JPS61247739A - Photosensitive ultra-thin film, its production and production of photopolymerized laminated film therefrom - Google Patents

Abstract

PURPOSE:To obtain a photopolymerized laminated film highly improved in an elaborateness of processing by facilitating lamination on a solid base and easily advancing photopolymerization, by using a monomolecular membrane of a specified compound. CONSTITUTION:A phenylenebisacrylic acid ester compound of the formula (wherein R is a 7-30 C hydrocarbon, and the two substitutents in the benzene nucleus are meta or para to each other is dissolved in, e.g., acetone (1-20 mg/100 ml) and this solution is cast on the surface of still water to obtain a monomolecular membrane. This membrane is compressed at 15-20 deg.C and a pressure of 3-10 mN/m and photopolymerized by irradiation with, e.g., ultraviolet rays. The obtained polymer film is laminated on the surface of the solid base rendered hydrophobic, while it is compressed by application of a pressure of 10-40 mN/m.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive ultra-thin IIK (monolayer film and cumulative film), a method for producing the same, and a method for photopolymerizing the photosensitive ultra-thin film.

In recent years, Langmuir Blodget, an organic ultra-thin film that can easily be used for ultra-fine resists, light modulators, electroluminescent devices, L°C, and orientation structures, has been developed.
gett) films have been reconsidered, and thin film elements using 7-nthracene derivatives (Japanese Unexamined Patent Publication No. 52-35579 and references thereof) have been proposed.

However, since the compounds constituting these monomolecular films are low-molecular compounds, they are polymerized by heat, ultraviolet rays, electron beams, etc., either in a sufficient monomolecular film state or after being made into a cumulative film. It has been proposed that
．． No. 229, Publications No. 56-432'2G, Journal of Polymer Science Polymer Chemistry-1 Edition (J, Poly, Sai, +
Po1y, Chem,) s1 engineering y1631 (197
9) *Journal of Cooid and Interface Science (J, Co11oid & I
nt, Sci.), 255, 521 (1977
) and Thin Solid Films (Th1n 5ol
id Films) 995Nh1-3 (1983
)] However, it is difficult to complete such a polymerization reaction by 100 polymers, and the problem remains that unreacted monomer remains raw.

As a result of our research, we found that a long-chain alkyl ester of m-p-phenylene diacrylic acid, represented by the following formula, forms a highly oriented monomolecular film on the water surface.
They discovered that they can be accumulated on a solid substrate while maintaining their orientation, and that the monomolecular S and accumulated film can be easily polymerized by actinic rays, leading to the completion of the present invention. That is, the present invention provides: 1. A photosensitive ultra-thin film consisting of a phenylene bisacrylic acid ester monomolecular film or a cumulative film thereof consisting mainly of a compound represented by the following formula.

2. Spread a monomolecular film-forming substance mainly composed of the compound represented by the following formula as a monomolecular layer, compress the formed film to form a solid monomolecular condensation model, and place it on a solid substrate. A method for producing a photosensitive ultra-thin film, characterized in that it is laminated as a monomolecular film or as a cumulative film thereof.

3. After irradiating a photosensitive ultra-thin film consisting of a phenylene bisacrylic acid ester monomolecular film mainly composed of a compound represented by the following formula or a cumulative film thereof with actinic rays to cause a photopolymerization reaction,
A method for producing a photopolymerized cumulative film, characterized in that it is deposited or laminated on a solid substrate, and 4. A phenylene bisacrylate monomolecular film made from a compound represented by the following formula, or its! ! This is a method for producing a photopolymerized cumulative film, which includes stacking or laminating a photosensitive ultra-thin film made of L-shaped on a solid substrate, and then irradiating the film with actinic rays and polymerizing it at °C.

The m- and p-phenylene bisacrylic acid esters used in the present invention can be prepared by the following known methods (R-Turn,
R, Kuhn+ Chem,
Ber, ) * Yu and + 304 f3 (19-60)] can be synthesized. The phenylene bisacrylic acid ester has a hydrocarbon group having 7 to 30 carbon atoms,
It has an acrylic ester group at the meta or meta position. These are added to an organic solvent such as chloroform, toluene, acetone, methyl ethyl ketone or tetrahydrofuran for 1 to 2 hours.
After dissolving 0 food/food, it is spread on a clean water surface to form a monomolecular film. The monomolecular film developed on the water surface can be polymerized by irradiating actinic rays directly on the water surface, or it can be accumulated on a solid substrate and then polymerized by irradiating actinic rays. It can be done. In order to perform photopolymerization on the water surface, it is first necessary to compress the membrane in order to make the monomolecular membrane suitable for polymerization. - As an example, in the case of metaphenylene bisacrylic acid ester, photopolymerization proceeds on the water surface when compressed at 15-20° C. and a pressure of 3-10 mN/m. As the active light irradiated at this time, ultraviolet rays, visible light, r-rays, electron beams, etc. can be used. The monomolecular film of the present invention photopolymerized on the water surface is used by accumulating it on a solid substrate whose surface has been made hydrophobic. During its accumulation, a single monolayer of light on the water surface is 10 to 40 m
By accumulating while applying pressure at a pressure of N/m 2 , preferably 20 to 30 mN/m 2 , it is possible to accumulate at a high accumulation ratio.

