JPH01213321A - Production of novel thin film polymer - Google Patents

Abstract

PURPOSE:To obtain the present polymer having reversible depolymerization by light and useful in preparation of electronic device, by repairing a built-up film consisting of (phenylene)-bis(cyano-pentadienoic acid) dialkyl ester, etc., and then irradiating the film with light. CONSTITUTION:A built-up film consisting of 5,5'-(1,4-phenylene)-bis(1-cyano-2,4- pentadienoic acid) dialkyl ester or a mixture of the above-mentioned dialkyl ester with a compound having amphipatic property is prepared and then irradiated with light to provide the aimed polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel method for producing a thin film polymer. More specifically, the present invention relates to a method for easily producing a crosslinking agent, a photosensitive material, an electronic device material, and a thin film polymer that is useful as a microorganism.

Prior art 5. S'-(1,4-)dinidine)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester is a thin film-like polymer due to its molecular structure. If it can be manufactured, it can be used as a raw material for various functional materials.

However, this polymer is polymerized by light in a crystalline state to produce a crystalline polymer, but this polymer is difficult to process and difficult to form into a thin film, and is usually treated as a crystal or powder. However, it has been difficult to use it in electronic devices.

Incidentally, the Langmuir-Blodgett method is known as a method for preparing a thin film having a certain molecular arrangement and a certain thickness on the order of angstroms. When preparing a thin film using this method, it is necessary to use a compound having a chemical structure capable of forming a monomolecular film, that is, an amphiphilic compound having a parent tree group and a hydrophobic group in the molecule.

Therefore, in order to produce a thin film-like polymer with excellent mechanical strength that can be used for electronic devices etc. by the Langmuir-Blodgett method, a cumulative film must be produced using an amphiphilic compound having a polymerizable functional group. Then, this can be polymerized. However, the synthesis of amphiphilic compounds having polymerizable functional groups is not always easy, and the compounds
Depending on its chemical structure, a monomolecular film is not necessarily formed.

Problems to be Solved by the Invention The present invention provides compounds 5 which are relatively easy to synthesize and are photoreactive.
, 5'-(1,4-phenylene)-bis(2-cyano-L4-pentagenoic acid) dialkyl ester, and provides a method for easily producing a thin film polymer thereof.

Means for Solving the Problems The present inventors have conducted intensive research to develop a method for easily producing a thin film polymer of the dialkyl ester. On the other hand, if the number of carbon atoms in the alkyl group is small, it is possible to form a monolayer by mixing it with an appropriate amphiphilic compound, and these monolayers can be deposited on a substrate such as a quartz plate. It was discovered that a thin film polymer can be easily obtained by irradiating this cumulative film with light because it can be accumulated and has photopolymerizability, and based on this knowledge, the present invention was completed. reached.

That is, the present invention provides S,5'-(1,4-7enylene)-bis( Production of a thin film-like polymer characterized by preparing a cumulative film consisting of a dialkyl ester of traano-2, topentadienoic acid) or a mixture of this and an amphiphilic compound, and then irradiating the film with light. The present invention provides a method.

The present invention will be explained in detail below.

5,5'-(1,4
-)1dicine)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester has a structure represented by the general formula (I), and R in the formula has 5 to 20 carbon atoms. is a saturated alkyl group. Although this substance has a hydrophobic group in its molecule, it was thought that it would not form a monolayer because it does not have a strong parent group, but it has a long alkyl chain of 5.5'-(1,4-
(phenylene)-bis(2-cyano-2, tohentagenoic acid) di-n-dodecyl ester forms a monomolecular film by itself. In addition, 5 with a small number of carbon atoms in the alkyl group
．． 5'-(1,4-phenylene)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester can be mixed with a suitable amphipathic compound to form a solution on the water surface or in aqueous cadmium chloride solution. Forms a stable monolayer on the liquid surface. The formation of such a monomolecular film is caused by the surface pressure -
This is clear from the fact that the presence of a solid condensed phase was confirmed in the occupied area curve.

Usually, the alkyl group has 12 to 2 carbon atoms.
0 long chain saturated fatty acids and long chain saturated alcohols are used. Examples of long-chain saturated fatty acids include tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, and arachidic acid. Examples of long-chain saturated alcohols include lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, and eicosyl alcohol. These amphiphilic compounds may be used alone or in combination of two or more.

