KR100200032B1 - Phthalocyanine polymers with good processability, producing method thereof, and polymer compositions and photosensitive polymer films produced therefrom - Google Patents

Abstract

The present invention relates to a phthalocyanine polymer which is soluble in an organic solvent, has high sensitivity to near-infrared rays and visible rays, and has excellent processability, a process for producing the same, a polymer composition using the same, and a photosensitive polymer thin film.

Description

A phthalocyanine polymer having excellent processability, a process for producing the same, a polymer composition using the same and a photosensitive polymer thin film

FIG. 1 is a diagram showing a UV / vis absorption spectrum of an oxy titanium phthalocyanine polymer,

FIG. 2 is a diagram showing an infrared absorption spectrum of an oxy titanium phthalocyanine polymer,

FIG. 3 is a view showing a thermogravimetric curve of the oxy titanium phthalocyanine polymer,

FIG. 4 is a diagram showing the UV / vis absorption spectrum of the oxyvanadium phthalocyanine polymer,

FIG. 5 is a diagram showing an infrared absorption spectrum of an oxy vanadium phthalocyanine polymer,

FIG. 6 is a diagram showing a thermogravimetric curve of an oxy vanadium phthalocyanine polymer,

FIG. 7 is a diagram showing the UV / vis absorption spectrum of the thin film of oxytitanium phthalocyanine polymer. FIG.

[Object of the invention]

The present invention relates to a method for producing a phthalocyanine polymer which is soluble in an organic solvent and which has high sensitivity to near-infrared rays and visible rays, and which has excellent processability, and a polymer composition and an optical recording medium using the phthalocyanine polymer prepared therefrom.

[TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]

Phthalocyanine has high absorption properties in visible light and near infrared rays, and is excellent in photo-conductivity, light-sensitive property, and optical memory characteristics and is used as an electrophotosensitive member, a solar cell, and a sensor in addition to a coloring agent such as a dye or a dye , Other display devices and optical devices. Particularly, laser beam printers and color printers using electrophotography are generally used as light sources 790 A near infrared ray semiconductor laser having an emission wavelength of 20 nm is used, so that development and application of a photosensitive member having sufficient sensitivity to near-infrared rays are required, and research has been continuously conducted. Among the research results, it has been found that, as a charge-generating substance having sensitivity to near-infrared rays, metal-free phthalocyanine and metal phthalocyanine such as oxytitanium phthalocyanine, oxy vanadium phthalocyanine, magnesium phthalocyanine, chloro-aluminum phthalocyanine, chloroindium phthalocyanine, Have been studied extensively. Japanese Patent Application Laid-open Nos. 49544/1984, 166959/1984, 239248/1986, 67094/1987, 366/1988, 116158/1988 , 198067/1988 and 17066/1989.

However, the phthalocyanine compound according to the contents disclosed in the above literature has a low synthesis yield, is difficult to purify, and has low solubility in general organic solvents. Therefore, when a photosensitive thin film for use in various devices is manufactured, processing is difficult and purity is increased There is a drawback that it can not. When the purity and the solubility are low, there is a problem that the sensitivity, the recording property and the reflectance of the medium are insufficient to provide an industrially useful photosensitive thin film. When a photosensitive thin film is prepared using the above phthalocyanine compound, a photosensitive thin film should be prepared by a sublimation or deposition apparatus or by using a binding polymer together with a bar coating method. At this time, a sublimation or deposition apparatus is expensive , It is impossible to apply a photosensitive thin film having a large area. In addition, when a photosensitive thin film is prepared by a method such as bar coating using a binding polymer together, there is a problem that phase separation occurs even after being made into a thin film because of a problem of phase separation with the binding polymer. In addition, since the light stability of the thin film is low, a stable recording signal can not be obtained, and there is a disadvantage that fatigue phenomenon occurs easily and life is shortened.