It is also possible to carry out the polymerization of the above molecules by once accumulating the monomolecular film of the present invention on a solid substrate and then irradiating it with actinic rays. The polymerization of the cumulative film progresses depending on the pressure applied during the creation of the cumulative film.

In the case of the phenylene bisacrylic ester of the present invention, a monomolecular film developed on the water surface is heated at 2 to 40 mN/me.
Preferably, when the layers are accumulated while being compressed at a pressure of 5 to 30 LTLN/KrI, photopolymerization of the accumulated film easily proceeds. The photopolymerization reaction in the above-mentioned cumulative film is generally thought to proceed as follows.

This polymerization changes the solubility of the film, and if the degree of polymerization is sufficiently high, the photopolymerized film becomes insolubilized.

Therefore, the monomolecular film and cumulative film of the present invention can be applied to ultrafine processing resists, ultrafinely patterned extremely dense films, etc. by taking advantage of their molecular-level orientation structure and photopolymerizability. The microfabrication degree (resolution) of conventionally known resist materials can be greatly improved.

Examples will be given below to explain the present invention in more detail.

Example 1 A four-necked round-bottomed flask equipped with a stirrer, thermometer, and flow vessel (
300TR1), isophthalaldehyde 6.70.
9 (0.05 mol), macinic acid 11.44.9 (0°11 mol), piperidine 4.3 Ii (0.11 mol)
and 100 lj of pyridine, and placed in a nitrogen atmosphere (7 ml).
The mixture was stirred at 0 to 80°C for 6 hours. 1 l of the mixture after reaction
of 1/1 ON HCl was added to water to neutralize the system,
Crystals precipitated. The crystals were separated by F, washed with water, and then dried under vacuum at 50°C to give the following formula. 7.69 of 1.4-)unilenebis(2-) was obtained. This compound was then added to thionyl chloride 100- and a catalytic amount of dimethylform 7.
The above carboxylic acid was converted to acid chloride by heating and refluxing for 6 hours in the presence of amide. The acid chloride was recrystallized from a mixed solvent of toluene and n-hexane (l:l (volume ratio)) and further purified by vacuum drying. (5.31 of the acid chloride obtained by purification was molten with 100 dK of polyproform, and in the presence of 3.2 g of pyridine,
250j' eicosanol-1 (CsaH4xOH)
The mixture was stirred for 8 hours under reflux. After the reaction, coulloform was removed from the thread by evaporation, and the precipitated solid product was washed with water and returned 9 times without trace.

The crude reaction product obtained was recrystallized three times from ethanol using the above procedure. From the I'R spectrum, NMR spectrum, and elemental analysis of tl, Y& obtained in
7 acrylate) [hereinafter abbreviated as m-PBF, k]: Next, in order to create a monomolecular film of this material, 10# of m-PBEA was dissolved in 25 times twice distilled chloroform, and then an aqueous phase of 5626Ilc # was dissolved. Surface pressure of Lan gmni r type with face mound - area m +! 11°C using an ultra micropipette on a water paddle for measuring 100μ of the above solution! 20μ! It was gradually added dropwise. After dropping, the membrane was allowed to stand still for 5 minutes, and then the partition plate was moved, and the surface pressure-area curve (
Hereinafter, the π-human curve) was measured. As a result, m -P B F A developed on the water surface was 25 to 55 mN
1.1 at 17°C under surface pressure of /rr! ! a membrane, whose molecular ultimate occupied area is 38. It was OA'.

Example 2 The m-PBKA monomolecular film on the water surface obtained in Example 1 was irradiated with two LOW low-pressure water lamps for 8 minutes from a position 5Lx above the water surface while maintaining a surface pressure of 5 mN/mK. . Two minutes after the start of light irradiation, the monomolecular film on the water surface began to expand, and six minutes later, the expansion of the film reached 1.8 times the initial film area. At that point, the light irradiation was stopped, and the surface of the irradiated film was subjected to hydrophobic treatment while being compressed again at 30 mN/m.
A cumulative film was obtained by repeating the operation of dipping and pulling up the calcium tsuride plate perpendicularly to the water surface (hereinafter abbreviated as LB method) 30 times. As a result of measuring the FT-IR spectrum of this d), νC=C(1635ffi') disappeared significantly, and ν
C=0 (1705cIL”) is 1725-1730a
It was shifted to a', suggesting photopolymerization of m-PBEA.

