JPS62265661A - Material sensitive to electromagnetic wave - Google Patents

Abstract

PURPOSE:To obtain a material sensitive to electromagnetic waves and causing easy gelatinization by polymn. with high sensitivity on being irradiated with electromagnetic waves at a low cost in large quantities by using a specified synthetic lipid monomer as the principal constituent of a material sensitive to electromagnetic waves. CONSTITUTION:A synthetic lipid monomer having at least one acyl chain derived from eleostearic acid and represented by the formula as a hydrophobic acyl chain is used as the principal constituent of a material sensitive to electromagnetic waves. The skeleton of the monomer is phospholipid, sphingolipid, glucolipid, glyceride, glycerol ether, dialkyl phosphate, dialkyl phosphonate, alkyl phosphinate monoalkyl ester, phosphonolipid or other prescribed compound. The material sensitive to electromagnetic waves contains an auxiliary coating agent, a stabilizer, a buffer, a chelating agent, a hydrophilic binder and a diluent besides the synthetic lipid monomer as required.

Description

Detailed Description of the Invention (1) Background of the Invention (Technical Field) The present invention relates to an electromagnetic wave sensitive material. Specifically, the present invention relates to an electromagnetic wave-sensitive material in which a hydrophobic chain having a polymerizable functional group is incorporated into a lipid molecule.

(Prior Art) In recent years, electromagnetic wave-sensitive materials such as ultraviolet-sensitive materials and electron beam-sensitive materials have attracted attention as electromagnetic energy base materials, sensor materials, photoresist materials, image recording element materials, and the like. Conventionally, this electromagnetic wave-sensitive material is a polymer with an epoxy structure, a carbon-carbon double bond, or a sensitive group such as an azide group introduced into the molecule, or a bis7
OH? Electromagnetic reactive compounds such as dido? 3, C0OH group,
Those mixed with polymers that have NH2 groups or unsaturated bonds and show little or no reactivity to electromagnetic waves, or those that use sensitive polymers or oligomers such as vinyl monomers and ethylene oligomers together with polymerization initiators. etc. are known. however,
These electromagnetic wave sensitive materials have low sensitivity to electromagnetic waves and are often impractical unless a sensitizer is used in combination (Japanese Patent Publication No. 46-42,363, etc.). Furthermore, in the field of photoresists, for example, miniaturization of pattern dimensions is desired, and photoresist materials with high resolution are required. To this end, attempts have been made to reduce the resist film thickness to improve resolution, and to improve contrast and improve resolution by installing an electromagnetic wave fading layer on the resist. Even with the method of reducing the resist film thickness, it is not possible to reduce the resist film thickness very much in order to obtain a resist film without producing pinholes, and when a fading layer is used, the fading layer Since the electromagnetic waves are irradiated through the , the irradiation time becomes long. As described above, it has been difficult to obtain satisfactory performance in terms of sensitivity, contrast, resolution, etc. in the electromagnetic wave-sensitive materials described above.

Recently, polymerizable lipids have been proposed as new N-magnetic wave sensitive materials, and various polyacetylene type lipids have been synthesized and numerous studies have been conducted. Regarding the manufacturing method of polyacetylene type lipids, U.S. Pat.
．． 941. o14@ and No. 3,065.283, etc., and Ringsdorff [H.

Macromolecule Chemistry [Hakromol, Chem, Co. 18
0. 1059 (1979)), and U.S. Patent No. 4,314 regarding its application as a rough image forming material.
, No. 021. In the case of such polymerizable lipids, unlike conventional electromagnetic wave-sensitive materials, extremely high resolution can be obtained because a homogeneous, extremely thin, and dense molecular layer can be formed by polymers on the lipid. Furthermore, the sensitivity is high and the use of polymerization initiators, sensitizers, reducing agents, etc. is unnecessary. However, in the case of polyacetylene-type lipids currently being developed, the conjugated triple bond within the molecule is synthesized through numerous reaction steps in a purely chemical manner based on extremely detailed molecular design, making it impractical. Not only is it difficult to synthesize on a large scale, but the final product, an electromagnetic wave-sensitive material, is extremely expensive.

