dissolve in organic solvents, it is generally handled as a powder, making it difficult to use it as a material as described above.
The object of the present invention is to provide useful materials such as photosensitive materials,
Another object of the present invention is to provide a novel thin film-like polymer having a cyclobutane ring in its main chain, which can be used for the production of various electronic devices and as an electron beam resist material in microlithography.
ところで一定の分子配列を有し、オングストロ
ームのオーダーで一定の厚さを持つ薄膜の調整方
法としては、ラングミユアブロジエツト法が知ら
れている。この方法を用いて薄膜を調整するに
は、分子内に親水性部分と長鎖アルキル基などの
疎水性部分を有することが必要とされている。上
記重合体の骨格構造はその条件を満たしていない
が本発明者は鋭意研究を重ねた結果、上記重合体
においてエステル残基中に疎水性部分として長鎖
アルキル基を有する重合体は、適当な両親媒性化
合物、例えばアラキン酸、ステアリルアルコール
などと混合することにより、水面上あるいは塩化
カドミウム水溶液などの液面上に安定な混合単分
子膜を形成することを見い出した。このような単
分子膜の形成は、表面圧−占有面積曲線におい
て、固体凝縮相の存在が確認されたことから明ら
かである。このような状態の単分子膜は垂直浸せ
き法により、適当な基板に移しとることができ
る。すなわち、本発明は一般式（）で表わされ
る重合体と両親媒性化合物を適当なモル比で混合
し単分子膜を形成させ、それを垂直浸せき法によ
り基板に移しとることにより分子のオーダーで膜
厚の調整可能な薄膜状重合体を作製する方法を提
供する。次に、該薄膜の好適な調整方法の１例に
ついて説明すると、まず長鎖アルキル基を有する
重合体、例えば、ポリ（ｐ−フエニレンジアクリ
ル酸ジドデシルエステル）とアラキン酸などのよ
うな両親媒性化合物とをモル比１：４の割合で、
クロロホルムなどの有機溶媒に溶解した後、この
溶液を蒸留水あるいは塩化カドミウム水溶液など
の液面上に徐々に滴下後、圧縮し、該液面上に重
合体と両親媒性化合物との混合単分子膜を形成さ
せる。この混合単分子膜中においてポリ（ｐ−フ
エニレンジアクリル酸ジドデシルエステル）とア
ラキン酸は互いに相分離をしており、前者ではベ
ンゼン部分が、後者ではカルボン酸部分が水面に
接し、両者とも長鎖アルキル基が水面に対し垂直
に立つような構造を保つている。この混合単分子
膜は基板を上下に移動させる操作を繰り返すこと
により基板上に累積することができ薄膜を作製す
ることができる（第１図）。膜の厚さは累積する
回数により調整できる。このようにして作製され
た薄膜は無色透明であり感光性である。例えば、
ポリ（ｐ−フエニレンジアクリル酸ジドデシルエ
ステル）の薄膜にシクロブタン環を開裂させると
考えられている波長の光（224nm）を照射すると
290nm付近の吸光度が照射時間の経過と共に増加
してくる（第２図）。この照射した薄膜の分子量
をゲルパーミエーシヨンクロマトグラフイーによ
り測定した結果、３〜４量体に相当するオリゴマ
ーであることがわかり、このことは主鎖中のシク
ロブタン環が光照射により開裂し、解重合が起つ
たことを示している。このオリゴマーの薄膜に極
大吸収290nm付近の光を照射すると吸収極大は
徐々に減少、消失し重合体の吸収スペクトルとな
る（第２図）。このことは、最照射によりオリゴ
マーから重合体への変化が起つた事を示してお
り、この過程は繰り返すことが可能である。すな
わち、本発明の製造方法によると薄膜状重合体は
光照射により可逆解重合性を有するものであるこ
とを示す。この光可逆解重合性は用いた重合体が
粉沫状の場合は観察されず、本製造方法により作
製された薄膜状重合体にのみ起る特異的なもの
で、この特性を活かして、これらは光記録材料、
各種デバイス作製用などして利用可能である。 By the way, as a method for preparing a thin film having a constant molecular arrangement and a constant thickness on the order of angstroms, the Langmiur Blossom method is known. In order to prepare a thin film using this method, it is necessary to have a hydrophilic portion and a hydrophobic portion such as a long-chain alkyl group in the molecule. Although the skeleton structure of the above polymer does not satisfy this condition, the present inventor has conducted extensive research and found that the above polymer has a long chain alkyl group as a hydrophobic moiety in the ester residue. We have discovered that by mixing with amphiphilic compounds such as arachidic acid and stearyl alcohol, a stable mixed monomolecular film can be formed on the surface of water or a liquid such as an aqueous cadmium chloride solution. The formation of such a monomolecular film is evident from the confirmation of the presence of a solid condensed phase in the surface pressure-occupied area curve. A monomolecular film in such a state can be transferred to a suitable substrate by a vertical dipping