Example 3 The m-PBEA water surface-deployed membrane obtained in Example 1 was spread over a 30 m
While compressing to N/m, 30 layers were deposited by the LB method on a calcium heptadide plate whose surface had been previously subjected to hydrophobic treatment. The average cumulative ratio was 0.94. The thus obtained cumulative film was irradiated with a 20W low-pressure mercury lamp and the change in absorption intensity of νC=C in the rR spectrum was tracked at regular intervals.As a result, after 1 minute and 5 minutes of light irradiation, νC= The absorption intensity of C decreased at the initial values of 32 cm and 100 cm, respectively, and completely disappeared after 60 minutes. νC=0 shifted to a longer wavelength from 1705 m→1725 to 1730 cm″ as νC=C decreased.

The above results suggested that cumulative photopolymerization of m-PBEA single molecules accumulated on the solid substrate occurred.

Example 4 In the synthesis of m-PBli:A of Example 1, telephthalaldehyde was used instead of inchophthalaldehyde,
By the same reaction route, rose-phenylenebis(eicosyl-2-acrylic acid) (abbreviated as P-PBEA) was obtained. This was dissolved in 10 drops and double-distilled diroform 254. Similarly, when a monomolecular film was formed on the water surface, it formed a condensed odor at a pressure of 35 to 65 mN/in, and its molecular ultimate occupied area was 55A2.

Example 5 A 5 m
When light was irradiated in the same manner as in Example 2 while a constant pressure of N/m was applied, the film expanded as the light irradiation time increased, and after 6 minutes, the film area was 1.85 times the initial value. . At this point, the light irradiation was stopped and the film was compressed to 3QmN/m while the L
By method B, a cumulative film was obtained on a CaF plate (30M cumulative).

As a result of measuring the FT-IR spectrum of this product, y
The absorption intensity of C=C(1637c!!L-”) decreased significantly, and νC=O(1710cWL″4・)・
? The P-PBEA monomolecular film spread on the water surface was polymerized by light irradiation.

Example 6 The P-PBEA water surface-deployed membrane obtained in Example 4 was spread over a 30 m
Thirty layers were accumulated on the surface-hydrophobically treated CaF plate while being compressed under a pressure of N/m.

(Average cumulative ratio: 0.83) This cumulative film was irradiated with light in the same manner as in Example 3, and the IR spectrum was measured. The initial value is 44chi,
and decreased to 16 inches.

In addition, with the decrease in the absorption intensity of νC=C, siC−0(
1710α4) shifted to 1735 signal-1. From the above results, it was suggested that the P-PBEA molecule-accumulated film undergoes % polymerization by light irradiation.

Comparative Example 1 Instead of forming the m-PBEA cumulative layer from a water surface spread film by the LB method, it was formed on the same C, F, plate by the spin code method.
The product was 7'! in the same manner as in Example 3 except that the m-PREA film was formed. 1 and irradiated with light, the absorption intensity of νC=C is 80 times the initial value at 1 minute and 5 minutes after light irradiation, respectively.

There were 50 and 50 remaining [7], and it became clear that the reaction was much slower than that of cumulative f* inertia.

Comparative Example 2 The thickness υK of the P-PBEA stacked film in Example 6
A film was formed and irradiated with light in the same manner as in Example 6.
After a few minutes, 86% and 73% of the initial values remained, respectively, and it became clear that the reaction r6 was extremely slower than that in the accumulated film.

Claims (1)

[Claims] 1. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R represents a hydrocarbon group having 7 to 30 carbon atoms, and the two substituents on the benzene nucleus are They are in meta or para position to each other. ] A photosensitive ultra-thin film consisting of a phenylene bisacrylic acid ester monomolecular film mainly composed of a compound represented by the above or a cumulative film thereof. 2. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. It is in. ] A monomolecular film-forming substance mainly composed of the compound represented by is spread as a monomolecular layer, the spread film thus formed is compressed to form a solid monomolecular condensed film, and it is applied as a monomolecular film on a solid substrate or A method for producing a photosensitive ultra-thin film characterized by laminating the film as a cumulative film. 3. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R represents a hydrocarbon group with 7 to 30 carbon atoms, and the two substituents on the benzene nucleus are in the meta or para position of each other. be. ] After irradiating a photosensitive ultra-thin film consisting of a phenylene bisacrylic acid ester monomolecular film mainly composed of the compound represented by the above or a cumulative film thereof with actinic rays to cause a photopolymerization reaction,
1. A method for producing a photopolymerized cumulative film, which comprises depositing or laminating it on a solid substrate. 4. The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc. It is in. ] Accumulating or laminating a photosensitive ultra-thin film consisting of a phenylene bisacrylic acid ester monomolecular film or a cumulative film thereof on a solid substrate, and then irradiating it with actinic rays to polymerize it. A method for producing a photopolymerized cumulative film characterized by: