JPH0231102B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD OF THE INVENTION The present invention relates to novel polymers suitable for use in optical recording elements. BACKGROUND OF THE INVENTION In response to the desire for reliable, high-capacity data storage and recovery systems, so-called optical disk recording systems have been researched and developed. These systems use a highly focused and modulated light beam, such as a laser beam, to impinge on a recording layer that can absorb significant amounts. The heat thus created chemically and/or physically alters the light-absorbing material in the area irradiated by the laser beam, changing its optical properties, such as transmittance or reflectance. For reading, the difference in the amount of light transmitted or reflected between the unexposed and recorded areas of the layer is measured. Examples of such recording systems are described in the literature mentioned in the patents and in numerous US patents, such as US Pat. No. 3,314,073 and US Pat. During data recording, a rotating disk having a light-absorbing recording layer is exposed to modulated radiation from a laser source. This radiation passes through a modulator and appropriate optics and is directed as a laser beam onto the disk, causing a number of extremely small marks to be formed along a circular path within the layer by chemical and/or physical reaction of the light absorbing layer. The frequency of marks is determined by the modulator input. By using a laser beam with a diameter of 1 μm or less, data can be stored at a density of 10 ⁸ bits/cm ² or more. The simplest optical disc consists of a dimensionally stable solid substrate and a layer of light-absorbing material, such as a metal layer, coated thereon. When this light-absorbing layer is irradiated with a focused light beam from a laser source, the light-absorbing material evaporates, chemically decomposes, and/or undergoes other physical or chemical changes to form the mark. This portion exhibits a different transmittance or reflectance than the adjacent non-marked portion. The desired properties of optical recording media are (1) high sensitivity, (2) high signal-to-noise ratio (SNR), (3) material changes, contaminants,
(4) high stability after long-term storage and/or recording and reading (J.Vac.Sci.Technology, Vol. 18, No. 1,
(See January/February, 1981, p. 70). Based on these conditions, research is continuing to obtain the best disc material. In particular, much of the research into materials for light absorbing or recording layers has focused on metals and chalcogenic materials such as tellurium, tellurium alloys, rhodium, bismuth, indium, lead, aluminum, platinum, nickel, titanium, and silver. . Of course, the most research has been done on tellurium and its alloys. Furthermore, much research has been carried out in the discovery of light-absorbing substances based on organic substances. The result is a metal/polymer composite or a dye/polymer composite. In the former, metal particles are dispersed in an organic polymeric medium. In the latter, dyes are dissolved or pigment particles are dispersed in an organic polymeric medium. The numerous patents relating to many dyes and dye/polymer dispersions are of great interest. The idea of using a thin layer of dye as an absorbing medium was first published in U.S. Patent No.
No. 4023185, No. 4097895, No. 4101907, No.
No. 4190843, No. 4218689, No. 4219826, No.
No. 4241355, No. 4242689 and No. 4315269. Other patents disclose the use of dye dispersions in organic polymeric media. For example, Becker, U.S. Pat. No. 3,314,073, describes dyed gelatin
The use of ink and Howe et al.
No. 4,360,908 discloses the use of (dialkylamino-benzylidene) ketone dyes dispersed in cellulose nitrate. US Pat. No. 3,723,121 to Hauser discloses a laser beam recording method using a colored thermochromic material that changes color when heated by the laser beam to be transparent to the laser beam. This material may be used as such or in the form of particles dispersed in a film-forming organic polymer such as polyvinyl alcohol and/or gelatin. Although in a different direction, Engler et al.
No. 4,360,583 discloses an optical recording method using ultraviolet exposure through a photomask. The light absorbing layer consists of a film containing functionally substituted tetraheterofulvalences and liquid halocarbons, which react with each other when exposed to light.