Next, one example of a suitable method for preparing the cumulative film will be described. ) The dialkyl ester alone or this and a suitable amphipathic compound are dissolved in an organic solvent such as chloroform at a molar ratio of usually 1:5 to 1:1, and then this solution is dissolved in distilled water or an aqueous cadmium chloride solution. 5.5'-(1,4-phenylene)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester after being gradually dropped onto the liquid surface, compressed, and placed on the liquid surface. , or a mixture of this material and an amphipathic compound to form a monomolecular film, and then transfer this monomolecular film onto a substrate such as a quartz plate. This process is repeated to create a cumulative film.

The absorption spectrum of the cumulative film created in this way is
There is an absorption maximum at 360 nm, which is similar to that of crystals or solutions (
It can be seen that the cumulative film has a molecular arrangement different from that of crystals or solutions.

When the cumulative film thus produced is irradiated with light using a xenon lamp or the like, addition polymerization easily occurs and a thin film-like polymer is obtained. For example, when a 10-layer film is irradiated with light of 420 nm or more, the absorbance gradually decreases in the ultraviolet absorption spectrum, while the absorption of double bonds (1610 cm-') decreases in the square absorption spectrum. , it can be seen that a reaction occurred between double bonds.

The thin film obtained by such light irradiation is soluble in tetrahydrofuran, and the molecular weight measured by gel permeation chromatography is 1000-300.
It is about 0. From these facts, it can be seen that the thin film is a dimer to pentamer low polymer having a cyclobutane ring produced by a cycloaddition reaction of double bonds. When this low polymer thin film is irradiated with light of 320 am or more, the absorbance decreases and the absorption maximum at 36 Gam almost disappears. This is thought to be because the reaction between the double bonds further progresses to form a high polymer, and the resulting thin film becomes difficult to dissolve in general organic solvents. When this high polymer film is irradiated with light of 290+++a or less, it depolymerizes and becomes a low polymer, and when this low polymer is irradiated with light of 32 ha or more, it becomes a high molecular weight polymer again.

This indicates that the thin film polymer produced by the production method of the present invention has reversible depolymerizability by light. Since the thin film polymer has such properties and high mechanical strength, it can be used as a resist material in the production of electronic devices and microlithography.

Effects of the Invention According to the method of the present invention, 5. By using S'-(1,4-7dinilene)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester as a monomer and irradiating the cumulative film with light, the thin film weight can be increased. Combinations can be easily manufactured.

The thin film polymer obtained by the method of the present invention has reversible depolymerizability by light and has good mechanical strength.
For example, it is useful in the production of electronic devices, as a resist material in microlithography, or as a crosslinking agent or photosensitive material.

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.

Example 1 Acetosaka: s, s' purified by several times of recrystallization
-・, -2,t (1,4-phenylene)-bis(2-cyano-2,topentadienoic acid) di-n-dodecyl ester in chloroform solution (O19XIF'M) was added to a cadmium chloride aqueous solution ( After the mixture was gradually dropped onto the liquid surface of 10-'M) and expanded, it was compressed to form a monomolecular film.

From the surface pressure-occupied area curve, 20-30 dy++/c
Since the existence of a solid condensed phase was confirmed by ra, the surface pressure was reduced to 2.
A monomolecular film was formed by setting 5 dy++/cta.

Next, the monomolecular film thus formed was transferred to a quartz plate by a vertical dipping method to produce a cumulative film consisting of 10 monomolecular film layers. This cumulative film has an absorption maximum at 3f+hm, and when it is irradiated with a xenon lamp, the absorption maximum gradually decreases, and the infrared absorption spectrum of the irradiated film shows a decrease in double bond absorption (1610 cm is seen,
It was shown that the reaction occurred between double bonds. A film that has been irradiated with light for 15 minutes is almost insoluble in common organic solvents, but a film that has been irradiated for a short time, for example, 1 minute, is soluble in tetrahydrofuran, and the molecular weight determined by gel permeation chromatography is ! 200 to 3000 (two-layer pentamer).