In order to solve the problem of the solubility and processability of the phthalocyanine compound, the position of 1, 2, 3, 4, 8, 9, 10, 11, 15, 16, 17, 18, 22, 23, 24, 25 of the phthalocyanine compound In which a variety of substituents are introduced. For example, Hanack et al. Chem. (1984) 23, 1065 disclose phthalocyanines having 8 substituents such as an alkoxy group, a tetrabutyl group, a nitro group, a halogen, an alkyl group and the like at positions 2, 3, 9, 10, 16, 17, W. Urban et al., J. Appl., Polym. Sci. (1993), 47, 2017, the phthalocyanine having four carboxyl groups was synthesized and then reacted with an alcohol group to prepare a phthalocyanine having an ester substituent having a long alkyl chain to increase the solubility. In addition, European Patent Publications 0373643 and 0353394, Japanese Patent Publication Nos. 197280/1986, 4298975 and 769307 disclose optical recording media using halogenalkyl substituted phthalocyanines. As a result, the solubility in the coating solvent and the stability of the coating solution are improved, but the disadvantage of insufficient sensitivity, refractive index, reflectance, and recording properties remains.

Many studies have been made on the phthalocyanine polymers for the purpose of improving the processability and stability of the solution. S. L. Yang et al., J. Photochem. and Photobio. 88, 183, (1995) disclose a compound having copper-phthalocyanine adducts in the basic skeleton of a poly (vinylcarbazole-acrylamide) copolymer and measuring the photoconductivity thereof. However, in this case, the phthalocyanine is introduced into the side chain, so that the photoelectric property can not be exhibited properly, and the photosensitive property is reduced.

As a result, a polymer having a phthalocyanine chain as a basic skeleton has been developed. As a result, a polymer having a phthalocyanine chain as a basic skeleton can be roughly divided into four types. The first type is a form of bridging phthalocyanine with an alkyl substituent, the second type is a fused form in which one benzene ring is shared by two phthalocyanines, and the third type is a phthalocyanine The bridged form by the substituent forms a ladder form, the benzocyclic ring is substituted with an exocyclic group to bridge the phthalocyanine, and the fourth type is a form in which the central metals of the phthalocyanine are bridged with each other by an oxygen atom or a halogen atom . One example of the first type is B. B. Simms et al., J. Polym. Sci. A-1 (1970), 8, 111 discloses the production of a phthalocyanine polymer for various metals by using an alkyl group containing a carborane as a bridging group together with a methylsiloxane or a urethane group, . However, these compounds have resulted in rather less stability of the phthalocyanine polymer due to the instability of the bridging group of the phthalocyanine and the influence of impurities. J. A. Parker et al., J. Polym. Sci. Polym. Chem. Ed. (1982), 20, 269 and 2073 synthesized phthalocyanine polymers using benzimidazole as a bridging group. However, these compounds were also poorly soluble in general organic solvents and inorganic solvents, I could not completely remove it. An example of a second type is described in J. A. Parker et al., J. Polym. Sci. Polym. Chem. Ed. (1982), 20, 1785, a phthalocyanine polymer was synthesized by reacting pyromellitic dianhydride with a metal salt and urea under catalytic conditions. These compounds were also soluble in sulfuric acid, NaOH, DMSO, DMF, DMAC But has a molecular weight of about 2,000, which indicates a very low degree of polymerization. An example of a third type is described in J. A. Parker et al., J. Polym. Sci. Polym. Chem. Ed. (1982), 20, 2773 and 2781 disclose the synthesis of a ladder-type phthalocyanine polymer by reacting benzophenone tetracarboxylic acid dianhydride and pyromellitic dianhydride each time with phthalocyanine tetraamine . These compounds are excellent in thermal stability, but have low solubility. Therefore, it is difficult to clearly analyze the structure even by elemental analysis or infrared spectroscopy. An example of the fourth type is R. P. Linstead et al., J. Chem. Soc. (1936), 1719, and M. E. Kenny et al., J. Amer. Chem. Soc. (1969), 91, 5210, etc., but these compounds were also poorly soluble.