The photoreacted film is then solvent developed to form a light-absorbing image portion that is read out by a laser beam. Furthermore, polymeric materials having electrical conductivity in the semiconductor field are known. These are commonly used by doping to modify their electrical properties. Such materials are described in US Pat. No. 4,222,903. Despite much research and development in this field, as well as a large number of materials tested, the possibility of forming optically suitable recording layers with low production costs and high reliability has not yet been demonstrated. In particular, the problem of economically achieving good sensitivity, high signal-to-noise ratio and smooth surface properties remains unsolved. SUMMARY OF THE INVENTION The present invention is a film-forming polymeric dye useful as a light absorbing layer in an optical recording element, which overcomes many of the disadvantages associated with such applications of dyes and dye polymer dispersions. More specifically, the present invention provides an aromatic polyamine and a didicarbonyl compound corresponding to the following general formula (a) in the presence of a strong protic acid; [In the formula, R ₁ and R ₅ are hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, aralkyl having 7 to 12 carbon atoms,
independently selected from the group consisting of alkaryl of 7 to 12 carbon atoms and cycloalkyl of 5 to 8 carbon atoms, or when R ₁ and R ₅ taken together are alkylene of 2 to 5 carbon atoms; , forming a ring having 5 to 8 carbon atoms as a whole, R ₂ , R ₃ and R ₄ are hydrogen,
independently selected from the group consisting of alkyl having 1 to 3 carbon atoms and halogen, and x is 0 or 1 to 3
is an integer. A film-forming poly(conjugated polymethine type) dye is provided which is a polycondensation product of Detailed Description 1 Monomer The polymer of the present invention is obtained by a condensation reaction of the above-mentioned aromatic polyamine or a salt thereof and a dicarbonyl compound in an organic solvent in the presence of a strong acid. The term polyamine means an aromatic compound having at least two reactive amine groups. Color-forming aromatic polyamines are preferred. The highly chromogenic polymer obtained by this reaction has a highly conjugated polymethine-type chromogenic system as part of its main chain structure. Polymethine-type structures are sometimes referred to as iminium or amidinium ionic groups. Such groups are found in cyanine type dyes. The reaction and the resulting polymer are represented by the following reaction formula: Preferred polyamines include: p-phenylene diamine, 4,4-diaminobenzophenone, Solvent Green 3, Direct Black 22, 1,4-diaminoanthraquinone, Numethylene Blue N, Oil Blue N, Pararosaniline Base, Thionin, acid black 48, cresyl violet acetate, 4,4-diaminodiphenylamine,
Solvent Blue 59, N,N,N,N-Tetrakis(p-aminophenyl)-p-phenylenediamine, Acid Fuyucin, Acid Blue 161, Acid Blue 45, Acid Alizarin Violet N, Nigrosine, 2,7-Diamino-9 -Fluorenone, 3,6-diamino-
9-fluorenone, 3,6-diaminoacridine, substituted 6,6-diphenyl-6H-chromoeno[4,3-6]indole and dicarbonium
ionic salt, 3,6-diamino-9-hydroxyfluorene analog of triphenylmethane, 3,6-diamino-12-dimethylamino fluorene analog of triphenylmethane HCl. The absorption spectrum of the polymer can be varied to the wavelength of the writing and reading laser beams by selecting the respective aromatic polyamine sequences. Regarding the dicarbonyl component, x is 0 or 1,
The use of a component in which R ₁ is -H is preferred in terms of reaction rate and economy. Therefore, the use of aliphatic dialdehydes such as malonaldehyde made from precursors such as bis(dimethyl acetal) is preferred. Other dicarbonyls that may be used include 1,2-cyclohexanedione, indan-1,3-dione, 1,3-cyclopentanedione and their 2-methyl derivatives. 2. Strong acid The third main component is a strong acid. Although in theory all strong acids can be used to carry out the polymerization reaction, in the present invention only very strong acids are suitable; other acids do not provide a sufficiently high molecular weight. Therefore, the term strong acid refers to protic acid having a PKa value of less than zero. Strong acids with a PKa of 5 or less are also preferred;