In general, polyacetylene-type lipids have two or more conjugated triple bonds in their molecules, and because they have a linear and rigid structure, they can only be polymerized by electromagnetic waves in the gel phase below the phase transition temperature, that is, in the crystalline state. It had the disadvantage that it required considerable expense to lower the temperature of the reaction system.

II. OBJECTS OF THE INVENTION Accordingly, the present invention aims to provide novel electromagnetic radiation sensitive materials. The present invention also provides light, ultraviolet light, β-rays,
The object of the present invention is to provide a highly sensitive electromagnetic wave-sensitive material that is easily polymerized and gelled by irradiation with electromagnetic waves such as γ-rays and X-rays. An object of the present invention is to provide an electromagnetic wave-sensitive material whose main component is a polymerizable lipid that is easy to synthesize and can be provided in large quantities at low cost.

In the above terms, the hydrophobic acyl chain has the general formula CH3 (
CH2)3 CH=CHCH=CHCH=CH(CH2
)7 C-(I) This is achieved using an electromagnetic wave-sensitive material whose main component is a synthetic lipid monomer having at least one acyl chain derived from eleostearic acid.

The present invention also provides that the synthetic lipid polymer is a phospholipid,
Sphingolipid, glycolipid, glyceride, glycerol ether, dialkyl phosphate, dialkyl phosphate phosphinate monoalkyl ester, phosphonolipid, N,N-disubstituted dimethylammonium halide,
An electromagnetic wave-sensitive material having a skeleton selected from the group consisting of trialkylmethylammonium halide, tetraalkylammonium halide, dialkylsulfosuccinic acid ester, and 2,3-cyasyloxysuccinic acid. It is.

The present invention further provides that the synthetic lipid compound has the general formula [wherein R is 10H2±2N'' (CH3)3, +CH2÷
2N0H3 or 10H20H (N0 to 13) -Coo
It is o. ] This is an eleostearic acid phospholipid, which is an electromagnetic wave-sensitive material. The present invention further provides an electromagnetic wave sensitive material having the general formula %.

IIl. Detailed Description of the Invention The present invention will be explained in more detail below based on examples.

The electromagnetic wave-sensitive JtA 1 of the present invention has the general formula (I) CH3(CH2)3 CH=CHCH=CHCH=CH as a hydrophobic acyl chain.
The main component is a synthetic lipid polymer having at least one acyl chain derived from eleostearic acid represented by (CH2)7C-(I).

As used herein, the term "lipid monomer" refers to an amphiphilic compound having a hydrophilic polar part and a hydrophobic non-polar part consisting of at least one long-chain aliphatic acyl chain, such as phosphatidylcholine, bosph-7-thiol, etc. Phospholipids such as diethanolamine, phosphatidylserine and phosphatidylglycerol, sphingolipids such as sphingomyelin, glycolipids such as ceredoside, plant glycolipids and gangliosides, glycerides such as phosphonoglycerides, glycerol ethers N,N-2-disubstituted dimethylammonium Those having a skeleton of lipids or lipid-related compounds such as halides, alkyl ammonium halides such as trialkylmethylammonium halides and tetraalkylammonium halides, dialkyl sulfosuccinates, and 2,3-cyasyloxysuccinic acids. As expected. These uraalkylammonium halides and other compounds that have a skeleton are those that have a horizontal structure in which a lyacyl chain is bonded to the end or side of the alkyl chain of the compound that serves as the skeleton through an ester bond. be. In addition, the names of the above lipids or lipid-related compound groups are used to indicate the groove structure that forms the skeleton of the lipid epidermis.
Therefore, it should be interpreted in a broad sense to include its substituted products and similar compounds, and includes, for example, compounds in which the moiety represented by "alkyl" in the name is an unsaturated hydrocarbon group such as alkenyl, alcadenyl, alcadenyl, alkynyl, etc. .

The synthetic lipid-based polymer having at least one hydrophobic acyl chain represented by the general formula (I), which is the main h1 component of the electromagnetic wave-sensitive material of the present invention, can be used as the above-mentioned [lipid-based polymer].
It is a type of J and its hydrophobic acyl chain has been synthetically introduced. In particular, the synthetic lipid compound has the general formula (III) [wherein R is 10H2±2
No(CH3)3 (phosphatidylcholine), +C
H2±2 N”R3 (cephalin) or -CH2CH
(N''R3>-Coo (phosphadecylserine), and R+ and R2 are saturated or unsaturated hydrocarbon groups.) Typical biological lipids are phospholipids, preferably phosphatidylcholine. One with a skeleton is desired.