method. That is, in the present invention, a polymer represented by the general formula () and an amphiphilic compound are mixed at an appropriate molar ratio to form a monomolecular film, and this is transferred to a substrate by a vertical dipping method to form a monomolecular film on the order of molecules. Provided is a method for producing a thin film-like polymer whose film thickness can be adjusted. Next, one example of a suitable method for preparing the thin film will be explained. First, a polymer having a long-chain alkyl group, for example, poly(p-phenylene diacrylic acid didodecyl ester) and an amylamide such as arachidic acid, etc. and a medium compound at a molar ratio of 1:4,
After dissolving in an organic solvent such as chloroform, this solution is gradually dropped onto the surface of a liquid such as distilled water or an aqueous cadmium chloride solution, compressed, and a mixed monomolecule of a polymer and an amphipathic compound is deposited on the liquid surface. Form a film. In this mixed monolayer, poly(p-phenylene diacrylic acid didodecyl ester) and arachidic acid undergo phase separation from each other, with the benzene moiety in the former in contact with the water surface and the carboxylic acid moiety in the latter in contact with the water surface. The long-chain alkyl group maintains a structure that stands perpendicular to the water surface. This mixed monomolecular film can be accumulated on the substrate by repeating the operation of moving the substrate up and down, and a thin film can be produced (FIG. 1). The thickness of the film can be adjusted by the number of times of accumulation. The thin film thus produced is colorless, transparent, and photosensitive. for example,
When a thin film of poly(p-phenylene diacrylic acid didodecyl ester) is irradiated with light at a wavelength (224 nm) that is thought to cleave the cyclobutane ring,
The absorbance around 290 nm increases with the passage of irradiation time (Figure 2). As a result of measuring the molecular weight of this irradiated thin film by gel permeation chromatography, it was found that it is an oligomer corresponding to a trimer or tetramer, which means that the cyclobutane ring in the main chain is cleaved by light irradiation. This indicates that depolymerization has occurred. When this oligomer thin film is irradiated with light with an absorption maximum of around 290 nm, the absorption maximum gradually decreases and disappears, giving rise to the absorption spectrum of the polymer (Figure 2). This indicates that a change from oligomer to polymer occurred upon re-irradiation, and this process can be repeated. That is, according to the production method of the present invention, the thin film polymer has reversible depolymerizability upon irradiation with light. This photoreversible depolymerization property is not observed when the polymer used is in the form of powder, and is unique to the thin film polymer produced by this production method. is an optical recording material,
It can be used for manufacturing various devices.