Even strong acids with a PKa of less than 10 can be used. Suitable strong acids are: Strong acid Pka HClO ₄ −10 HI −10 H ₂ SO ₄ −10 (calculated) Aromatic sulfonic acid −7 HCl −7 FSO ₃ H <−12 CF ₃ SO ₃ H <− 12 CF ₃ CO ₂ H 0 Fluorosulfonic acid and trifluoromethanesulfonic acid are particularly preferred. Although a strong acid is essential to the polymerization reaction, virtually any acid can be added when the condensation polymerization is complete to change the salt form. 3 Solvent In order to carry out the polycondensation reaction, it is necessary that the monomer and the resulting polymer be completely dissolved in the solvent medium. For this purpose, it is necessary to use highly polar neutral solvents, preferably those with a boiling point at atmospheric pressure below 150°C, more preferably below 200°C. Moderately volatile solvents are preferred since they can be removed by gently heating the reaction mixture or solution of the polymer to evaporate the solvent. Also, preferred are solvents that are soluble in water-soluble solvents, such as methanol and dimethyl ketone, so that the polymerization solvent can be removed by extraction. The preferred reaction solvent is dimethyl sulfoxide (DMSO),
N,N-dimethylformamide (DMF), hexamethylphosphoamide (HMPA), dimethylacetamide (DMAC) and n-methylpyrrolidone (NMP). 4. Method The polymerization reaction system is preferably heated to increase the reaction rate. The preferred operating temperature is about 180°C. However, temperatures below about 100°C can also be used for many reaction systems of this type. The time of the polymerization reaction is not critical, but must be sufficient to obtain film-forming properties of the polymer. The exact time to obtain good film formation will vary depending on the polymerization reaction system and reactants used. However, suitable operating ranges may be readily determined by those skilled in the art. To obtain adequate film-forming properties, the intrinsic viscosity of the polymer (in DMSO at 25 °C) must be at least
0.2, preferably at least 0.3. On the other hand, it is necessary that the molecular weight is not so high that it cannot be dissolved in the polymerization solvent. Therefore, the maximum intrinsic viscosity of the polymer of the present invention varies depending on the solvent used in the polymerization reaction. The term film-forming means that the polymeric dye is solid or semi-solid at room temperature and can be formed into a film by conventional coating or extrusion techniques. Marechal manufactures polymer dyes by condensation copolymerization
by Pure & Applied Chemistry, Volume 5,
1980, pp. 1923-1928 and “Polymeric Dyes
―Synthesis, Properries and Uses''.
Progress in Organics, October 1982 No. 251~
It was described on page 287. Additionally, Eslarger et al., U.S. Pat. No. 3,419,584, discloses condensation polymer salts of low molecular weight solutions of 4,4'-sulfonyldianiline compounds and dialdehydes, which are antimalarial and antileprosy agents. There is. Although the dianiline reaction is color-forming, the resulting polymer is liquid and not film-forming. The following terms are from Hackhs Chemical Dictionary
4th Edition, Mc Graw-Hill Book Company, New York, 1969, definition used: "Oxochrome" is a radical that enhances the color of a chromophore or develops color from a chromogen. "Bathochrome" is an organic radical that shifts the absorption spectrum of organic molecules toward the red. "Chromogen" is one of many colored organic substances.
