JPH0649783B2 - Photosensitive ultra-thin film, method for producing the same, and method for producing a photopolymerization cumulative film using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive ultrathin film (monomolecular film and cumulative film).
And a method for producing the same, and a method for polymerizing the photosensitive ultrathin film by light.

In recent years, the Langmur Blodgett film, which is an organic ultra-thin film that easily has an oriented structure, has been reexamined as an ultra-fine processed resist, a light modulation element, and an electroluminescent element, and an anthracene derivative (Japanese Patent Laid-Open No. 52-35579 and the same publication). No. 52-35587) and a metal salt of a long-chain aliphatic carboxylic acid (see JP-A-52-117146), and the like have been proposed. However, these monomolecular films do not have sufficient mechanical strength because the compounds constituting them are low molecular weight compounds.
Therefore, in order to improve the strength of the film, it has been proposed to polymerize a monomolecular-forming monomer that can be polymerized in the state of a monomolecular film or as a cumulative film, and then polymerize it by heat, ultraviolet rays or electron beams. [JP-A-56-4229, JP-A-56-4229]
43220, Journal of Polymer Science Polymer Chemistry Edition (J.
Poly. Sci., Poly. Chem.), 17 , 1631 (197)
9), Journal of Colloid & Interface Science (J. Colloid & Int. Sci.), 25
5 , 521 (1977) and Thin Solid Films 99 , No. 1-3 (1983).
However, it is difficult to complete such a polymerization reaction to 100%, and there remains a problem that unreacted monomers are likely to occur.

In view of such a situation, the present inventors have made the polymerization reaction 100
% As a result of diligent research on a monomolecular film and a cumulative film that can progress,
Long-chain alkyl ester of m- and p-phenylenediacrylic acid represented by the following formula However, it is possible to form a highly oriented monomolecular film on the water surface and accumulate it while maintaining the oriented state on the solid substrate. Furthermore, the monomolecular film and the accumulated film are easily polymerized by actinic rays. It was possible to complete the present invention. That is, the present invention is: 1. A photosensitive ultrathin film consisting of a phenylene bisacrylic acid ester-based monomolecular film mainly composed of a compound represented by or its cumulative film, 2. A monomolecular film-forming substance mainly consisting of the compound represented by is developed as a monomolecular layer, and the developed film thus formed is compressed into a solid monomolecular agglomerate film, or as a monomolecular film on a solid substrate or its accumulation. A method for producing a photosensitive ultra-thin film characterized by laminating as a film, 3. The following formula The photopolymerization accumulation is characterized in that a photosensitive ultra-thin film mainly composed of a compound represented by is irradiated with an actinic ray on a photosensitive ultra-thin film to cause a photo-polymerization reaction, and then stacked on a solid substrate. Membrane manufacturing method,
And 4. The following formula Characterized in that a photosensitive ultrathin film consisting of a phenylene bisacrylic acid ester-based monomolecular film mainly composed of a compound represented by or a cumulative film thereof is formed on a solid substrate, and then it is irradiated with actinic rays to be polymerized. It is a method for producing a photopolymerization cumulative film.

The m- and p-phenylene bisacrylic acid esters used in the present invention can be prepared by the following known method {Ear Coon,
Hemitzie Berichte (R.Kuhn, Chem.Ber,), 93 , 3
048 (1960)} Can be synthesized by. The above-mentioned phenylene bisacrylic acid ester has a hydrocarbon group having 7 to 30 carbon atoms,
It has an acrylic ester group at the meta or para position. These are added to an organic solvent such as chloroform, toluene, acetone, methyl ethyl ketone or tetrahydrofuran in 1-2 parts.
After dissolving 0 mg / 100 ml, a monomolecular film can be formed by spreading the solution on a clean water surface. The monomolecular film developed on this water surface is irradiated with active rays on the water surface to polymerize, or once accumulated on a solid substrate, and then irradiated with active rays to polymerize to be insoluble in a solvent. can do. In order to carry out photopolymerization on the water surface, it is first necessary to compress the monomolecular film in order to make the condensed state suitable for polymerization. As an example, in the case of metaphenylene bisacrylic acid ester, when it is compressed at a pressure of 3 to 10 mN / m at 15 to 20 ° C., photopolymerization on the water surface proceeds. The actinic ray irradiated at this time is
Ultraviolet rays, visible rays, γ rays, electron rays, 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 is hydrophobized. At the time of accumulation, the photopolymerized monolayer on the water surface is compressed at a pressure of 10 to 40 mN / m, preferably at a pressure of 20 to 30 mN / m while accumulating, thereby achieving a high accumulation ratio.