Example 2 5,5'-(1,
4-7enylene)-bis(2-cyano-2,4-pentagenoic M) di-n-hexyl ester in chloroform solution (0,89X 10-3M) and arachidic acid in chloroform solution (0,19X to- 3M) were mixed at a molar ratio of 1:5, and this solution was gradually dropped onto the surface of a cadmium chloride aqueous solution (10-3M) to develop it, and then the surface pressure-occupied area curve was measured. The presence of a solid condensed phase was observed in this curve, confirming the formation of a monomolecular film.

Therefore, the surface pressure was set to 25 dya/cm to form a monomolecular film. Next, the monomolecular film formed in this way was transferred to a quartz plate by the vertical dipping method, and the monomolecular film 1
A cumulative film consisting of 0 layers was produced. The absorption spectrum of this cumulative film has an absorption maximum at 360 nm, and a xenon lamp is used as a light source, and a filter (Corning 3-72) is used.
When irradiated with light of 420 nm or more, the absorbance gradually decreased.After 3 minutes of irradiation, the accumulated film was dissolved in tetrahydro7 run, and the molecular weight was examined by gel permeation chromatography. It turned out to be. When this low polymer was further irradiated with light of 320 nm or more, the absorption maximum decreased and almost disappeared.

This membrane is insoluble in common organic solvents and is a high polymer.

When this high polymer was irradiated with short wavelength light (λ (290 nm)), an absorption maximum of 360 am gradually appeared, indicating depolymerization to a low polymer. Then, it becomes a high polymer again, and the conversion from high polymer to low polymer proceeds reversibly by light.

Example 3 5,S'-(1,
A chloroform solution of 4-phenylene)-bis(2-cyano-2, topentagenoic acid) di-n-dodecyl ester (0,89X 1G-'M) and a chloroform solution of arachidic acid (0,19X I O- 'M) in molar ratio 1
A portion of this solution is dropped onto the surface of distilled water, developed, and then gradually compressed to reduce the surface pressure.
The occupied area curve was measured. The presence of a solid condensed phase was observed in this curve, confirming the formation of a monomolecular film. Therefore, the surface pressure was set to 30 dy+/cm to form a monomolecular film.

Next, the monomolecular film thus formed was transferred onto a quartz plate by a vertical dipping method to produce a cumulative film consisting of 10 monomolecular film layers. The absorption spectrum of this cumulative film is 36h
It has an absorption maximum at 300 nm using a xenon lamp as a light source and a filter (Corning 0-52).
When irradiated with light of m or more, the absorbance gradually decreases, and the infrared absorption spectrum of the irradiated film shows a decrease in double bond absorption (1610 cm"'), and there is a decrease in absorption between double bonds. It was found that a reaction had occurred. Films irradiated with light for 10 to 15 minutes were almost insoluble in common organic solvents, but films irradiated for a short period of time, for example 2 minutes, were soluble in tetrahydrofuran, and gelpermini -The molecular weight determined by Sikon chromatography was 1200 to 2500 (two-layer tetramer).

Example 4 A chloroform solution (0.89×10-”M) of di-n-amyl ester ((2-cyano-2-cyano-2,tohentagenoic acid)) and a chloroform solution of arachidic acid ( 0.89
The surface pressure-occupied area curve was measured by gradually dropping it onto the liquid surface of M) and then gradually compressing it. was confirmed. Therefore, the surface pressure was set to 30 dyn/cm,
A monolayer was formed.

Next, this monomolecular film was transferred to a quartz plate by a vertical dipping method to produce a cumulative film consisting of six monomolecular film layers. The absorption spectrum of this mixed cumulative film had an absorption maximum at layer 36 m, and when it was irradiated with light of 300 am or more using a xenon lamp as a light source and a filter (Corning O-52), the absorbance gradually decreased. . The infrared absorption spectrum of the irradiated film shows double bond absorption (lslocm-
') was observed, indicating that a reaction occurred between double bonds. A film irradiated for 10 to 15 minutes is almost insoluble in common organic solvents, but a film irradiated for a short time, for example 2 minutes, is soluble in tetrahydrofuran and has a molecular weight of 9.
50 to 2500 (dimer to tetramer).

Claims (1)

[Claims] 1 5,5'-(1,4- phenylene)-bis(2-cyano-2,4-pentagenoic acid) dialkyl ester or a mixture of this and an amphipathic compound, and then irradiating the film with light. A method for producing a thin film polymer.