[Technical Problem]

In order to solve the above problems, the present inventors have studied a method of synthesizing a functional polymer having a thermally stable and good photosensitivity to the near infrared region and improved solubility, and when a phthalocyanine has a structure of a proper chain, And thus a phthalocyanine polymer capable of dissolving in the phthalocyanine polymer can be obtained. It was also found that the prepared phthalocyanine polymer forms a thin film by coating on a general support or electrode such as an aluminum plate, a Mylar film, a conductive glass (ITO glass), a PET resin, and a platinum electrode in a solution state dissolved in a solvent, (PVB), polycarbonate (PC) or the like to improve the transparency of the photosensitive layer, and thus the present invention has been completed.

[Structure and operation of the invention]

Thus, according to the present invention there is provided a phthalocyanine polymer of formula 1, which is soluble in organic solvents and has a high sensitivity to near-infrared and visible light;

(Wherein M is a hydrogen atom or a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide, m and n are integers of 2 or more, and R ¹ is a hydrogen atom, a lower alkyl group, alkyl ether group or a substituted benzene group (C ₆ R ^la _5: where R ^la is a hydrogen atom, the number of carbon atoms 1-6 lower alkyl group or alkyl ether group), and, R ² is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl group, an alkyl ether having 3 to 10 carbon atoms, a substituted benzene group (C ₆ R ^la _5: where R ^la is as defined above Or OR ^3a wherein R ^3a is a lower alkyl group having 1 to 6 carbon atoms or a hydrogen atom, R ³ , R ⁴ and R ⁵ have the same meaning as R ² , X is a halogen atom of F, Cl, Br or I, Polymers of learning 1 as there is no bridge polymer or bridge by Y, when a bridge Y is _{^{O, S, CR l 2,}} NH or NR ^1, the molecular weight range of the polymer of formula (I) is 3,000 to 200,000).

According to the present invention, there is also provided a process for preparing the phthalocyanine polymer of Formula 1, wherein the substituted anhydride of Formula 2 is reacted with a metal salt and urea;

Wherein R ¹ , R ² and X are as defined in the above formula (1), said diphthalic acid anhydride is a bridged or bridged anhydride by Y, when bridged Y is O, S, CR ^l is _2, NH or NR ^l.)

Examples of the substituted or unsubstituted alkyl group in Formulas 1 and 2 of the present invention include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- , n-pentyl, isopentyl, neopentyl, 1,4-dimethylpropyl, n-hexyl, cyclohexyl, 1,3-dimethylbutyl, Ethyl-3-methylbutyl group, an n-octyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 3-methylbutyl group, A hydrocarbon group such as a methyl-1-isopropylbutyl group, a 2-methyl-1-isopropylbutyl group, a 1-t-butyl-2-methylpropyl group and an n-nonyl group; Alkoxy groups such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethyl group ethyl group and diethoxyethyl group An alkyl group; And halogenated alkyl groups such as a chloromethyl group, a 2,2,2-trichloroethyl group, a trifluoromethyl group, and a 1,1,1,3,3,3-hexafluoro-2-propyl group.

Examples of the preferable alkyl group in the alkyl group include an alkyl group having 2 to 4 secondary, tertiary and quaternary carbon atoms, particularly 1,2-dimethylpropyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, Methylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, -Isopropylbutyl group and 1-t-butyl-2-methylpropyl group.

In the above formulas (1) and (2) of the present invention, preferred examples of X include F or Cl.

The anhydride of the formula (2) of the present invention can be a commercially available compound and is also synthesized by a known method [Auman, B. C. (1993) in Advances in Polyimide Science and Technology; Proceedings of the 4th Interantional Conference on Polyimides (Feger, C., Khojatseh, M. M. and Htoo, M. S., eds), pp. 15-32, Technomic].