実施例
次に実施例により本発明をさらに詳細に説明す
るが、本発明はこれらの例によつてなんら限定さ
れるものではない。Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例 １
エタノールから数回再結晶することにより精製
したｐ−フエニレンジアクリル酸ジドデシルエス
テル（100mg）の結晶を水中で撹拌、分散させ
500Wキセノンランプで１時間照射すると定量的
に高分子量重合体が得られる。この重合体のクロ
ロホルム溶液（１×10-3M）とアラキン酸のクロ
ロホルミ溶液（１×10-3M）をモル比１：５の割
合で混合した溶液をフイルムバランス装置を用い
て塩化カドミウム水溶液（１×10-3M）の液面上
に徐々に滴下して展開後、圧縮し単分子を形成さ
せた。表面圧−占有面積曲線から20−30dyn／cm
で固体凝縮相の存在が確認されたので、表面圧を
20dyn／cmに設定して、単分子膜を形成させた。
この単分子膜を垂直浸せき法により、石英板に移
しとつた。この時、石英板の下降、上昇時共に単
分子膜が石英板に移行し、この操作をくり返すこ
とにより、単分子膜が石英板に累積される。この
ようにして20層累積した薄膜は無色透明であり、
260nm以上の領域に吸収はない。この薄膜に単色
光照射装置を用いて224nmの光を60秒照射すると
薄膜の吸収スペクトルは290nmの吸収極大を有す
る吸収スペクトルとなつた。この時の薄膜をテト
ラビドロフランに溶解して、ゲルパーミエーシヨ
ンクロマトグラフイーにより、その分子量を測定
すると３〜４量体であり重合体はオリゴマーへ解
重合したことがわかつた。この薄膜に再び290nm
の光を照射すると吸収極大は徐々に減少し重合体
の吸収スペクトルとなり、再び重合体となつた。Example 1 Crystals of p-phenylene diacrylic acid didodecyl ester (100 mg) purified by recrystallizing several times from ethanol were stirred and dispersed in water.
A high molecular weight polymer can be quantitatively obtained by irradiating with a 500W xenon lamp for 1 hour. A chloroform solution of this polymer (1 x 10 -3 M) and a chloroform solution of arachidic acid (1 x 10 -3 M) were mixed at a molar ratio of 1:5, and a cadmium chloride aqueous solution was added using a film balance device. (1×10 -3 M) was gradually dropped onto the liquid surface, expanded, and then compressed to form a single molecule. 20-30dyn/cm from the surface pressure-occupied area curve
Since the existence of a solid condensed phase was confirmed in
A monomolecular film was formed by setting at 20 dyn/cm.
This monomolecular film was transferred to a quartz plate by a vertical dipping method. At this time, the monomolecular film is transferred to the quartz plate both when the quartz plate is lowered and raised, and by repeating this operation, the monomolecular film is accumulated on the quartz plate. The thin film accumulated by 20 layers in this way is colorless and transparent.
There is no absorption in the region above 260 nm. When this thin film was irradiated with 224 nm light for 60 seconds using a monochromatic light irradiation device, the absorption spectrum of the thin film became an absorption spectrum with an absorption maximum at 290 nm. When the thin film was dissolved in tetrahydrofuran and its molecular weight was measured by gel permeation chromatography, it was found that it was a trimer to tetramer, indicating that the polymer had depolymerized into an oligomer. 290nm to this thin film again
When irradiated with light, the absorption maximum gradually decreased to become the absorption spectrum of a polymer, and it became a polymer again.
