JPS6038431A - Polymer dyeing polymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel polymers suitable for use in optical recording elements.

In response to the need for a reliable, large-capacity data storage and recovery system, so-called optical disk recording systems are being 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. Nos. 3,314,073 and 3,474,457. 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 suitable 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 densities of 102 bits/cffi2- or more.

The simplest optical desk consists of a dimensionally stable solid substrate overlaid with a layer of light-absorbing material, such as a metal layer. 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.

Desired properties of optical recording media include (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 retrieval (
J, Vac, Sci, Tec-hnology
, Vol. 18, No. 1, January 72, 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 introduced in U.S. Pat. No. 4,023,185, no.
No. 97895, No. 4101907, No. 4190843
No., No. 42181189, No. 4219828, No. 4
No. 241355, No. 4242688 and No. 43152
It is described in No. 89. Other patents disclose the use of dye dispergebons in organic polymeric media. For example, Becker US Pat. No. 1,331,4073
The number refers to dyed gelatin, or India.
a) The use of ink and Howe et al.
No. 4,380,908 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 to be transparent to the laser beam when heated by the laser beam. This material is used as such or in the form of particles dispersed in film-forming organic polymers such as polyvinyl alcohol and/or gelatin.

Although in a different direction, U.S. Pat. No. 43 to Engler et al.
No. 80583 discloses an optical recording method using ultraviolet exposure through a photomask. The light absorbing layer consists of a film containing functionally substituted tetraheterofluorenes 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 U.S. Pat. No. 422
No. 2903.

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.

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 relates to a strong protic acid of an aromatic polyamine and a dicarbonyl compound corresponding to the following general formula; [wherein R1 and Rs are hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, and 12 aralkyl, carbon number 7~
independently selected from the group consisting of alkaryl of 12 carbon atoms and cycloalkyl of 5 to 8 carbon atoms, and when Ri and R1 taken together are alkylene of 2 to 5 carbon atoms, thus forming a ring of 5 to 8 carbon atoms. formed, R2, R3 and R+ are hydrogen,
independently selected from the group consisting of alkyl having 1 to 3 carbon atoms and halogen, and X is O or an integer from 1 to 3. is a polycondensation product in the presence of ]. Film-forming poly(conjugated polymethine type) dyes are provided.

Monomer The polymer of the present invention can be obtained by a condensation reaction of the aromatic polyamine or its salt 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, and the resulting polymer is represented by the following reaction scheme: Preferred polyamines include: P-phenylenediamine, 4,4-diaminobenzophenone, Solvent Green 3, Direct Black 22 .1.4-Diaminoanthraquinone, New Methylene Blue N, Oil Blue N, Pararosaniline Bayes, Thionin,
Acid Plaque 4B, Cresyl Violet Acetite, 4,4-Diaminodiphenylamine, Solvent Blue 59, N, N, N, N-tetrakis (p-
Aminophenyl)-p-phenylenediamine, Acid Thyushin, Acid Blue 161, Acid Blue 45, Acid Alizarin Violet N, Nigrosine, 2゜7-Diamitsu-9-Fluorenone, 3.6
-Diamitsu-9-fluorenone, 3,6-cyamitsuacridine, substituted 6,6-siphenylated-6H-chromonino
[4,3-6] Indole and carbonium ion salts, 3,6-diami-9-hydroxyfluorene analogs of triphenylmethane, 3,6-diami-2-12-dimethylamino fluorene analogs of triphenylmethane) ICI.

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 O or 1, R4 is -H
It is preferable to use the following components from the viewpoint 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 can be used are 1,2-cyclohexanedione, indan-1,3-
dione, 1,3-cyclobentanedione and these two
- Contains 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 acids having a PKa value of 0 or less. Strong acids with a PKa of less than -5 are also preferred, and even strong acids with a PKa of less than -10 can be used. Suitable strong acids are: 1-1-P Ka HClO4-10 HI-10 H, SO2-1o (calculated) Aromatic sulfonic acid -7 HC1-7 FSO3H<-12 CF, 5o3H<-12 Particularly preferred are CF, CO2HO, fluorosulfonic acid and trifluoromethanesulfonic acid.