Examples of the divalent metal represented by M in the formula 1 of the present invention include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn and Sn. Examples of the metal oxide include VO ₂ and Si ₃ O ₄ , and examples of the substituted tetravalent metal include SiCl ₂ , SiBr ₂ and SiF _2. Examples of the metal oxide include VO ₂ , TiO2.

The phthalocyanine polymer of Formula 1 may be prepared by mixing the diphthalic anhydride of Formula 2 with a metal salt or urea in the presence of a catalyst, stirring the resultant mixture sufficiently at room temperature, To 400 , Preferably 240 To 260 At a temperature in the range of 0.5 to 10 hours, preferably 1.5 to 2.5 hours, by slowly heating the resulting mixture.

For example, the titanium oxide phthalocyanine polymer may be a mixture of a tetrabutoxy titanium salt (Ti (OBu) ₄ ), 4,4- (hexafluoroisopropylidene) diphthalic anhydride, and a mixture of urea and a catalyst and a molybdenum tetraoxide (NH ₄ ) ₂ MoO ₄ ) in the following manner. That is, the mixture was sufficiently stirred so as to mix well at room temperature, and then gradually heated to 100 To 400 , Preferably 250 Deg.] C for 0.5 to 10 hours, preferably 2 hours, to obtain a cyan-blue oxytitanium phthalocyanine polymer.

Since the process for preparing the phthalocyanine polymer prepared by heating from the mixture of the diphthalic anhydride of the formula (2) and the metal salt, urea and catalyst, which is provided according to the present invention, is prepared without using a solvent, Cleaning and the like are not required, and the manufacturing process of the near-infrared ray polymer is simplified and the cost is reduced.

The method of the present invention can also be carried out in the presence of a solvent. In this case, a high-boiling solvent is added to a mixture of a diphthalic anhydride and a metal salt, urea and a catalyst, and the mixture is heated at a high temperature Phthalocyanine polymer is prepared. Examples of high boiling solvents used in the process include -Methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene or mixtures of one or more of these. In this method, the phthalocyanine polymer is separated through a washing process of the reaction mixture, a drying process of the solvent and a purification process.

The thus prepared phthalocyanine polymer of the present invention has a number average molecular weight of about 3,000 to 200,000 and is used in a polar solvent such as acetone, acetonitrile, lower alcohol, dimethylformamide (DMF), dimethylsulfoxide (DMSO), pyridine, NMP, To about 20% by weight, and the UV spectrum of the solution dissolved in DMSO shows the maximum absorption peak at 700 nm as shown in FIG.

In the above method, when a metal salt is converted to vanadium pentoxide (V ₂ O ₅ ), an oxy vanadium-phthalocyanine polymer is prepared. In this case, the oxyvanadium-phthalocyanine polymer can be dissolved in the polar solvent at a ratio of 20 wt% (0.20 g / A solution can be prepared.

Another object of the present invention is to provide a composition comprising a phthalocyanine polymer having high solubility as a main component, and according to the present invention, there is provided a polymer composition as described below; At least one polar solvent selected from the group consisting of acetone, acetonitrile, lower alcohol, dimethylformamide (DMF), dimethylsulfoxide (DMSO), pyridine, NMP, sulfuric acid and water or a mixture thereof and the phthalocyanine polymer ; A polymer composition comprising at least one resin selected from the group consisting of polyvinyl butyral, polycarbonate, polyester, polymethyl methacrylate, and polyurethane and the phthalocyanine polymer of formula 1; At least one resin selected from the group consisting of polyvinyl butyral, polycarbonate, polyester, polymethacrylate and polyurethane is dissolved in toluene, butyl alcohol, 1,2-dichloroethane or a mixed solvent thereof (for example, phthalocyanine In the production of the photosensitive thin film using the polymer, 20 to 80% by weight, preferably 60 to 40% by weight of toluene and 80 to 20% by weight, preferably 40 to 60% by weight of butyl alcohol are mixed It is preferable to use one mixed solvent) and a composition comprising the phthalocyanine polymer of Formula 1 above; Sulfuric acid, Nafion hydrochloride, AsF ₆ , iodine, and the phthalocyanine polymer of the above formula (1).