It is a structural arrangement of atoms such that N=N-. In all cases, the use of equimolar amounts of monomers is preferred for the polymerization reaction. However, an excess of up to 10 mol % of the dicarbonyl compound can be used with the triamines and tetraamines. A small amount of protic acid is required as a catalyst for the polycondensation reaction. However, at least molar equivalents of acid are required to form a soluble polymer salt. Although water is not essential to the polymerization reaction, when using malonaldehyde (dimethyl acetal) as the dicarbonyl reactant,
The presence of at least molar equivalents of water for hydrolysis is preferred. Of course, the polymerization reaction is preferably carried out with all components thoroughly mixed. The polymer salts of the present invention can be treated with oxidants such as Ag, As, _F6 to increase their ability to absorb light at longer wavelengths. It can also be treated with electron acceptor charge transfer complexes for similar increases in absorption capacity. Alternatively, stable charge transfer complexes are prepared using electron acceptors such as tetracyanoethylene (TCNE) or tetracyanoquinodimethane (TCNQ). In particular, 800-900nm for TCN
It shows a strong absorption band in the range of . Therefore, they are useful as near-infrared diode laser sources. The polymers of the present invention sometimes exhibit electrical conductivity in the semiconductor region, and they are chemically stable and have low toxicity. The invention is illustrated by the following examples. Examples 1-5 A. Polymerization The reaction forming the polymerized dye is the condensation of an aromatic diamine with 1,3-poropandialdehyde (malonaldehyde) to give a highly conjugated polymethylene-type color system, such as the one described below. : The absorption spectrum of this polymer can be changed to the wavelength of writing and reading lasers by changing the structure of the aromatic diamine. Polymers were produced that had absorption in the visible and infrared wavelength ranges. The aromatic diamines used in this reaction were listed above. The reaction is performed using dimethyl sulfoxide (DMSO), N,
It is carried out in N-dimethylformamide (DMF), N-methylpyrrolidone (NMP) or mixtures of these solvents. Higher molecular weights are obtained by leaving the product in solution. A small amount (1-25 g) of the aromatic diamine is dissolved in the solvent in a 500 ml resin kettle equipped with a _N2 inlet and an agitator. After a _N2 purge, malonaldehyde (same molar amount) is added. Malonaldehyde itself is very unstable, so it is added as bis(dimethyl acetal). Acetal (Aldrich, _BP =183℃, ^n20D =
1.4081, d=0.997, flammable liquid) readily decomposes to aldehydes in the presence of acids. After the malonaldehyde is thoroughly mixed into the solution, add equimolar amounts of trifluoromethanesulfonic acid (CF ₃ SO ₃ H,
Aldrich, BP=163℃, ^n20D =1.327, d= _1.696 ,
(hygroscopic, corrosive) is added to the reaction mixture using a syringe. Soak the resin kettle in a steam bath for 4 to 48 hours. The viscosity of the reaction mixture increases as the reaction progresses. Often a gelatinous mixture is obtained. The amount of solvent is selected to obtain a 5-10% (by weight) reactant solution. The second method was used to control the release of malonaldehyde from the acetal during the reaction. In this method, the aromatic diamine and acid are combined in a solvent (usually
Dissolve in DMSO). Malonaldehyde bis(dimethyl acetal) is dissolved in up to 50 ml of solvent in a dropping funnel and added to the slurried, steam-heated reaction mixture over a period of up to 4 hours. Continue the reaction until polymerization occurs. In the examples below, all polymeric dyes were made by one of these methods. B. Purification The most research has been done on polymers () made from thionine () and malonaldehyde. Therefore, unless stated otherwise, the following description relates to this thionine-containing polymer. Thionin was purchased from Aldrich Chemical Co. as the acetate salt (94-97% purity). Chloride can also be used, but the resulting polymer is poorly soluble in dimethyl sulfoxide. If thionine acetate is used in the polymerization, the reaction mixture becomes a gelatinous mass after 16 hours. An interesting property of this polymer is that the gel liquefies rapidly when exposed to laboratory atmosphere (after the polymerization reaction under nitrogen).
Apparently dimethyl sulfoxide absorbs enough water to substantially reduce the viscosity of the mixture. Since gelation is due in part to electrostatic interactions between charged polymer chains, water blocks this interaction. The film-forming properties of the products were tested by placing a few drops of the reaction mixture on a glass slide and removing the solvent by gentle heating on a hot plate. A highly reflective film with a brown color was obtained. This film was brittle but adhered well to glass. Films kept in the oven (up to 125°C) for several months showed no significant loss in reflectivity or physical properties. The product contained impurities that were easily removed from the polymer by conventional aqueous extraction techniques. The polymer was produced by precipitation in distilled water. The reaction mixture (in DMSO) was poured into excess distilled water with stirring in a Waring blender. The solids were filtered off with suction, remixed and filtered again. This operation was continued until the filter was clean. After air drying,
The solid was soluble in concentrations of H ₂ SO ₄ but did not redissolve rapidly in DMSO. Redissolution required prolonged grinding in dilute solution. After resolventing all solids (4-6 weeks), the solution was filtered through a series of Willipore filters (10, 5, 1, 0.5 μm) or a 0.2 μm polyethylene transverse flow filter. Avoiding drying of the polymer prevents crosslinking and facilitates redissolution. Film Coating A Laser Film Formation Films were formed by spin coating on glass slides 2 inches wide and 3 inches long from purified and unpurified solutions in dimethyl sulfoxide. Film thickness is determined by solution viscosity (approximately 15 poise or less)
And by adjusting the rotation speed, it was easily changed in the range of 1 micron to several microns. Headway Research.Inc. model for all spin coaching
I used EC101-CB15 photoresist spinner. 1
More viscous liquids required rotation up to 3000 rpm to obtain micron uniform films. The film was dried with an infrared lamp while rotating. B Laser marking of polymer film Glass microscope slide (2 inch x
Samples for laser imaging were prepared by spin-coating a small portion of the DMSO/polymer solution onto a 3 inch x 1 mm sample. A polymer solution with a viscosity of 1 to 15 poise formed a film thickness of about 10 μm at 2000 to 3000 rpm. The film on glass is equipped with Ar+ power up to 33 mW and 5 mW, respectively, on the sample surface.
(488 nm) and HeNe (633 nm) pulsed lasers were used to test the write sensitivity and read ability. Place the sample on a computer-driven
A linear image (a typical pit) was formed by moving at a speed of 400 microns/second at intervals of 10 msec. Reading was performed at a reduced power (less than 1 mW) at the writing wavelength. The image was detected by the decrease in the intensity of the light reflected to the photodetector. The reflection of the polymer film surface was 5-15% and that of the image area was 0-5%. Representative results for several polymers are summarized in the table below:

【table】

[Table] The writing sensitivity was very reproducible and was almost unaffected by changes in film thickness. Sample readout was performed by rescanning the linear pit with laser power reduced to 100-800 μW. The signal from the reflected light collected by the photodetector was displayed on a screen and printed out on an XY recorder. Even short pulse widths gave good contrast between the unimaged area and the imaged pit area. Readout sensitivity was also very reproducible. Sample stability was tested on a hot stage microscope. After forming a series of pits at room temperature, the pits were tested at various temperatures at a heating rate of 5°C/min. Heat the sample to 250℃,
When then cooled to room temperature, the pits were clearly visible and undamaged. The only effect of heat treatment was the sublimation of some material on the sample surface when the temperature was increased. This material appeared to be unreacted aromatic diamine. However, this sublimation occurred at 250°C.
Nevertheless, the samples still retained a high degree of reflectivity after heat treatment. Example 6 2.81 in a solution of 75 ml dimethylformamide and 75 ml dimethyl sulfoxide under nitrogen atmosphere.
A reaction system was prepared containing g (0.0094 mol) of pure 4,4'-diaminodiphenylamine sulfate and 1.55 g (0.0094 mol) of malonaldehyde bis(dimethylacetal). Steam heating (approx.
100°C) and continuous stirring to dissolve. After complete dissolution, 1.02 g (0.0068 mol) of trifluoromethanesulfonic acid was added dropwise, followed by 0.45 g (0.0045 mol) of fluorosulfonic acid with continuous heating and stirring. Samples were removed after 30 minutes and cast on glass slides. Slides were heated on a hot plate (80°C) for 20 minutes. A metallic green film is formed and the glass
Peeled off the slide. The conductivity of this film at room temperature (23°C) and 0% relative humidity is 1.1×
It was 10 ^-2 ohm ^-1 cm ^-1 . Example 7 A mixture of 6.00 g (0.02 mol) pure 4,4'-diaminodiphenylamine sulfate, 3.313 g (0.02 mol) malonaldehyde bis(dimethyl acetal) and 300 ml dimethyl sulfoxide is brought to 100° C. with stirring. Stirred. After complete dissolution, 2.188 g (0.015 mol) trifluoromethanesulfonic acid and then 0.978 g (0.01 mol)
of fluorosulfonic acid was added dropwise. The reaction was completed in 2 hours under nitrogen atmosphere. This solution was cast on a glass slide to form a film sample. Slides were placed on a hot plate (80°C) for 20 minutes.