The hydrophobic acyl group represented by general formula (1) can be easily introduced into a lipid monomer having the above-described skeleton structure by a known method using eleostearic acid as a starting material. This eleostearic acid has the general formula (IN CH3(CH2)3 CH=CliCH:CHCH=C
It is a natural unsaturated fatty acid with a conjugated double bond at the 9th, 11th, and 13th position represented by H(CH2)y C00N (I -), and it can be easily extracted from tung oil and contains 80 to 95% by weight of mixed fatty acids. %. The tung oil fatty acid obtained by hydrolyzing this tung oil contains 6 eleostearic acids.
It is contained in an amount of 0% by weight or more, preferably 80% by weight or more, and the remaining components include saturated acid, oleic acid, linoleic acid, etc. In order to prepare the electromagnetic wave-sensitive resin of the present invention, this tung oil fatty acid may be used as it is as a natural unsaturated fatty acid, or if necessary, it may be purified by column chromatography and/or recrystallization to obtain only eleostearic acid. You may take it out and use it.

For example, to introduce an acyl chain represented by the general formula (I>) from the backbone of phosphat lipid,
This is done as follows. Another starting material, the hydrophilic polar portion of a lipid, is a natural phospholipid, many of which have a hydrophobic nonpolar portion of a saturated aliphatic acyl chain.

) can be obtained more easily and in large quantities. Natural phospholipids are hydrolyzed and subjected to an esterification reaction with eleostearic acid, especially as their metal complexes, such as cadmium. In the esterification reaction, a natural phospholipid hydrolyzate or its metal complex is added to a medium such as chloroform, carbon tetrachloride, or methylene chloride and suspended in a stirred solution, and eleostearic acid is added to this suspension. 200 to 400 parts by weight, preferably 300 to 370 parts by weight, and an appropriate amount of a catalyst per 100 parts by weight of the phospholipid hydrolyzate are added, and the reaction system is heated with an inert gas such as argon, nitrogen, or helium. The reaction is preferably carried out at a temperature of 15-25°C in the dark for 24-90 hours, preferably 40-72 hours.

Catalysts include 4-dimethylaminopyridine,
50 to 1 per 100 parts by weight of bospholipid hydrolyzate
00 parts by weight, preferably 80 to 85 parts by weight.

After the reaction, white insoluble matter precipitates, which is filtered off, and the medium d is distilled off under reduced pressure at air temperature, and then redissolved in a mixed solvent of chloroform/methanol/water (volume ratio = 415/1) for ion exchange. Contact with resin and then wash off. After distilling off the mixed solvent under reduced pressure, it was dissolved in a small amount of chloroform and purified using a chloroform and methanol mixed solvent using a silica gel column, etc.
General formula (II) [wherein R is 10H2±2 No (CH3)3,
Φ + CH2±2NH3 or 1082 CH(N”R3
)-Co00, etc. ] Eleostearic acid phosphoribide is obtained.

The electromagnetic wave-sensitive material obtained varies depending on the starting material used. For example, when using egg yolk lecithin, phosphatidylcholine eleostearate represented by general formula (Iv), or when using cephalin or phosphatidylserine, etc. Electromagnetic wave sensitive materials corresponding to these can be obtained.

In addition to the above-mentioned synthetic lipid monomers, the electromagnetic wave-sensitive material of the present invention also contains coating aids, stabilizers,
Additives such as buffers, chelating agents, or e.g. gelatin, polyvinyl alcohol, poly(N-vinyl-2
hydrophilic binders such as polyacrylamide and acrylamide copolymers, acrylic polymers and copolymers, or diluents.