The above-mentioned polymer composition of the present invention A high boiling point solvent selected from the group consisting of methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, nitrobenzene, May be further contained.

The composition ratio of each component of the composition of the present invention may differ depending on the intended use of the composition. However, when the composition is used in the production of a photosensitive thin film as described below, the phthalocyanine polymer of Formula By weight to 90% by weight, and the other components in a proportion of 90 to 10% by weight. When each component of the composition of the present invention deviates from the above-mentioned component ratio, the mechanical properties of the resultant photosensitive polymer thin film become poor, which is not preferable.

Various additives, lubricants, thickeners, and the like obvious to those skilled in the art may be added to the polymer composition of the present invention to improve the heat resistance, mechanical properties, processing characteristics, and the like.

Still another object of the present invention is to provide a photosensitive thin film having photosensitivity to visible light and near-infrared light in the region of 500 to 900 nm using the above-mentioned polymer composition.

As described above, the phthalocyanine polymer of formula (1), which is produced under solvent-free conditions, can be used as a conductive electrode support or plastic and / or plastic film selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, Mylar film, copper plate, conductive glass, A metal oxide-phthalocyanine polymer thin film is provided which, when coated on an insulating support selected from the group consisting of glass, exhibits good absorption in the wavelength region of 600 to 800 nm. As the coating, a method such as roll coating or spin coating can be used.

The phthalocyanine polymer of Formula 1 may be dissolved in a polar solvent selected from the group consisting of acetone, acetonitrile, lower alcohol, DMF, DMSO, pyridine, NMP, sulfuric acid and water, A conductive electrode support selected from the group consisting of a drum, an aluminum plate, a platinum, a mylar film, a copper plate, a conductive glass and a conductive plastic, or an insulating support selected from the group consisting of plastic and glass, , A photosensitive thin film having photosensitivity between 500 and 900 nm is provided.

In addition, the phthalocyanine polymer of Formula 1 of the present invention may be dissolved or processed in a solvent selected from the group consisting of ether, alcohol, aromatic hydrocarbons, monoterpene hydrocarbons and liquid paraffin, or a polyvinyl butyral (PVB), polycarbonate (PC) or the like, followed by milling, and then coating the mixture on the support.

The phthalocyanine polymer and the phthalocyanine polymer thin film provided in the present invention exhibit absorption peaks in the region of 500 to 900 nm and a thermal stability of 200 It is very likely to be applied to a photocopier using visible light or near infrared rays, a color copying machine, a photoconductive drum of a printer, a solar cell, a sensor, and other recording and optical elements, and these are also within the scope of the present invention.

Thickness of the thin film is not particularly limited, but when it is used in an electrophotographic copying machine or a laser printer, the thickness of the thin film is 0.2 to 2 . The features and other advantages of the present invention as described above will be more clearly described with reference to the following examples, but the scope of the present invention is not limited to the following examples.

[Examples 1 to 5]

[Preparation of phthalocyanine polymer]

[Example 1]

[Preparation of oxytitanium phthalocyanine polymer]

A commercially available 4,4- (hexafluoroisopropylidene) di-phthalic anhydride 8.89g, urea 12g, four molybdenum oxide ammonium salt _{((NH 4) 2 MoO 4} ) 0.03g and tetrabutoxy titanium salt (Ti (OBu) ₄ 3.40 g was placed in a 250 ml reaction vessel, stirred in a nitrogen atmosphere, and then 250 For 2 hours. After cooling to room temperature, the product was washed with distilled water, acetone, 1M hydrochloric acid solution, and then dried in a vacuum oven at 60 , An oxytitanium phthalocyanine polymer having a maximum absorption peak at 700 nm is obtained at a yield of 60% by weight as shown in FIG. The result of the elemental analysis of this compound is as follows.