実施例 ２
アセトンから再結晶をして精製した５，5′−
（１，４−フエニレン）−ビス（２−シアノ−２，
４−ペンタジエノイツク酸）ジヘキシルエステル
（100mg）の結晶を水中で撹拌、分散させ500Wキ
セノランプで30分間光照射すると定量的に重合体
が得られる。この重合体のクロロホルム溶液（１
×10-3M）とアラキン酸のクロロホルム溶液（１
×10-3M）をモル比１：４の割合で混合した溶液
を蒸留水の液面上の展開後、圧縮し単分子膜を形
成させた。表面圧−占有面積曲線から20〜
30dyn／cmで固体凝縮相の存在が確認されたの
で、表面圧を25dyn／cmに設定して、単分子膜を
形成させた。この単分子膜を垂直浸せき法によ
り、ガラス板に移しとつた。この時、石英板の下
降、上昇時共に単分子膜はガラス板に移行し、こ
の操作をくり返すことにより20層の累積膜を作製
した。このようにして作製された薄膜は無色透明
であり、単色光照射装置を用いて289nmの光を５
秒照射すると薄膜状の吸収スペクトルは360nmに
吸収極大があらわれる。この状態における薄膜の
分子量をゲルパーミエーシヨンクロマトグラフイ
ーで調べると２〜３量体のオリゴマーであること
がわかつた。この薄膜に360nmの光を照射すると
吸収極大は徐々に減少し、重合体と同じ吸収スペ
クトルとなり、再び重合したことがわかつた。こ
の過程は数回繰り返すことが可能であつた。Example 2 5,5'- purified by recrystallization from acetone
(1,4-phenylene)-bis(2-cyano-2,
When crystals of dihexyl 4-pentadienoic acid (100 mg) are stirred and dispersed in water and irradiated with light using a 500 W xeno lamp for 30 minutes, a polymer can be quantitatively obtained. A chloroform solution of this polymer (1
×10 -3 M) and a chloroform solution of arachidic acid (1
×10 -3 M) at a molar ratio of 1:4 was spread on the surface of distilled water and then compressed to form a monomolecular film. From the surface pressure-occupied area curve, 20~
Since the presence of a solid condensed phase was confirmed at 30 dyn/cm, the surface pressure was set to 25 dyn/cm to form a monomolecular film. This monomolecular film was transferred to a glass plate by a vertical dipping method. At this time, the monomolecular film transferred to the glass plate both when the quartz plate was lowered and raised, and by repeating this operation, a cumulative film of 20 layers was fabricated. The thin film produced in this way is colorless and transparent, and is irradiated with 289 nm light at 50 nm using a monochromatic light irradiation device.
When irradiated for seconds, the absorption spectrum of the thin film shows an absorption maximum at 360 nm. When the molecular weight of the thin film in this state was examined by gel permeation chromatography, it was found to be a dimer to trimer oligomer. When this thin film was irradiated with 360 nm light, the absorption maximum gradually decreased and the absorption spectrum became the same as that of the polymer, indicating that it had been polymerized again. This process could be repeated several times.
実施例 ３
アセトンから再結晶して精製した５，5′−（１，
４−フエニレン）−ビス（２−シアノ−２，４−
ペンタジエノイツク酸）ジドデシルエステル
（100mg）の結晶を水中で撹拌、分散させ500Wキ
セノンランプを光源としフイルター（コーニング
No.３−72）を用いて430nm以上の光を60分照射す
ると定量的に分子量2000から3000の黄色の低重合
体が得られる。この低重合体のクロロホルム溶液
（１×10-3M）とアラキン酸のクロロホルム溶液
（１×10-3M）をモル比１：５の割合で混合した
溶液を蒸留水の液面上のに徐々に滴下して展開後
圧縮し単分子膜を形成させた。表面上−占有面積
曲線ら20〜30dyn／cmｄで固体凝縮相の存在が確
認されたので、表面圧を20dyn／cmに設定して、
単分子膜を形成させた・。この単分子膜を垂直浸
せき法により、石英板に移しとつた。この時、石
英板の下降、上昇時共に単分子膜が石英板に移行
し、この操作をくり返すことにより、30層の累積
膜を作製した。このようにして作製された薄膜は
黄色透明であり、360nmに吸収極大を持つ。この
薄膜に360nmの光を３分間照射すると360nmの吸
収極大は消失し分子量の高い重合体となつた。こ
の薄膜状重合体に289nmの光を照射すると、薄膜
の吸収スペクトルは再び360nmに吸収極大を有す
るオリゴマーの吸収スペクトルとなる。この低重
合体から高重合体またこの逆の変化は光照射によ
り可逆的に起ることがわかつた。Example 3 5,5′-(1,
4-phenylene)-bis(2-cyano-2,4-
Crystals of didodecyl ester (pentadienoitsuccinic acid) (100 mg) were stirred and dispersed in water, and a 500W xenon lamp was used as the light source.