The electromagnetic wave sensitive material of the present invention obtained in this way is
Since the main component is a synthetic lipid having an acyl chain derived from eleostearic acid and having three conjugated double bonds in the chain as represented by the general formula (I>), it By irradiating electromagnetic waves such as ultraviolet rays, β rays, γ rays, and X-rays, especially ultraviolet rays, the three conjugated double bonds in this hydrophobic acyl chain easily cause a crosslinking reaction, and the polymers on the synthetic lipid polymerize together. This conjugated triene-type synthetic lipid polymer has a maximum wavelength of 2701 m or more in its absorption spectrum, which is a relatively low energy position (see Figure 2), and it itself cannot be polymerized by light energy. Because this process is carried out, polymerization initiators, sensitizers, reducing agents, etc. are not required.

Furthermore, while conventional polyacetylene-type lipids polymerize only in a crystalline state below the gel-liquid crystal phase transition temperature, this conjugated triene-type synthetic lipid monomer has a relatively flexible grooved hydrophobic acyl chain. Polymerization reactions caused by electromagnetic waves occur in any state above or below the phase transition temperature.

The electromagnetic wave sensitivity of the present invention is that before being irradiated with electromagnetic waves, it is soluble in chloroform, ether, methanol, dimethylformamide, etc.; completely insoluble in
A significant difference in solubility occurs due to electromagnetic irradiation.

The electromagnetic wave-sensitive material of the present invention can be used for various purposes. For example, when it is used as an image forming element, the synthetic lipid material constituting the electromagnetic wave-sensitive material can be coated on various substrates, such as glass material. It can be obtained by supporting it on the surface of synthetic resin, fibrous material, rubber material, etc. Although there are various methods for supporting the support, a simple method is to coat the substrate with a solution in which a synthetic lipid-based polymer is dissolved in a suitable solvent, and then evaporate the solvent. When this image forming element is exposed to electromagnetic waves such as ultraviolet rays through a photographic negative or the like, and the 7-mer is washed off with a solvent, only the exposed portion remains on the substrate as a crosslinked polymer.

If the hydrophobic surface material 1 is used as a substrate, the hydrophobic non-polar part 85 of the synthetic lipid layer will be oriented toward the substrate surface, and the hydrophilic polar part will face outward, so the exposed area will remain hydrophilic. This makes it possible to directly apply water-soluble ink and transfer images onto paper, etc.

The electromagnetic wave-sensitive material of the present invention can also be spread on a water surface to form a monolayer film. If ultraviolet rays are irradiated in this state, the polymerization reaction will proceed in a monomolecular layer state, and an ultra-thin polymer film can be obtained. If necessary, the Langmuir-Ploget method may be used.
-Blodgett method.

It is also possible to form a cumulative film in which monomolecular layers are regularly accumulated using the LB method. Since such ultra-thin films have very good resolution, they are expected to be applied to the electronics field, including IC-FLSI insulating films, and even to molecular devices.

Furthermore, synthetic resin 71 constituting the electromagnetic wave sensitive material of the present invention
When Nanatsumar is dispersed in an aqueous solvent by ultrasonication or the like, it automatically forms a so-called liposome, which is an endoplasmic reticulum consisting of a lipid bilayer structure. Even in this liposome state, a polymerization reaction occurs upon irradiation with electromagnetic waves. Therefore, a hydrophilic binder containing a large number of such liposomes can be used as an electromagnetic wave-sensitive material. In this case, the progress of the polymerization reaction can be monitored by observing the ultraviolet absorption spectrum of the liposome suspension and observing the decrease in absorbance in the ultraviolet absorption band based on conjugated triene.

Next, the present invention will be more specifically prepared based on Examples.

Example Preparation of anhydride of eleostearic acid Tung oil fatty acid corresponding to 180 (l) of eleostearin was dissolved in 600 d of carbon tetrachloride immediately after dehydration distillation. 32.6 G of dicyclohexylcarbodiimide was added to this solution.
Purge the inside of the container with argon gas, seal it, and leave it for 25 minutes.
The mixture was allowed to stand at ℃ for 24 hours (with occasional stirring). Insoluble components were filtered off and distilled to dryness.

When this was purified with silica gel using dichloromethane as a developing solvent, eleostearic anhydride was obtained in a yield of 29%.