Element C N O H

45.80% 13.65 14.32 2.29

The resulting oxytitanium phthalocyanine polymer has a maximum absorption peak at 700 nm and shows solubility in DMSO, DMF, pyridine, NMP and the like. The UV / vis absorption spectrum dissolved in DMSO is shown in FIG. The oxy titanium phthalocyanine polymer thus prepared had a number average molecular weight of 10643 and its infrared absorption spectrum is shown in FIG. The prepared oxytitanium phthalocyanine polymer was 250 And thermal analysis results are shown in FIG. 3.

[Example 2]

Except that 10 g of 9-phenyl-9-trifluoromethyl-2,3,6,7-xanthanetetracarboxylic dianhydride was used instead of 4,4- (hexafluoroisopropylidene) diphthalic anhydride The same procedure as in Example 1 was used, with a yield of 50%.

[Example 3]

[Preparation of oxyvanadium phthalocyanine polymer]

4,4- (hexafluoroisopropylidene) di-phthalic anhydride 8.89g, 12g of urea, use of molybdenum oxide and ammonium salts 0.03g vanadium pentoxide (V ₂ O ₅₎ 3.40g of 250 ml were placed in a reaction vessel, a nitrogen atmosphere, Lt; RTI ID = 0.0 > 200 & For 1 hour. After cooling to room temperature, the product is washed with distilled water, acetone, 1M hydrochloric acid solution and dried to obtain oxyvanadium phthalocyanine polymer in a yield of 25%. The result of the elemental analysis of this compound is as follows.

Element C N O H

% 44.67 10.97 23.24 2.36

The maximum absorption peak of the resulting oxytitanium phthalocyanine polymer was 684 nm and was soluble in DMSO, DMF, pyridine, NMP, sulfuric acid, and had a number average molecular weight of 15924. The UV / vis absorption spectrum obtained by dissolving the oxyvanadium phthalocyanine polymer prepared above in DMSO is shown in FIG. FIG. 5 shows an infrared absorption spectrum of the obtained oxyvanadium phthalocyanine polymer prepared by grinding the oxyvanadium phthalocyanine polymer together with KBr to prepare pellets. The results of thermogravimetric analysis of the oxyvanadium phthalocyanine polymer prepared above are shown in FIG.

[Example 4]

The reaction temperature was 210 And the reaction was carried out in the same manner as in Example 3 except that the reaction was conducted for 2 hours or more. The maximum absorption peak of the polymer obtained was 684 nm, and the yield was 40%.

[Example 5]

30 ml of 1-chloronaphthalene was added as a reaction solvent to prepare 250 And the solvent was removed through a steam distillation method. Subsequently, the same procedure as in Example 3 was carried out except that the solvent was removed and then purified with distilled water, acetonitrile, and 1 M hydrochloric acid solution. The maximum absorption peak of the resulting polymer was 692 nm, with a yield of 80%.

[Examples 6 to 29]

[Production of phthalocyanine polymer composition and thin film]

[Example 6]

1 g of the oxytitanium phthalocyanine polymer prepared in Example 1 was added to 10 ml of DMSO and stirred for 1 hour to prepare a solution of choline chloride. The prepared solution was applied to a conductive glass (ITO glass) Lt; 0 > C for 6 hours to form a 0.5 micron thick phthalocyanine polymer thin film. At this time, the maximum absorption peak of the thin film was 700 nm.

[Examples 7 to 9]

The same method as in Example 6 was used except that DMF, NMP, and sulfuric acid were used instead of DMSO.

[Example 10]

0.543 ml of concentrated sulfuric acid solution was added to 0 to 2 , And the mixture was rapidly stirred. 0.1 g of the phthalocyanine polymer obtained in Example 1 was added in small portions to adjust the temperature to be 2 Respectively. The mixture was stirred for 1 hour to form an overall uniform paste, followed by addition of acetone, mixing with an ultrasonic mixer, and then coating on conductive glass. The thickness of the thin film was 1 micron and the UV / vis absorption spectrum is shown in FIG. 7.