It is also possible to polymerize the monomolecular film of the present invention by once accumulating the monomolecular film of the present invention on a solid substrate and then irradiating it with an actinic ray. The polymerization of the cumulative film proceeds depending on the film compression force at the time of forming the cumulative film.

In the case of the phenylene bisacrylic acid ester of the present invention, when the monomolecular film spread on the water surface is accumulated while being compressed at a pressure of 2 to 40 mN / m, preferably 5 to 30 mN / m, its accumulation In that case, photopolymerization of the cumulative film easily proceeds. The photopolymerization reaction in the cumulative film is generally considered to proceed as follows.

By this polymerization, the solubility of the film is changed, and when the degree of polymerization is sufficiently high, the photopolymerized film becomes insoluble.
Therefore, the monomolecular film and the cumulative film of the present invention can be applied to ultra-fine processed resists, ultra-fine patterned insulating films, etc. by taking advantage of the alignment structure and photopolymerization characteristics at the molecular level. It is possible, and the degree of fine processing (resolution) is significantly improved as compared with the conventionally known resist material. Examples will be given below to explain the present invention in more detail.

Example 1 6.70 g of isophthalaldehyde in a 4-neck round bottom flask (300 ml) equipped with a stirrer, thermometer and reflux.
(0.05 mol), malonic acid 11.44 g (0.11 mol), piperidine 4.3 g (0.11 mol) and pyridine 100 ml were added, and at 70-80 ° C. in a nitrogen atmosphere,
Stir for 6 hours. After the reaction, mix the mixture with 1 / 10N HCl.
When the system was poured into water to neutralize the system, crystals were precipitated. The crystals are separated, washed with water, dried in vacuum at 50 ° C., and represented by the following formula: 1,4-phenylenebis (2-acrylic acid) 7.6g was obtained. Subsequently, this compound was added to 100 ml of thionyl chloride, and the above carboxylic acid was converted into an acid chloride by heating and refluxing for 6 hours in the presence of a catalytic amount of dimethylformamide. The acid chloride was purified by recrystallization from a 1: 1 (volume ratio) mixed solvent of toluene and n-hexane, followed by vacuum drying. 5.3 g of the acid chloride obtained by the above purification was added to chloroform 10
After dissolving in 0 ml, it was stirred with 250 g of eicosanol-1 (C ₂₀ H ₄₁ OH) under reflux in the coexistence of 3.2 g of pyridine for 8 hours. After removing chloroform from the system after the reaction by evaporation, the precipitated solid product was washed with water and repeated.

By the above-mentioned post-treatment, the obtained crude reaction product was recrystallized from ethanol three times. From the IR spectrum, NMR spectrum and elemental analysis of the thus obtained crystal, it was confirmed that this was m-phenylenebis (eicosyl-2-acrylate) [hereinafter abbreviated as m-PBEA]: Was identified. Next, in order to prepare a monomolecular film of this product, 10 mg of m-PBEA was dissolved in 25 ml of twice-distilled chloroform, and then Lan having an aqueous phase surface area of 562 cm ² was prepared.
20 μ of 100 μl of the above solution was placed on a gmuir type water tank for measuring surface pressure / area curve using an ultramicropipette.
The solution was gradually added dropwise in increments of 1. After finishing the dropping, apply the water surface spreading film to 5
After standing for a minute, the partition plate was started to move, and the surface pressure-area curve (hereinafter abbreviated as π-A curve) of the membrane was measured.
As a result, m-PBEA spread on the surface of the water was 25-5.
At 17 ° C. under a surface pressure of 5 mN / m, a condensed film was provided, and the molecular occupied area was 38.0Å ² .

Example 2 While keeping the surface pressure of the m-PBEA monomolecular film obtained in Example 1 at 5 mN / m, two 10 W low-pressure mercury lamps were irradiated from a position 5 cm above the water surface for 8 minutes. Two minutes after the start of light irradiation, the monolayer on the water surface began to expand, and after 6 minutes, the expansion of the film reached 1.8 times the initial film area. At that point, the light irradiation was stopped, and the film thus light-irradiated was again exposed to 30 mN
While compressing at / m, the surface-hydrophobicized calcium fluoride plate was immersed and pulled up vertically to the water surface (hereinafter, abbreviated as LB method), which was repeated 30 times to obtain a cumulative film. As a result of measuring the FT-IR spectrum of this product, νC = C
(1635 cm ^-1 ) disappeared significantly, and νC = 0 (1705
cm ^-1) are shifted to 1725~1730cm ^-1, m
-Suggested photopolymerization of PBEA.

Example 3 The water surface spreading film of m-PBEA obtained in Example 1 was 30 mN /
While compressing to m, it was accumulated by a 30-layer LB method on a calcium fluoride plate that had been surface-hydrophobicized in advance. The average cumulative ratio was 0.94. The cumulative film thus obtained has 2
When the change in absorption intensity of νC = C in the IR spectrum was traced at regular intervals after irradiation with a 0 W low-pressure mercury lamp, the absorption intensity of νC = C was the initial value after 1 minute and 5 minutes of light irradiation. It dropped to 32% and 10% in every corner, and disappeared almost completely after 60 minutes. νC = 0 is not accompanied a decrease in νC = C, and long wave number shifted from 1705 cm ^-1 to 1725~1730cm ^-1.

From the above results, it was suggested that the m-PBEA monomolecular cumulative film accumulated on the solid substrate was photopolymerized.

Example 4 In the synthesis of m-PBEA of Example 1, terephthalaldehyde was used instead of isophthalaldehyde, and para-phenylenebis (eicosyl-
2-acrylic acid) [abbreviated as P-PBEA] was obtained. This product was dissolved in 10 mg of double-distilled chloroform (25 ml) and a monomolecular film was formed on the water surface in the same manner as in Example 1. The product was a condensed film at 35-6 mN / m. Was formed, and its molecular limit occupation area was 55Å ² .

Example 5 5 mN was added to the water surface spreading film of P-PBEA obtained in Example 4.
When light was irradiated in the same manner as in Example 2 while applying a constant pressure of / m, the film expanded with the light irradiation time, and after 6 minutes, the film area reached 1.85 times the initial value. At this point, the light irradiation was stopped, and a cumulative film was obtained on CaF ₂ by the LB method while compressing the film to 30 mN / m (30 layers accumulated). As a result of measuring the FT-IR spectrum of this product, νC = C
The absorption intensity at (1637 cm ^-1 ) decreased significantly, and νC = 0.
(1710cm ^-1) is shifted to 1730~1735cm ^-1. From the above results, it was suggested that the monomolecular film of P-PBEA spread on the water surface was polymerized by light irradiation.

Example 6 The water-spreading film of P-PEBA obtained in Example 4 was 30 mN /
Ca subjected to a surface hydrophobic treatment while being compressed under a pressure of m
30 layers were accumulated on the F ₂ plate. (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 absorption intensity at νC = C (1637 cm ⁻¹ ) was 1 minute and 5 minutes after irradiation with light. , 44% of the initial value,
And decreased to 16%. Further, as the absorption intensity of νC = C decreases, νC = 0 (1710 cm ⁻¹ ) becomes 1735.
Shifted to cm ^-1 . From the above results, it was suggested that the P-PBEA monomolecular cumulative film was polymerized by light irradiation.

Comparative Example 1 Instead of forming the m-PBEA cumulative film from the water surface spread film by the LB method, m-PBEA was formed on the same CaF ₂ plate by spin coating.
When a laminate was formed and light was irradiated in the same manner as in Example 3 except that the PBEA film was formed, the absorption intensity of νC = C was 80% of the initial value after 1 minute and 5 minutes of light irradiation, respectively.
% And 50% remained, which revealed that the reaction was much slower than in the cumulative film.

Comparative Example 2 Instead of the P-PBEA cumulative film in Example 6, the same
A P-PBEA film was formed on a CaF ₂ plate by a spin coating method and irradiated with light in the same manner as in Example 6, and the absorption intensity of νC = C was 1 and 5 minutes after irradiation with light. , 86% and 73% of the initial values respectively remained, and it became clear that the reaction was extremely slower than in the cumulative film.

Claims (4)

[Claims] 1. The following formula A photosensitive ultra-thin film composed of a phenylene bis (acrylic acid ester) -based monomolecular film mainly composed of a compound represented by or its cumulative film. 2. The following formula A monomolecular film-forming substance mainly composed of a compound represented by the formula (1) is developed as a monomolecular layer, and the developed film thus formed is compressed into a solid monomolecular aggregated film, or as a monomolecular film on a solid substrate or A method for manufacturing a photosensitive ultrathin film, which comprises stacking as a cumulative film. 3. The following formula The photopolymerization accumulation is characterized in that a photosensitive ultra-thin film mainly composed of a compound represented by is irradiated with an actinic ray on a photosensitive ultra-thin film to cause a photo-polymerization reaction, and then stacked on a solid substrate. Membrane manufacturing method. 4. The following formula Characterized in that a photosensitive ultrathin film consisting of a phenylene bisacrylic acid ester-based monomolecular film mainly composed of a compound represented by or a cumulative film thereof is formed on a solid substrate, and then it is irradiated with actinic rays to be polymerized. A method for producing a photopolymerization cumulative film.