Egg yolk lecithin (Kewpie PL-100 > 45g was dissolved in 1 Yuesui Ether 450IIJi, and after filtering off the insoluble matter,
A 10% strength methanol solution of tetrabutylammonium hydroxide 50III was added and vigorously shaken at a temperature of 25°C. As the reaction progressed, the solution became cloudy and the layers gradually separated, so the solution was allowed to stand, a brown oil was sufficiently precipitated, and the supernatant was decanted. The brown oil was washed three times with 100 II Jl of dehydrated ether, then heated and dissolved in 125 dK of dehydrated methanol, 1 g of decolorizer was added under reflux at the boiling point, and the mixture was filtered while hot. After cooling, 250 ml of dehydrated ether was added to the filtrate, the precipitate was left behind and decanted, and the precipitate was dissolved in 140 ml of hot water.

To this was added 8 g of cadmium chloride hemihydrate dissolved in 20 d of pure water, and then 2.5 g of activated carbon and 2 g of a decolorizing agent were added, and after refluxing to the boiling point, the mixture was filtered using filter paper and a 0.25 μm Millipore filter. . Add 10 ethanol to this
When 0 to 150 m of III was added, a colored precipitate was formed, which was removed and only a cloudy white solution was collected. When 100 to 150 m of ethanol was added to a colander and shaken vigorously, white crystals were precipitated. Leave to stand overnight at a temperature of 0 to 5°C, collect the precipitated crystals by filtration, wash the crystals in the order of dehydrated methanol, dehydrated ether and 100% benzene, and rinse over phosphorus pentoxide overnight at a temperature of 80°C. When dried under vacuum, a cadmium complex of phosphatidylcholine hydrolyzate was obtained with a yield of 56%.

Preparation of synthetic lipid supernatant by esterification To 6.74 g of egg yolk lecithin hydrolyzate cadmium complex was added 160 II dl of chloroform immediately after distillation and suspended under stirring. To this, 24.70 g of tung oil fatty acid anhydride and 5.61 g of 4-dimethylaminopyridine as a catalyst were added, and after replacing the inside of the container with argon gas, the container was tightly stoppered and kept in the dark for 25 minutes.
The reaction was allowed to proceed for 60 hours with stirring at a temperature of .degree. At this time, a white insoluble material was precipitated, so this was filtered off, the solvent was distilled off under reduced pressure at room temperature, and methanol/chloroform/water = 5.
/4/11 Redissolve in combined IR1ooId. This solution was filtered again and the filtrate was collected using ion exchange resin ΔG-501-
It was injected into a X8 (D> (Bio-Rad) column and washed off with the previously mixed solution tR500m.

After distilling off this solvent under reduced pressure at a temperature of 25°C, it was redissolved in chloroform and purified using a silica gel column.
Tidylcholine was obtained. Its infrared absorption spectrum was as shown in FIG.

Preparation Example of Imaging Element 100fIIIJ of phosphazylcholine eleostearate obtained in the above example was dissolved in 10-methanol to prepare a 1% by weight methanol solution of phosphazylcholine eleostearate. This solution was temporarily coated with polystyrene and dried in a dark place under a nitrogen atmosphere. Layer pole paper with a round hole of 2 cm in diameter on this polystyrene plate.
It was exposed to a 5W mercury lamp for 6 hours at 30'C in a nitrogen atmosphere.

Thereafter, the polystyrene was washed with methanol, unpolymerized portions were removed, and the polystyrene was dried. When water-soluble ink was applied to the remaining ridge-shaped portion and pressed onto the paper surface, a circular image with a diameter of 2 cm was obtained on the paper surface.

IEJ construction of liposomes from synthetic lipid monomers 200 mg of phosphatidylcholine eleostearate was dissolved in chloroform 6d. The lipid solution thus obtained was placed in an eggplant-shaped flask, and the solvent was completely removed using an evaporator to form a lipid film on the bottom of the eggplant-shaped flask.

Hebesbatshu on this? (Hepes buffer)
(10mM, pH 8,0 > 10yt) was added and shaken with a portex mixer, and then treated with a chip-type ultrasonic irradiation machine (40-50W) for 10 minutes under an argon stream.The treated solution changed from a cloudy state to a clear state. A dispersion liquid was formed, and the formation of liposomes was confirmed. Furthermore, spherical particles with a diameter of 0.2 to 0.5 μm were observed using a scanning electron microscope, and the formation of liposomes was confirmed.