[Examples 11 to 15]

The same method as in Example 6 was used except that 1 g of oxyvanadium phthalocyanine polymer was used instead of 1 g of oxytitanium phthalocyanine polymer. The thickness of the thin films was 0.5 ~ 1.2 microns and the absorption range was 500 ~ 840 nm.

[Example 16]

20 ml of cooling water was dropwise added dropwise to the oxytitanium phthalocyanine polymer dough prepared in Example 10 to form a precipitate. It is washed several times with distilled water so that the pH of the filtrate becomes neutral, then washed with acetone and dried. When the prepared polymer is dissolved in DMSO to prepare a thin film, a polymer thin film having a maximum absorption peak at 700 nm is produced.

[Examples 17 to 27]

The compositions of Examples 6 to 16 are applied onto a mylar film. The thickness of the film was 2 m, and the above film is dried in a vacuum oven. This film shows good absorption at 600 to 800 nm.

[Example 28]

0.2 g of the oxytitanium phthalocyanine polymer is added to a 125 ml Erlenmeyer flask, and 0.3 g of polyvinyl butyral is added thereto, and then 4.5 ml of a 1-butyl alcohol mixed solvent of the same ratio as toluene is added. Add glass beads, stopper, and stir in a mill for more than 18 hours. This mixed solution is applied on a mylar film using a bar coating. The thickness of the film is 1 m and the above film was placed in a vacuum oven at 60 ≪ / RTI > This film shows good absorption at 600 to 800 nm.

[Example 29]

In a 125 ml Erlenmeyer flask, 0.2 g of the phthalocyanine polymer of the present invention is added, and 0.5 ml of DMF is added. Then, 0.3 g of polyvinyl butyral is added, and 2 ml of a 1-butyl alcohol mixed solvent of the same amount of toluene is added. Add the glass beads, stop the stopper, and stir in the mixer for 18 hours or more.

The above mixed solution is applied on a mylar film using a bar coating. The thickness of the film is 1 m and the above film is dried in a vacuum oven. This film shows good absorption at 600 to 800 nm.

[Effects of the Invention]

As described above, according to the present invention, it is possible to produce a phthalocyanine polymer and a photosensitive thin film which are highly soluble in an organic solvent and exhibit good sensitivity to near infrared rays and visible light.

Claims (17)