Although strong acids are critical to the polymerization reaction, virtually any acid can be added when the condensation polymerization is complete to change the salt form.

3. In order to carry out the solvent condensation polymerization reaction, it is necessary that the monomer and the resulting polymer be completely dissolved in the solvent medium.

For this purpose, highly polar neutral solvents, preferably
Boiling point at atmospheric pressure is 150℃ or less, more preferably 200℃ or less
It is necessary to use a solvent below ℃. 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. Suitable reaction solvents are dimethylsulfoxide (CDMSO), N,N-dimethylformamide (DMF), hexamethylphosphoramide (H
MPA), 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 in 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.) should be at least 0.2. It is 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.

The production of polymer dye stripping by condensation copolymerization was carried out by Marechal in Pure & Applied Chemig.
try, Vol. 5, 1980, pp. 1923-1928 and rPol-ymeric Dyes-Syn
thesis, properties and [J
Under the title seSJ, PROGRESS IN ORG
anics.

1041982, pages 251-287.

Additionally, U.S. Patent No. 34195 to E. Slarger et al.
No. 84 discloses condensation polymers 39 of low molecular weight solutions of 4,4'-sulfonyldianiline compounds and dialdehydes, which are antimalarial and antileprosy agents. Although the dianiline reaction is color-forming, the resulting polymer is liquid and not film-forming.

The following terms are Hackhs Che+5ical D
1ctionary, 4th edition, Mc Graw-Hil
l Book Company+ New York, 19
1969: "Oxochrome" is a radical that enhances the color of a chromophore or develops color from a chromogen.

"Bacchrome" is an organic radical that shifts the absorption spectrum of organic molecules toward the red.

A "chromogen" is a structural arrangement of atoms, such as N=N-, in many colored organic materials.

The use of 1 equimolar amount of monomers in all cases is preferred for the polymerization reaction. However, an excess of up to 10 mol % of 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 non-woody in the polymerization reaction, when malonaldehyde (dimethyl acetal) is used as the dicarbonyl reactant, the presence of at least a molar equivalent of water is preferred for hydrolysis.

Of course, it is preferable that the polymerization reaction be carried out with all components thoroughly mixed.

The polymer salts of the present invention can be treated with oxidants, such as AgAsF, 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 I transfer complexes are prepared using electron acceptors such as tetracyanoethylene (TCNE) or tetracyanoquinodimethane (TCNQ). In particular, TCNQ is 800 = 8
Strong absorption in the 00 nm range? shows. Therefore, they are useful as near-infrared diode laser sources.

The polymer of the present invention has recently shown electrical conductivity in the semiconductor region,
They are chemically stable and have low toxicity.

The invention is illustrated by the following examples.

Examples 1-5 A, Reaction to form polymerized polymer dyes with aromatic diamines and 1.3-
The absorption spectrum of this polymer can be changed by changing the structure of the aromatic diamine. The wavelength of the writing and reading laser can be changed.

Polymers have been produced that have absorption in visible and infrared wavelengths. 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. 500m including N2 entrance/exit and IF equipment
A small amount of aromatic diamine (1 to 25 g) is dissolved in the solvent in 1 resin bottle. After N2 purge, malonaldehyde (4 molar amounts) is added. Malonaldehyde itself is very unstable, so His (dimethyl acetal)
It is added as. Acetal (A Idrich,
BP=183°0. np=1.4081, d=0゜9
97, flammable liquids) readily decompose to aldehydes in the presence of acids. After the malonaldehyde is thoroughly mixed into the solution, an equimolar amount of trifluoromethanesulfonic acid (CF
3S 03H, A 1drich, BP= 1630
0, n; = 1.327, d = 1.686, hygroscopic, corrosive) is added to the reaction mixture using a syringe. Soak the resin kettle in a steam bath for 4-48 hours. The viscosity of the reaction mixture increases as the reaction progresses. Often a gelatinous mixture is obtained. The amount of solvent is 5~x+)? (by weight) selected to obtain a 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 dissolved in a solvent (usually DFISO). Malonaldehyde bis(dimethylacecool) 5
Dissolve it in a solvent up to 0+il and add it dropwise into Noanel,
Add to the slurried, steam-heated reaction mixture for up to 4 hours. Continue the reaction until polymerization occurs. In the examples below, all polymeric dyes were made by one of these methods.