It was heated for a minute. The conductivity of this film measured at room temperature was 1×10 ^-2 ohm ^-1 cm ^-1 . Example 8 A mixture of 6.00 g (0.02 moles) of pure 4,4'-diaminodiphenylamine sulfate, 3.315 g (0.02 moles) of malonaldehyde bis(dimethyl acetal) and 200 ml of dimethyl sulfoxide was prepared. This was heated with steam to about 100° C. while stirring under a nitrogen atmosphere to dissolve it. After completely dissolving, add 2.42g while continuing to heat and stir.
(0.024 mol) of fluorosulfonic acid was added dropwise.
After 2 hours, the solution was cast on a glass slide to form a film sample. Slides were heated on a hot plate (80°C) for 20 minutes.
A metallic green film was formed, which could be peeled off from the glass slide. The conductivity of this film measured at room temperature (23° C.) and 0% relative humidity was 1.3×10 ⁻³ ohm ⁻¹ cm ⁻¹ . Example 9 1.00 g (0.0034 mol) of pure 4,4'-diaminodiphenylamine sulfate, 0.55 g (0.0034 mol)
A mixture of mol) of malonaldehyde bis(dimethyl acetal) and 75 ml of dimethyl sulfoxide was heated to 100° C. with stirring. When completely dissolved, 0.64 g (0.0034 mol) of para-toluene sulfonic acid was added dropwise. The reaction was carried out for 1 hour under nitrogen atmosphere. Film samples were prepared as described above. Conductivity at room temperature is 5×10 ^-4 ohm ^-1 cm ^-1
It was hot. The films of Examples 6-9 all have a conductivity of the semiconductor region at 23° C. and 0% relative humidity, e.g.
It has an order of 10 ^-3 ohm ^-1 cm ^-1 . The conductivity of the dye polymers of the present invention allows them to be used in electrical applications such as conductive materials for electromagnetic interference (EMI) protection and static electricity control. As an EMI shield, fiber-containing composites are useful as housings for circuits to prevent the emission or absorption of electromagnetic radiation. For static electricity control, fibers of this material are used in pulse materials, flooring, bench tops,
Used as cloth, etc. Example 10 Yet another dye polymer was synthesized. To a 500 ml resin kettle equipped with nitrogen inlet and outlet, thermometer, stirring and heating mantle was added 4-24 ml of dimethylformamide (DMF), liver toxin, embryotoxin solution. 12.6
g (0.0267 mol) of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, 4.4 g (0.0267 mol) of malonaldehyde bis(dimethyl acetal) and 4.0 g
(0.0267 mol) of trifluoromethanesulfonic acid was added at room temperature with stirring. Heat the mixture for 24 hours with stirring (steam temperature above the mixture 70~
100℃). A red, viscous solution was obtained. Using a bellows pump lined with Teflon(TM) fluoropolymer and operated by compressed air,
Membrana Inc. Dynasep Sampler I, 0.2μm
-Filter the solution through a polypropylene transverse flow filter. The viscosity of the filtered solution varied from 2 to 200 cp depending on the molecular weight of the polymer. Vacuum distillation (0.20 mmHg, 50 °C) or DMF to obtain viscosities up to approximately 15 poise.