A phthalocyanine polymer represented by the following Formula 1: (Wherein M is a hydrogen atom or a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide, m and n are integers of 2 or more, and R ¹ is a hydrogen atom, a lower alkyl group, alkyl ether group or a substituted benzene group (C ₆ R ^la _5: where R ^la is a hydrogen atom, the number of carbon atoms 1-6 lower alkyl group or alkyl ether group), and, R ² is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl group, an alkyl ether having 3 to 10 carbon atoms, a substituted benzene group (C ₆ R ^la _5: where R ^la is as defined above Or OR ^3a wherein R ^3a is a lower alkyl group having 1 to 6 carbon atoms or a hydrogen atom, R ³ , R ⁴ and R ⁵ have the same meaning as R ² , X is a halogen atom of F, Cl, Br or I, The polymers of formula (1) as there is no bridge polymer or bridge by Y, when a bridge Y is _{^{O, S, CR l 2,}} NH or NR ^1, the molecular weight range of the polymer of formula (I) is 3,000 to 200,000). A process for preparing a phthalocyanine polymer represented by the following Chemical Formula 1, wherein a substituted anhydride of the following Chemical Formula 2 is reacted with a metal salt and urea; (Wherein M is a hydrogen atom or a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide, m and n are integers of 2 or more, and R ¹ is a hydrogen atom, a lower alkyl group, alkyl ether group or a substituted benzene group (C ₆ R ^la _5: where R ^la is a hydrogen atom, the number of carbon atoms 1-6 lower alkyl group or alkyl ether group), and, R ² is a hydrogen atom, an alkyl group of 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl group, an alkyl ether having 3 to 10 carbon atoms, a substituted benzene group (C ₆ R ^la _5: where R ^la is as defined above Or OR ^3a wherein R ^3a is a lower alkyl group having 1 to 6 carbon atoms or a hydrogen atom, R ³ , R ⁴ and R ⁵ have the same meaning as R ² , X is a halogen atom of F, Cl, Br or I, Based polymers of formula (1) as there is no bridge polymer or bridge by Y, when a bridge Y is _{^{O, S, CR l 2,}} NH or NR ^1, the range of the molecular weight of the polymer of formula (I) is 3,000 to 200,000 ). Wherein R ¹ , R ² and X are as defined in the above formula (1), said diphthalic acid anhydride is bridged or bridged anhydride by Y, and when bridged Y is O, S, CR ^l _2, is NH or NR ^1.) 3. The method of claim 2, The reaction is carried out in a high boiling point solvent selected from the group consisting of methyl naphthalene, methoxynaphthalene, chloronaphthalene, diphenyl ethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, ≪ / RTI > 4. The process according to claim 2 or 3, wherein 100 to 100 < RTI ID = 0.0 > To 400 ≪ / RTI > is heated to react. At least one polar solvent selected from the group consisting of acetone, acetonitrile, lower alcohol, dimethylformamide, dimethyl sulfoxide, pyridine, NMP, sulfuric acid and water or a mixture thereof and the phthalocyanine polymer of formula (1) ≪ / RTI > 6. The method of claim 5, A high boiling point solvent selected from the group consisting of methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, nitrobenzene, ≪ / RTI > 1. A polymer composition comprising at least one resin selected from the group consisting of polyvinyl butyral, polycarbonate, polyester, polymethyl methacrylate, and polyurethane, and a phthalocyanine polymer of formula 1 as claimed in claim 1. 8. The method of claim 7, A high boiling point solvent selected from the group consisting of methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, nitrobenzene, ≪ / RTI > A solution prepared by dissolving at least one resin selected from the group consisting of polyvinyl butyral, polycarbonate, polyester, polymethacrylate and polyurethane in toluene, butyl alcohol, 1,2-dichloroethane or a mixed solvent thereof; A polymer composition comprising a phthalocyanine polymer of formula (I) as claimed in claim 1. 10. The method of claim 9, A high boiling point solvent selected from the group consisting of methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, nitrobenzene, ≪ / RTI > Sulfuric acid, Nafion hydrochloride, AsF ₆ , iodine, and a phthalocyanine polymer of formula (I) as claimed in claim 1. 12. The method of claim 11, A high boiling point solvent selected from the group consisting of methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene, nitrobenzene, ≪ / RTI > A conductive electrode support selected from the group consisting of an aluminum foil, an aluminum drum, an aluminum plate, a platinum, a mylar film, a copper plate, a conductive glass and a conductive plastic or an insulating support selected from the group consisting of plastic and glass, A photosensitive polymer thin film comprising the phthalocyanine polymer claimed in claim 1. A composition containing the phthalocyanine polymer of formula (I) as claimed in claim 1 is applied to a conductive electrode support or plastic and / or plastic support selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, Mylar film, copper plate, conductive glass and conductive plastic, Wherein the solvent is coated on the insulating support selected from the group consisting of glass, and the solvent is dried. An organic photosensitive drum consisting essentially of a phthalocyanine polymer of formula (I) as claimed in claim 1, and comprising a recording layer formed on the surface of the support and a support. A recording element composed mainly of a phthalocyanine polymer of the formula (1) as claimed in claim 1, comprising a recording layer formed on the surface of the support and a support. An optical element mainly composed of a phthalocyanine polymer of the formula (1) as claimed in claim 1, comprising a recording layer formed on the surface of the support and a support.