The most research has been carried out on polymer (II) prepared from B. purified thionine CI) and malonaldehyde.

Therefore, unless otherwise stated, the following description relates to this thionine-containing polymer.

Thionin is A 1drich Che+5ical C
It was purchased as acetite 1jA (sa~87χ purity) from O.O. Ij1 compound can also be used, but the resulting polymer is difficult to dissolve in dimethyl sulfoxide. If thionin acetyl I. 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 the dimethyl sulfoxide absorbs enough wood 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 using a solvent hot plate. A brownish, highly reflective film 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. Reaction mixture (in DMSO)
was injected into excess distilled water using a Waring blender at 1W. 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 is soluble in concentrated H2SO+, but
It did not redissolve rapidly in DMSO. Redissolution required prolonged grinding in dilute solution. After redissolving all solids (4-6 weeks), a series of Willipore
The solution was filtered through a 7 Ilter (10,5j, 0.5 pLm) or 0.2 gm polyethylene transverse Flora filter. Avoiding drying of the polymer prevents crosslinking and facilitates redissolution.

2nd grade Ju A. Laser Film Formation Films were formed by spin coating on 1112 inch by 3 inch long glass slides from purified and unpurified solutions in dimethyl sulfoxide. The film thickness varied from 1 micron to several microns from WjJJ to volume A by adjusting the solution viscosity (approximately 15 poise or less) and rotation speed. I eadway for all spin coaching
Model EC l of Research, Inc.
ot-C B 15 photo 1/cyst spinner was used. 1
To obtain a uniform film of microns, the more viscous liquid is 3
Rotation up to 000 rpm was required. The film was dried with an infrared lamp while rotating.

B. Polymer Film Laser Marking Glass Microscope Slide (2" x 3"
Samples for laser imaging were made by spin-coating a small portion of the DMSO/polymer solution onto the i: mm). Polymer solution with viscosity 1-15 voids is 2000 ~
A film thickness of about 10 pLm was formed at 3000 rpm. Each glass film was 33 m long on the sample surface.
A 1 + (488 nm) with power up to W and 5 mW
The write sensitivity and read ability were tested using a H e Ne (ft33 nm) pulsed laser.

The sample is placed on a computer-driven X-Y translation table and the incoming laser pulse train (
Variable up to 100 g sec c pulse, -10+ss
ec spacing) at a speed of 400 microns/sec to form a linear image (typical peat). Reading was performed at reduced power (1 mW or less) 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 some polymers:
Table I summarizes: Laser marking of polymer films (633 nm
) 490 1 (eNe 18% I Psec 3.5
mW■1 1-I 11 550 1-1eNe 12% 700 n5ec
2-5 1TIW630 nm IIeNe 15%
3 (10n5ee 2.5 mWll, 1 (i33
HeNe in nm: Ar″l− in 488n− The writing sensitivity was very reproducible and was hardly affected by film thickness changes.The readout of the sample was
This was done by rescanning the linear bits with the laser power reduced to 800p, W. The signal from the reflected light collected by the photodetector was displayed on a screen and printed out on an X-Y recorder. Even at short pulse widths there was good contrast between the unimaged and imaged bit areas and the sensitivity was also very reproducible.

Sample stability was tested on a hot stage microscope. After forming a series of PiI at room temperature,
The bits were tested at various temperatures with a heating rate of 5°C/min.

When the sample was heated to 250°C and then cooled to room temperature, the bits were clearly visible and undamaged. The only effect of the heat treatment was some material agglomeration 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.

Length JL! Under a Lu nitrogen atmosphere, 751 dimethylformamide and 7
2,81 g (0
．． A reaction system containing 0.0094 mol) of pure 4.4'-diaminodiphenylamine sulfate and 1.55 g (0.0094 mol) of malonaldehyde bis(dimethyl acetal) was prepared. Dissolution was achieved by steam heating (approximately 100° C.) and continuous stirring. After complete dissolution, 1.02 g (
0.00138 mol) of trifluoromethanesulfonic acid was added dropwise, followed by the addition of 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. The slides were heated on a hot plate (80°C) for 20 minutes. A metallic green film was formed and peeled off from the glass slide. Room temperature (2
The conductivity of this film at 3 °C) and relative humidity Oz is 1
．． I x 10 ohm cm 1).

Length J111 e. oog (0.02 mol) of pure 4,4'-diaminodiphenylamine sulfate, 3.313 g (0.02 mol) of pure 4,4'-diaminodiphenylamine sulfate;
A mixture of 02 mol) of malonaldehyde bis(dimethyl acetal) and 30 hl of dimethyl sulfoxide was heated to 100° C. with stirring. After completely dissolving,
2.188 g < 0.015 mol) of 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. The slides were heated on a hot plate (80°C) for 20 min. The conductivity of this film measured at room temperature is l×10 ohm
It was am.

8.00 g (0.02 mol) of pure 4,4'-diaminodiphenylamine sulfate, 3.315 g (0.02 mol) of pure 4,4'-diaminodiphenylamine sulfate.
A mixture of 0.02 mol) of malonaldehyde bis(dimethyl acecool) 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 complete dissolution, 2.42 g (0.024 mol) of fluorosulfonic acid was added dropwise while continuing heating and stirring. 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 the glass slide. The conductivity of this film measured at room temperature (23°C) and relative humidity Oz is 1.3 X 10 oha+ cll
1.00 g (0,0034 mol) of pure 4,4'-diaminodiphenylamine sulfate, 0.55 g (0,0034 mol)
A mixture of 751 moles of malonaldehyde bis(dimethyl acetal) and 751 moles of dimethyl sulfoxide is heated to 100°C with stirring.1. Ta. When completely dissolved, 0.84 g (o, oo moles) 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.

The conductivity at room temperature was 5 x 10 ohm cm.

The films of Examples 6-9 all have conductivities in the semiconducting range, eg, on the order of 10 ohm cm, at 23° C. and oz. relative humidity. The conductivity of the dye polymers of the present invention makes them suitable for electrical applications such as ``TrL magnetic interference (E
MI) Can be used in applications such as conductive materials for protection and static electricity control. For EMI shielding, fiber-containing composites are useful as housings for circuits to prevent the emission or absorption of electromagnetic radiation. For static electricity M control, #a fibers of this material are used in panel phases, flooring, bench tops, fabrics, etc. to provide the anti-static environment necessary for electrical, explosives and fine material handling industries. It is used as such.

Furthermore, another dye polymer was synthesized. 500+ with nitrogen inlet and outlet, thermometer, stirrer and heating mantle
dimethylformamide (DMF) in a w l resin kettle.
, liver toxin, embryotoxin (
Embryotoxin) solution M4-24+I+ was added. 12-6 g (0,0267 mol) of N, N,
N', N'-tetrakis (P-aminophenyl)
-p-phenylenediamine, 4.4 g (0,02111
7 mol) of malonaldehyde bis(dimethyl acetal) and 4.0 g (0.0287 mol) of trifluoromethanesulfonic acid were added at room temperature with stirring. The mixture was heated with stirring for 24 hours (vapor temperature of the mixture: 70-100°C). A red, viscous solution was obtained. Using a bellows pump lined with Teflon(TM) fluoropolymer and operated with compressed air, Membrana
Inc, c7) Dynasep Sa, +gpler
The solution was filtered through a polypropylene transverse flora filter. The viscosity of the filtered solution varies from 2 to 200 cρ depending on the molecular acid of the polymer.
It varied within the range. It was possible to concentrate the solution by vacuum distillation (0.20 m+sHg, 5°C) or dilution with DMF to obtain a viscosity of up to about 15 boids. The maximum absorption of this polymer in film form is 47
It was 5 nm.