Polymerization example of liposomes Irradiation path 1i112CI using a 75W mercury lamp as a light source
When sample 111 was irradiated with ultraviolet rays in a water bath with a water temperature of 25°C under deaerated conditions with a tie of 10 mc+/m, the absorbance at 272 nm based on triene decreased with the passage of irradiation time, as shown in Figure 2. This confirmed that the polymerization had regressed.

TV, Effects of the Invention As described above, the present invention provides a synthetic lipid-based polymer having at least one acyl chain derived from eleostearic acid represented by the general formula (I>) as a hydrophobic acyl chain as a main component. Because it is an electromagnetic wave-sensitive material, it has high sensitivity and easily polymerizes and gels when irradiated with electromagnetic waves such as light, ultraviolet rays, β-rays, gamma-rays, and X-rays. - It is suitably used as a U material, a resist material, an image recording element v1,
Furthermore, it can be easily synthesized from starting materials that exist in large amounts in nature, is inexpensive, and can be provided to humans. Roughly speaking, the sensitive site on the synthetic lipid that constitutes the electromagnetic wave-sensitive material of the present invention has a conjugated triene structure, and its molecular structure is more flexible than that of conventional polyacetylene-type lipid monomers. Since the synthetic lipid monomer starts a polymerization reaction by electromagnetic irradiation even if it is in any state above or below the phase transition temperature, it is necessary to keep the reaction system at a low temperature below the phase transition temperature, as in the case of polyacetylene type lipid monomers. Nor. In addition, the synthetic lipid membrane can be spread on, for example, a water surface to form a very thin monolayer film and can provide very high resolution.

The above-mentioned effects can be obtained when synthetic lipids such as phospholipids, sphingolipids, glycolipids, glycerides, glycerol ethers, dialkyl phosphates, dialkyl phosphonates, alkyl phosphinate monoalkyl esters, bosphonolipids, N,N-disubstituted dimethylammonium halides, When the monomer has a skeleton selected from the group consisting of trialkylmethylammonium halide, tetraalkylammonium halide, dialkylsulfosuccinic acid ester, and 2,3-cyasyloxysuccinic acid, and furthermore, a synthetic lipid monomer. Eleostearic acid phospholipid represented by the general formula (II), especially eleostearic acid phospholipid?
It is even better when it is tidylcholine.

[Brief explanation of drawings]

Fig. 1 is an infrared absorption spectrum chart of an example of the electromagnetic wave-sensitive material of the present invention, and Fig. 2 shows the degree of polymerization of liposomes formed from the electromagnetic wave-sensitive material of the present invention by ultraviolet irradiation. It is a chart showing an example of an ultraviolet absorption spectrum.

Claims (4)

[Claims] (1) As a hydrophobic acyl chain, general formula (I)▲mathematical formula,
Chemical formulas, tables, etc. are available ▼ (I) An electromagnetic wave-sensitive material whose main component is a synthetic lipid monomer having at least one acyl chain derived from eleostearic acid. (2) The synthetic lipid monomer is phospholipid, sphingolipid, glycolipid, glyceride, glycerol ether, dialkyl phosphate, dialkyl phosphonate, alkyl phosphinate monoalkyl ester, phosphonolipid, N,N-disubstituted dimethylammonium halide, trialkylmethyl Claim 1, which has a skeleton selected from the group consisting of ammonium halide, tetraalkylammonium halide, dialkyl sulfosuccinic acid ester, and 2,3-diacyloxysuccinic acid. Electromagnetic sensitive material. (3) The synthetic lipid monomer has the general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [However, R in the formula is -(CH_2)-_2N^■(CH_
3)_3, -(CH_2)-_2N^■H_3 or -
CH_2CH(N^■H_3)-COO^■. ]
The electromagnetic wave-sensitive material according to claim 1 or 2, which is eleostearic acid phospholipid represented by: (4) R in general formula (II) is -(CH_2)-_2N^■
The electromagnetic wave-sensitive material according to claim 3, which is (CH_3)_3.