When irradiated with light of 430 nm or more for 60 minutes using No. 3-72), a yellow low polymer with a molecular weight of 2,000 to 3,000 is quantitatively obtained. A solution of a chloroform solution of this low polymer (1 x 10 -3 M) and a chloroform solution of arachidic acid (1 x 10 -3 M) mixed at a molar ratio of 1:5 was poured onto the surface of distilled water. It was gradually dropped, expanded, and compressed to form a monomolecular film. Since the presence of a solid condensed phase was confirmed from the surface-occupied area curve at 20 to 30 dyn/cmd, the surface pressure was set to 20 dyn/cm, and
A monomolecular film was formed. This monomolecular film was transferred to a quartz plate by a vertical dipping method. At this time, the monomolecular film was transferred to the quartz plate both when the quartz plate was lowered and raised, and by repeating this operation, a cumulative film of 30 layers was produced. The thin film prepared in this way is transparent and yellow, and has an absorption maximum at 360 nm. When this thin film was irradiated with 360 nm light for 3 minutes, the absorption maximum at 360 nm disappeared and it became a polymer with a high molecular weight. When this thin film polymer is irradiated with 289 nm light, the absorption spectrum of the thin film becomes that of an oligomer having an absorption maximum at 360 nm. It was found that this change from low polymer to high polymer and vice versa occurs reversibly by light irradiation.
第１図は薄膜の製造プロセスを示し基板１を水
中に下降あるいは上昇させることにより水面上に
形成された混合単分子膜２が基板に移し取られ
る。これを繰り返すことにより膜は累積され光反
応性薄膜状重合体３が製造される。第２図は光反
応薄膜状重合体の特徴である光反応性挙動を示
す。すなわち、短波長光（224nm）を薄膜状重合
体１に照射すると解重合を起し薄膜状オリゴマー
２となる。これに290nmの光を照射すると再び薄
膜状重合体となる。
FIG. 1 shows a process for manufacturing a thin film, and by lowering or raising a substrate 1 into water, a mixed monomolecular film 2 formed on the water surface is transferred onto the substrate. By repeating this process, the film is accumulated and a photoreactive thin film polymer 3 is produced. FIG. 2 shows the photoreactive behavior that is characteristic of photoreactive thin film polymers. That is, when the thin film polymer 1 is irradiated with short wavelength light (224 nm), it undergoes depolymerization and becomes the thin film oligomer 2. When this is irradiated with 290 nm light, it becomes a thin film-like polymer again.
Claims (1)
数６〜22の飽和アルキル基を有するエステル残基
または炭素数６〜22の飽和アルキル基を有するシ
アノアクリル酸エステル残基、ｎは２〜200の整
数である。） で表わされる重合体と長鎖脂肪酸あるいは長鎖ア
ルコールなどの両親媒性化合物との混合物からな
る混合単分子膜を水面上に形成し、これを垂直侵
せき法により基板上に累積することにより、光反
応性膜とすることを特徴とする薄膜状重合体の製
造方法。[Claims] 1. General formula (In the formula, R is hydrogen or a cyano residue R' is an ester residue having a saturated alkyl group having 6 to 22 carbon atoms or a cyanoacrylic acid ester residue having a saturated alkyl group having 6 to 22 carbon atoms, and n is 2 A mixed monomolecular film consisting of a mixture of a polymer represented by 1. A method for producing a thin film polymer, the method comprising forming a photoreactive film by accumulating it on a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2841889A JPH02208306A (en) | 1989-02-07 | 1989-02-07 | Production of new photoreactive thin-film polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2841889A JPH02208306A (en) | 1989-02-07 | 1989-02-07 | Production of new photoreactive thin-film polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02208306A JPH02208306A (en) | 1990-08-17 |
| JPH0368044B2 true JPH0368044B2 (en) | 1991-10-25 |
Family
ID=12248107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2841889A Granted JPH02208306A (en) | 1989-02-07 | 1989-02-07 | Production of new photoreactive thin-film polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02208306A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007270146A (en) * | 2006-03-10 | 2007-10-18 | Nagoya Institute Of Technology | Conductive polymer thin film for display element, method for producing the same, and electrochromic display element using the same |
-
1989
- 1989-02-07 JP JP2841889A patent/JPH02208306A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02208306A (en) | 1990-08-17 |
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