It was possible to concentrate the solution by dilution with . The maximum absorption of this polymer in film form is
It was 475nm. Example 11 A similar polymer was prepared and filtered by the same method as Example 10. However, in the filtered solution, molar excess of oxidant dissolved in DMF,
_AgAsF6 was added. The viscosity of the filtered solution was 2 cp before addition of the AgAsF ₆ /DMF solution. The absorption spectrum of the film produced from this oxidized polymer solution was 830 nm. Example 12 A similar polymer was prepared and filtered by the same method as Example 10. However, a molar excess of 7,7,8,8-tetracyanoquinone dimethane (TCNQ) was added to the filtered solution. The solution turned from red to yellow-green. Solution viscosity (2-20 cp depending on polymer molecular weight) was adjusted by vacuum distillation or dilution as described in Example 10. The maximum absorption of this polymer solution was at 830 nm.

Claims (1)

[Claims] 1 General formula NH ₂ - in the presence of a strong protic acid
An aromatic polyamine represented by Ar—NH ₂ (where Ar is an aromatic group) and a dicarbonyl compound corresponding to the following general formula (a); [In the formula, R ₁ and R ₅ are hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, aralkyl having 7 to 12 carbon atoms,
independently selected from the group consisting of alkaryl having 7 to 12 carbon atoms and cycloalkyl having 5 to 8 carbon atoms, or when R ₁ and R ₅ are combined, it is alkylene having 2 to 5 carbon atoms; taken together to form a group consisting of rings of 5 to 8 carbon atoms, R ₂ , R ₃ and R ₄ are independently selected from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms and halogen, and x is It is 0 or an integer from 1 to 3. A film-forming (conjugated polymethine type) polymeric dye polymer which is a polycondensation product of the formula (b) below and has an intrinsic viscosity of at least 0.2 as measured in dimethyl sulfoxide at 25°C. 2. The dye polymer according to claim 1, wherein the aromatic polyamine is color-forming. 3. The dye polymer according to claim 1, which is formed in a highly polar neutral solvent. 4. The dye polymer of claim 1, wherein the aromatic polyamine is thionine. 5. The dye polymer according to claim 1, wherein the aromatic polyamine is N,N,N',N'-tetrakis-(p-aminophenyl)-p-phenylenediamine. 6. The dye polymer of claim 1, wherein x is 0 or 1. 7. The dye polymer according to claim 1, wherein x is 0 and R ₁ to R ₅ are hydrogen. 8. The dye polymer of claim 1, wherein the polymer is a polyazomethine salt having the general formula: 9 General formula NH ₂ - in the presence of a strong protic acid
An aromatic polyamine represented by Ar—NH ₂ (where Ar is an aromatic group) and a dicarbonyl compound corresponding to the following general formula (a); [In the formula, R ₁ and R ₅ are hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, aralkyl having 7 to 12 carbon atoms,
independently selected from the group consisting of alkaryl having 7 to 12 carbon atoms and cycloalkyl having 5 to 8 carbon atoms, or 2 carbon atoms when R ₁ and R ₅ are combined;
~5 alkylene, thus forming a ring having 5 to 8 carbon atoms as a whole, R ₂ , R ₃ and R ₄ are hydrogen,
independently selected from the group consisting of alkyl having 1 to 3 carbon atoms and halogen, and x is 0 or 1 to 3
is an integer. A process for producing a film-forming (conjugated polymethine type) polymer dye polymer which is a polycondensation product of and to which is added at least 1 mole of strong acid per mole of aromatic polyamine. Production method. 10 Strong acids include perchloric acid, fluorosulfonic acid,
10. The method of claim 9, wherein the acid is selected from the group consisting of trifluoromethanesulfonic acid, p-toluenesulfonic acid, and hydroiodic acid. 11. The method of claim 9, wherein the solvent is selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and mixtures thereof. 12 The above polymer is a polyazomethine salt having the following general formula, [where HX is an acid or a mixture of acids. 10. The method of claim 9, wherein at least about 1 mole of strong acid is added per mole of 4,4' diaminodiphenylamine or its salt and malonaldehyde bis(dimethyl acetal).