A similar polymer was prepared and filtered by the same method as in Example 10. However, the filtered solution contains a molar excess of oxidant, A g A s F, dissolved in DMF.
was added. The viscosity of the filtered solution was 2 cp before addition of the AgAsF,/DMF solution. The absorption spectrum of the film made from this oxidized polymer solution is 83
It was 0nri.

A similar polymer was prepared and filtered by the same method as Example 1O. However, there is an excess of 7.7 molar in the filtered solution.
, 8.8-tetracyanoquinone dimethane (TCNQ) was added. The solution turned from red to yellow-green. Example 1
The solution viscosity (2-20 cp depending on the molecular weight of the polymer) was adjusted by vacuum distillation or dilution as described in 0. The maximum absorption of this polymer solution was 830 nm.

Claims (1)

[Scope of Claims] 1. A strong protic acid of an aromatic polyamine and a dicarbonyl compound corresponding to the following general formula; [wherein R4 and RE
is independently selected from the group consisting of hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, 7-ralkyl having 7 to 12 carbon atoms, alkaryl having 7 to 12 carbon atoms, and cycloalkyl having 5 to 8 carbon atoms; and R5 are alkylene having 2 to 5 carbon atoms and therefore form a ring having 5 to 8 carbon atoms, and R2, R2 and R4 are selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and halogen. independently selected,
and X is O or an integer of 1 to 3. A film-forming poly(conjugated polymethine type) dye polymer which is a polycondensation product in the presence of ]. 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 according to claim 1, wherein the aromatic polyamine is thionine. 5. The aromatic polyamine is N,N,N',N'-tetrakis-(p-aminophenyl)-p-phenylenediamine. A dye polymer according to claim 1. 6. The dye polymer of claim 1, wherein x is 0 or 1. 7. The dye polymer of claim 1 treated with an oxidant. 8. The oxidant is AgAsF6. A dye polymer according to claim 1. 9. The dye polymer of claim 1, wherein x is O and R1 to R5 are hydrogen. 10. The dye polymer according to claim 1, wherein the polymer is a polyazomethine salt having the following general formula. [where HX is an acid or a mixture of acids. ]If, a strong propylene acid of an aromatic polyamine and a dicarbonyl compound corresponding to the following general formula: [wherein R2 and R5 are hydrogen, alkyl having 1 to 4 carbon atoms, phenyl, 7 to 4 carbon atoms
independently selected from the group consisting of aralkyl having 12 carbon atoms, alkaryl having 7 to 12 carbon atoms, and cycloalkyl having 5 to 8 carbon atoms, and when R and R5 are taken together, C2 to
5, thus forming a ring of 5 to 8 carbons Ia, and 1. R2, R3 and R4 are independently selected from the group consisting of hydrogen, alkyl having 1 to 3 carbon atoms, and halogen, and X is O or an integer from 1 to 3. A process for producing a film-forming poly(conjugated polymethine type) dye polycondensate, which is a polycondensation product, in the presence of a highly polar A process as described above, in which at least 4j1 moles of strong acid are added per mole of aromatic polyamine, dissolved in a neutral solvent. 12. The method of claim 11, wherein the method is formed into a film from a solution. 13. The method of claim 11, wherein the strong acid is selected from the group consisting of perchloric acid, fluorosulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and hydroiodic acid. 14. The method of claim 11, wherein the solvent is selected from the group consisting of dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, and mixtures thereof, wherein the polymer has the following general formula: A polyazomethine salt having the formula: where HX is an acid or a mixture of acids. ]4.4'
- diaminodiphenylamine or a salt thereof and malonaldehyde bis(dimethyl acetal) are dissolved in a solvent in a proportion of substantially equal moles of the latter per mole of the former, or up to 1.5 moles, and at least about 1 mole of strong acid per mole of the former; 12. The method of claim 11, characterized in that: