KR19990085367A - Poly (phthalocyanine) copolymer having excellent processability and method for producing same, polymer composition using same and method for producing phthalocyanine polymer thin film - Google Patents

Abstract

The present invention provides a poly (phthalocyanine) copolymer selected from the group consisting of poly (phthalocyanine) imide of Formula 1 and poly (phthalocyanine) carboxylic acid of Formula 2 or ester thereof, a method for preparing the same, a polymer composition comprising the same, and It relates to a polymer thin film using these. The poly (phthalocyanine) copolymer of the present invention is soluble in organic solvents and has excellent photosensitivity and processability, and thus can be used in fields such as color filters, organic photosensitive drums, recording elements or optical elements.

[Wherein R ¹ and R ² independently of one another are a hydrogen atom, a substitutable linear or branched C _1-20 alkyl or alkoxy group, a substitutable linear or branched C _1- having 1 to 10 oxygen atoms in the chain; _{A 20} alkyl or alkoxy group, or a substituted phenyl or phenoxy group (which may have from 1 to 5 C _1-6 alkyl or alkoxy groups as substituents);

R ³ and R ⁴ have the same meaning as R ¹ ;

X and Y independently represent a single bond, O, S, CO, SO ₂ , C (CF ₃ ) ₂ , CR ¹ ₂ , NH or NR ¹ , or two phenyl rings of the tetracarboxylic anhydride May be fused to each other without a linking group X and Y to form a naphthyl ring, or only one of X or Y may form a biphenyl structure connected by a single bond;

p, q and r are each an integer of 0 or more, and p + q + r is an integer of 1 or more;

W represents a hydrogen atom or the symbol M, wherein M represents a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide group;

The molecular weight range of the polymer of formula 1 or 2 is preferably 3,000 to 200,000.]

Description

Poly (phthalocyanine) copolymer having excellent processability and method for preparing same, polymer composition and method for producing phthalocyanine polymer thin film using same

The present invention relates to a poly (phthalocyanine) copolymer, a method for producing the same, a polymer composition comprising the same, and a polymer thin film using the same. More specifically, the present invention is a poly (phthalocyanine) imide, poly (phthalocyanine) carboxylic acid or ester thereof, which is soluble in an organic solvent, has high sensitivity to near infrared rays and visible light, and has excellent processability. Phthalocyanine) copolymers, a method for producing the same, and a method for manufacturing a thin film using the same, which can be used in fields such as color filters, organic photosensitive drums, recording elements, or optical elements.

Phthalocyanine has high absorption characteristics in the visible and near infrared region, and has excellent photoconductivity, photosensitivity, and optical memory characteristics, and is used as an electrophotosensitive member, a solar cell, a sensor, and the like. Many applications are expected. In addition, phthalocyanine has high thermal stability and high photochemical stability, and is used not only as colorants such as dyes and dyes, but also as color filters for liquid crystal display elements, blue toners for copiers and printers, and the like. For example, as a charge-generating material having sensitivity to near infrared rays, metal phthalocyanine and metal phthalocyanine such as oxytitanium phthalocyanine, oxyvanadium phthalocyanine, magnesium phthalocyanine, chloro-aluminum phthalocyanine, chloro-indium phthalocyanine, chloro-gallium phthalocyanine, etc. The most studied, the contents of which are described in Japanese Patent Laid-Open Nos. 49544/1984, 166959/1984, 239248/1986, 67094/1987, 366/1988, 116158/1988, 198067/1988 and 17066/1989 and the like. A blue toner composed of metal phthalocyanine is described in International Publication No. 96-703246, and a method of manufacturing an optical recording medium is disclosed in Publication No. 96-15421, Publication No. 95-13391, Publication No. 93-517 , Publication No. 96-22856 and Publication No. 96-10332. Blue filters for LCDs comprising phthalocyanine dyes are described in Announcement Number: 93-6714, Announcement Number: 93-2920, Announcement Number: 93-2918, and also reactive dyes (Notification Number: 95-11364, Announcement Number: 95-7219, 93-6467), green color masterbatch composition (notification number: 95-8899), method for preparing infrared absorption phthalocyanine compound (notification number: 94-369), method for preparing ink concentrate (publication number: 97- 27239), transparent optically-acting elements (publication number: 97-27093), pigment compositions (publication number: 97-10892), phthalocyanine photosensitizers for photodynamic therapy and methods for their synthesis and use (publication number: 96-704980) , Title of the invention: recordable organic optical recording medium (publication number: 96-32362), topical pharmaceutical composition (publication number: 96-28918), bactericidal composition (publication number: 95-702386), gas sensor and its gas How to measure the relative resistance value of the sensor (publication number: 95-19718) Composition (Publication No.: 96-14754), there is known. With such wide applicability, various phthalocyanines and polymers have been studied, and for example, a method for preparing dimethylaminomethyl copper phthalocyanine (notification number: 96-13077), a method for preparing copper phthalocyanine (public number: 97-1473), substitution Phthalocyanine (publish number: 96-13076, publication number: 96-6675, publication number: 96-1062, publication number: 97-702328, publication number: 97-10770), improved organic compounds and methods for their preparation (notification No .: 96-2658), halogenated phthalocyanine compound (notification number: 96-1743), method for producing pigmented copper phthalocyanine (notification number: 94-6240), method for producing metal phthalocyanine (notification number: 94-6069), aluminum Phthalocyanine reactive dye (published number: 97-10888), method for preparing a non-aqueous dispersion of copper phthalocyanine (published number: 97-700733), mixture of substituted phthalocyanine isomers and preparation method thereof (Publication No. 96-10646), Alkyl phthalocyanine near infrared absorbers and recording / display materials using the same (Publication No. 89-16418) have been studied and published.

However, since the phthalocyanine compound according to the contents known in the literature is low in its synthesis yield, difficult to purify, and low in solubility in general organic solvents, it is difficult to process when producing a photosensitive thin film for application to various devices, The drawback is that it is impossible to increase the purity. If the purity and solubility are low, there is a problem that the sensitivity, the recording properties, and the reflectance of the medium are insufficient, thereby providing an industrially useful photosensitive thin film. When the photosensitive thin film is manufactured using the phthalocyanine compound, the photosensitive thin film should be manufactured by using a sublimation or vapor deposition apparatus or a combination polymer together with a bar coating method, wherein the sublimation or vapor deposition apparatus is It is expensive and there is a problem in that large area photosensitive thin film coating is impossible. In addition, when the photosensitive thin film is manufactured by a method such as bar coating using a binding polymer together, there is a problem in that phase separation occurs even after the thin film is manufactured because of a phase separation problem with the binding polymer. When phase separation occurs, the light stability is not low, and thus a stable recording signal cannot be obtained, and it is easily decomposed to cause a fatigue phenomenon and shorten the life. In addition, the phthalocyanine compound known in the above-mentioned document is produced by agglomeration or crystallinity, and there is a problem in that the transmittance of the thin film is low and scattering of incident light is large after the thin film is manufactured.

In order to solve the problems of solubility and processability of the phthalocyanine compound, 1, 2, 3, 4, 8, 9, 10, 11, 15, 16, 17, 18, 22, 23, 24, 25, etc. of the phthalocyanine compound Studies have been attempted to introduce various substituents at the position. For example, Hanack et al., Inorg. Chem. (1984) discloses phthalocyanines having 8 substituents at the positions 2, 3, 9, 10, 16, 17, 23, 24 at 23, 1065, such as alkoxy groups, tetrabutyl groups, nitro groups, halogens, alkyl groups, and the like. In addition, W. Urban et al., J. Appl. Polym. Sci. (1993), 47, 2017, after synthesis of phthalocyanine having four carboxyl groups, reacted with alcohol groups to produce phthalocyanine with ester substituents with long alkyl chains, showing increased solubility. Also, European Patent Publication Nos. 0373643 and 0353394, Japanese Patent Publication Nos. 197280/1986, US Patent Nos. 4298975 and 769307 disclose optical recording media using halogen alkyl substituted phthalocyanines. As a result, the solubility in the coating solvent and the stability of the coating solution are improved, but the disadvantages of insufficient sensitivity, refractive index, reflectance, recordability, etc. remain.

Much research has been conducted on phthalocyanine polymers for the purpose of improving solution processability and stability. S. L. Yang et al., J. Photochem. and Photobio. 88, 183, (1995) discloses a result of measuring a photoconductivity by preparing a compound in which copper-phthalocyanine is present as a side chain in the basic skeleton of a poly (vinylcarbazole-acrylamide) copolymer. In addition, a method of introducing a phthalocyanine into the side chain by an acrylic copolymerization reaction to produce a polymer dye is also disclosed (Publication Number: 97-27224). However, in this case, phthalocyanine is introduced into the side chain, so that the photoelectric properties are not properly exhibited, which causes a problem of reducing the light sensitivity.

As a result, since a polymer having a phthalocyanine chain as a basic skeleton has been developed, polymers having a phthalocyanine chain as a basic skeleton can be classified into four types. The first type is in the form of bridging phthalocyanine to an alkyl substituent, the second type is a fused form of a whole by sharing two phthalocyanines in one benzene ring, and the third type is phthalocyanine. The form bridged by a substituent forms a ladder form, in which a exocyclic group is substituted in the benzene ring to bridge a phthalocyanine, and the fourth type is that the central metals of the phthalocyanine are bridged by an oxygen atom or a halogen atom. It is a form. An example of a first type is B. B. Simms et al. J. Polym. Sci. A-1 (1970), 8, 111 discloses the preparation of phthalocyanine polymers for various metals using an alkyl group containing a carborane as a bridging group together with methylsiloxane or urethane groups. It can be mentioned as. However, these compounds resulted in rather reducing the stability of the phthalocyanine polymer due to the instability of the bridging group of phthalocyanine and the influence of impurities.

Parker et al., J. Polym. Sci. Polym. Chem. Ed. (1982), 20, 269 and 2073 synthesized a phthalocyanine polymer using a benzimidazole as a bridge group to synthesize a compound having excellent thermal stability, but these also had low solubility in common organic and inorganic solvents, and a small amount of impurities Could not be removed completely. Examples of the second type include J. Polym. J. A. Parker et al. Sci. Polym. Chem. Ed. (1982), 20, 1785, synthesized planar phthalocyanine polymers by reacting pyromellitic dianhydride with metal salts and urea under a catalyst, and these compounds are also soluble in sulfuric acid, NaOH, DMSO, DMF, DMAC, etc. Although the molecular weight is about 2,000, there is a problem of showing a very low degree of polymerization. Examples of third types include J. Polym. J. A. Parker et al. Sci. Polym. Chem. Ed. (1982), 20, 2773, and 2781, which synthesized a ladder type phthalocyanine polymer by reacting benzophenone tetracarboxylic acid dianhydride and pyromellitic dianhydride with phthalocyanine tetraamine, respectively. . These compounds are excellent in thermal stability but cross-linked in two dimensions to form a ladder shape, so that their solubility is low, making it difficult to clearly analyze the structure even by using elemental analysis or infrared spectroscopy. Examples of the fourth type include R. P. Linstead et al., J. Chem. Soc. (1936), 1719, M. E. Kenny et al., J. Amer. Chem. Soc. (1969), 91, 5210, and the like, but these compounds were also poorly soluble.

In order to solve the above problems, the present inventors have studied thermally stable functional polymers which exhibit good photoelectricity in the near infrared region, and have improved solubility, and a method for synthesizing the same, and include phthalic anhydride and substitutable benzophenone tetra The preparation of phthalocyanine polymers from carboxylic dianhydrides, metal oxides or salts thereof has found that poly (phthalocyanine) imide copolymers having a low degree of crosslinking, linearity and improved solubility in common solvents can be obtained.

The poly (phthalocyanine) carboxylic acid copolymer prepared by hydrating the produced poly (phthalocyanine) imide under an acidic or basic solution and converting the imide group to a carboxyl group is an aluminum plate or mylar in a solution state in a general solvent. It has been further discovered that a thin film can be formed by coating on a common support or electrode such as a film, conductive glass (ITO glass), PET resin, or platinum electrode.

Furthermore, the poly (phthalocyanine) ester copolymer prepared by reacting the poly (phthalocyanine) carboxylic acid copolymer with an esterifying agent such as an alcohol or a halide may not only provide excellent photosensitivity and optical properties, but also further improved mechanical and solubility characteristics. Found to have

In addition, the poly (phthalocyanine) copolymers of the present invention can be mixed with other general purpose resins such as polyvinylbutyral (PVB), polycarbonate (PC), and the like, without impairing their mechanical properties. It has been found that more improved photosensitive thin films can be produced.

The present invention has been completed based on the above findings.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a characteristic curve showing spectral absorption characteristics measured by dissolving poly (oxytitanium phthalocyanine) imide prepared in Example 1 in DMF;

2 is an infrared absorption spectral diagram of the poly (oxytitanium phthalocyanine) imide prepared in Example 1;

3 is a diagram showing a thermogravimetric curve of poly (oxytitanium phthalocyanine) imide prepared in Example 1;

4 is a diagram showing a spectral absorption spectrum (concentration: 0.01% by weight) of a solution in which poly (oxytitanium phthalocyanine) imide prepared in Example 9 is dissolved in DMF;

5 is a spectral absorption spectrum of a poly (oxytitanium phthalocyanine) carboxylic acid prepared by Example 20, dissolved in DMF;

FIG. 6 is a diagram showing a spectral absorption spectrum (DMF solution having a concentration of 0.0063, 0.0019, 0.00057% by weight from top to bottom) of the poly (oxytitanium phthalocyanine) carboxylic acid prepared by Example 22; FIG.

FIG. 7 is a diagram showing an infrared absorption spectrum of the poly (oxytitanium phthalocyanine) decanoyl ester prepared in Example 25.

Accordingly, the first object of the present invention is a poly (phthalocyanine) imide of Formula 1 or poly (phthalocyanine) of Formula 2, which has excellent solubility, mechanical properties, and the like for organic solvents, and has high sensitivity to near-infrared and visible light. To provide carboxylic acids or esters thereof.

[Formula 1]

[Formula 2]

[Wherein R ¹ and R ² independently of one another are a hydrogen atom, a straight or branched C _1-20 alkyl or alkoxy group, a straight or branched C _1-20 alkyl or alkoxy having 1 to 10 oxygen atoms in the chain Group, or a substituted phenyl or phenoxy group (which may have 1 to 5 C _1-6 alkyl or alkoxy groups as substituents);

R ³ and R ⁴ have the same meaning as R ¹ ;

X and Y independently represent a single bond, O, S, CO, SO ₂ , C (CF ₃ ) ₂ , CR ¹ ₂ , NH or NR ¹ , or two phenyl rings of the tetracarboxylic anhydride May be fused to each other without a linking group X and Y to form a naphthyl ring, or only one of X or Y may form a biphenyl structure connected by a single bond;

p, q and r are each an integer of 0 or more, and p + q + r is an integer of 1 or more;

W represents a hydrogen atom or the symbol M, where M represents a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide group.]

Here, the molecular weight range of the polymer of the formula (1) or (2) is preferably 3,000 to 200,000.

It is a second object of the present invention to provide a method for preparing the poly (phthalocyanine) copolymer of Chemical Formula 1 or 2 above.

According to the present invention, the poly (phthalocyanine) imide copolymer of the formula (1) is substituted with a phthalic anhydride of the formula (3), a substituted diphthalic anhydride of the formula (4), for example, benzophenone tetracarboxylic dianhydride (bezophenone tetracarboxylic acid dianhydride), urea, and metal compounds of formula 5 are prepared by a process consisting of heating in the absence or in the presence of a solvent.

(Wherein R ¹ is as defined above)

(Wherein R ² is as defined above)

M _a Z _b

[Wherein M is a divalent metal, a trivalent or tetravalent substituted metal or metal oxide group, p, q and r are each an integer of 0 or more, a and b are an integer of 1 or more, Z is Cl, Br, I, OR ¹ , where R ¹ is as defined above, and examples thereof include Ti (OBu) ₄ , V ₂ O _5, and the like.]

In the preparation method of the present invention, the poly (phthalocyanine) imide copolymer of Chemical Formula 1 prepared above is prepared in an acidic aqueous solution such as sulfuric acid or a basic aqueous solution such as sodium hydroxide at a temperature of 50 to 100 ° C. for 1 to 5 hours. By heating under stirring, and optionally by cooling, washing and purifying, a poly (phthalocyanine) carboxylic acid copolymer of formula (2) in which an imide group is converted to a carboxyl group can be obtained, whereby the poly (phthalocyanine) copolymer is organic Solubility in solvents increases by 1 to 100 times or more.

In addition, the poly (phthalocyanine) carboxylic acid copolymer of Formula 2 prepared above is dissolved in an acidic aqueous solution such as hydrochloric acid, and then reacted with an esterifying agent, such as a compound of Formula 6, under stirring, and in some cases, in general, organic A poly (phthalocyanine) ester copolymer of formula (2) with better solubility in solvents can be prepared.

R^OneOH or R^OneZ

(Wherein R ¹ and Z are as defined above).

A third object of the present invention is to provide a polymer composition composed of the poly (phthalocyanine) copolymer of Formula 1 or 2 and a polar solvent, which polymer composition can be used for thin film production. Examples of the polar solvent include acetone, acetonitrile, lower alcohols, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, 1-methyl-2-pyrrolidone (NMP), sulfolane, sulfuric acid, water, Or one or more mixtures thereof. It is, of course, possible to add other polar solvents or nonpolar solvents to the extent that they do not adversely affect the object of the present invention.

For example, α-methylnaphthalene, sulfolane, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, xylene or mixtures of one or more thereof It may further contain a high boiling point solvent.

It is a fourth object of the present invention to provide a polymer thin film comprising a poly (phthalocyanine) copolymer of formula (1) or (2), wherein the thin film is, for example, aluminum foil, aluminum drum, aluminum plate, platinum, mylar The film may be coated on a conductive electrode support selected from the group consisting of film, copper plate, conductive glass and conductive plastic or an insulating support selected from the group consisting of plastic and glass.

A fifth object of the present invention is to provide a method for producing a polymer thin film consisting of coating a polymer composition comprising a poly (phthalocyanine) copolymer of formula 1 or 2 on the above-described support and then drying the solvent.

A sixth object of the present invention is to provide a color filter, an organic photosensitive drum, a recording element or an optical element, for example, comprising a poly (phthalocyanine) copolymer of the formula (1) or (2).

Hereinafter, the present invention will be described in more detail.

In the above Chemical Formulas 1 to 6 of the present invention, examples of the substituted or unsubstituted alkyl group are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group , n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2- Dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3 Hydrocarbon groups such as -methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group, 1-t-butyl-2-methylpropyl group and n-nonyl group; Alkoxy such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group and diethoxyethyl group Alkyl group; And halogenated alkyl groups such as chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, and 1,1,1,3,3,3-hexafluoro-2-propyl group.

Examples of preferred alkyl groups among the alkyl groups include alkyl groups having 2 to 4 secondary, tertiary and quaternary carbon atoms, especially 1,2-dimethylpropyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2 -Dimethylbutyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1 -Isopropylbutyl group and 1-t-butyl-2-methylpropyl group are mentioned.

In Formulas 1 and 2 of the present invention, preferred examples of X and / or Y include>CO,> SO ₂ ,> C (CF ₃ ) ₂ ,> NH or> NR ¹ .

Substituted phthalic anhydride of formula (3) and substitutable diphthalic anhydride of formula (4) of the present invention can be used commercially available compounds, are also synthesized by known methods [Auman, BC (1993) in Advances in Polyimide Science and Technology Proceedings of the 4th International Conference on Polyimides (Feger, C., Khojatseh, MM and Htoo, MS, eds), pp. 15-32, Technomic.

In the above Chemical Formulas 1 and 2 of the present invention, examples of the divalent metal represented by M or W may mention Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn and Sn, and may be substituted. Examples of trivalent metals mentioned may refer to Al-Cl, Al-Br, In-Cl, In-Br and In-I, and examples of substituted tetravalent metals refer to SiCl ₂ , SiBr ₂ , SiF ₂ In addition, examples of the metal oxide group include VO and TiO.

According to the present invention, the poly (phthalocyanine) imide copolymer of formula (1) comprises a phthalic anhydride of formula (3), a diphthalic anhydride of formula (4), a metal oxide or metal salt of formula (5), and urea of a catalyst commonly used in the synthesis of phthalocyanine After mixing in the presence, the resulting mixture is sufficiently stirred to mix well at room temperature, and then at a temperature of 100 ° C. to 400 ° C., preferably 150 ° C. to 300 ° C., for 0.5 to 20 hours, preferably 1.5 to 5 hours. It may be produced by a method consisting of a slow heating reaction.

Specifically, as one example, the titanium oxide phthalocyanine polymer is tetrabutoxytitanium [Ti (OBu) ₄ ], 4,4- (hexafluoroisopropylidene) diphthalic anhydride, phthalic anhydride, and urea and yarns. Molybdenum ammonium oxide salt [(NH ₄ ) ₂ MoO ₄ ] was mixed and the resulting mixture was sufficiently stirred to be well mixed at room temperature, and then slowly heated to a temperature of 100 ° C. to 400 ° C., preferably 190 ° C. to 260 ° C. When heated for 0.5 to 10 hours, preferably 2 hours, a dark blue green oxytitanium phthalocyanine polymer is obtained.

The method for preparing poly (phthalocyanine) imide of formula 1 according to the present invention has an advantage that can be performed without using a solvent. That is, the reactants can be mixed and reacted without a solvent, and since there is no need for a process such as solvent removal / drying or washing after preparing a copolymer as a product, there is a significant advantage in the manufacturing process. Therefore, in the near-infrared polymer manufacturing process, there is an effect of simplifying the process, environmental benefits, and thereby cost reduction.

In addition, the method for preparing poly (phthalocyanine) imide of formula 1 according to the present invention may be carried out using a solvent, in which case phthalic anhydride of formula 3 and dianhydride of formula 4, metal compound or salt of formula 5 After adding a mixture of a solvent and an optional high boiling point solvent to a mixture of, urea and a catalyst, and reacting in the same manner as described above, a poly (phthalocyanine) imide copolymer of the formula (1) is prepared.

Examples of the high boiling point solvent used in the method include α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylenecarbonate, tetramethylenesulphone, xylene or one or more kinds. Mention may be made of mixtures thereof. In this method, the poly (phthalocyanine) copolymer is separated by washing the reaction mixture, drying and purifying the solvent.

The poly (phthalocyanine) copolymer of the present invention prepared as described above has a number average molecular weight of about 3,000 to 200,000, preferably acetone, acetonitrile, lower alcohol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridine, It can be dissolved in a polar solvent such as NMP, sulfuric acid, water and the like at a ratio of 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. 1.

In the above-described preparation method given by way of example, when vanadium pentoxide [V ₂ O ₅ ] is used instead of tetrabutoxytitanium [Ti (OBu) ₄ ] as the metal salt compound, an oxyvanadium-phthalocyanine polymer is prepared, in this case In the above polar solvent, a solution which can be dissolved at a ratio of 20% by weight (0.20 g / ml) can be prepared.

In the method for producing a poly (phthalocyanine) copolymer of the present invention, the poly (phthalocyanine) imide of the formula (1) prepared according to the above-described method is dissolved in an acidic aqueous solution such as sulfuric acid or an aqueous solution of a base and salt such as sodium hydroxide. After reacting by heating under stirring at a temperature of 50 to 100 ° C. for 1 to 5 hours, and then cooling, washing and purifying in some cases, poly (2) having a solubility in organic solvents increases by 1 to 100 times or more. Phthalocyanine) carboxylic acid copolymer is prepared.

As an example of the preparation method of the poly (phthalocyanine) carboxylic acid copolymer of the formula (2), concentrated sulfuric acid (H₂SO₄20 ml of distilled water 4 ml To an mL to prepare an acidic aqueous solution, to which 0.15 g of poly (oxytitanium phthalocyanine) imide copolymer prepared from 6FDA was added as described above, followed by heating for 2 hours under stirring, followed by precipitation, washing and Upon drying, a poly (phthalocyanine) carboxylic acid copolymer of formula (2) with improved solubility is prepared. At this time, the heating temperature is not limited, but is preferably 70 to 110 ℃.

In addition, the poly (phthalocyanine) ester copolymer of formula (2) is an ester such as an alcohol or a halide compound of formula (6) after dissolving the poly (phthalocyanine) carboxylic acid copolymer prepared by the above method in an acidic or basic solution. It may be prepared by mixing with a topical agent and heating under stirring. As an example of the preparation method, 0.5 g of K ₂ CO _{3 and} 0.5 g of CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl were added to a mixture of 30 ml of butyl ether and 30 ml of distilled water. To the resulting mixture was added 0.5 g of poly (titayloxy phthalocyanine) carboxylic acid prepared as described above and 0.7 g of CH ₃ (CH ₂ ) ₁₁ Br followed by heating at about 89 ° C. under stirring. Treatment as described above provides a poly (phthalocyanine) decanoyl ester derivative of formula (2) with good solubility.

According to the present invention there is provided a polymer composition composed of at least one polar solvent and a poly (phthalocyanine) copolymer of formula 1 or 2, and any one or more other polymers and any one or more high boiling organic solvents.

Examples of the at least one polar solvent include acetone, acetonitrile, lower alcohols, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), sulfolane, xylene, 3-nitro-α, α, α-trifluorotoluene Mention may be made of pyridine, NMP, sulfuric acid and water.

As said at least one other polymer, mention may be made of polyvinylbutyral, polycarbonate, polyolefin, polyester, polymethylmethacrylate and polyurethane.

As the at least one high boiling organic solvent, α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, sulfolane, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate and xylene may be mentioned.

As specific examples of the polymer composition of the present invention, the following may be mentioned.

A polymer composition composed of the polar solvent and a copolymer of the present invention;

A polymer composition composed of said polar solvent, said other polymer and a copolymer of the invention;

One or more resins selected from the group consisting of polyvinyl butyral, polycarbonate, polyolefin, polyester, polymethacrylate, polyurethane and toluene, butyl alcohol, 1,2-dichloroethane or a mixed solvent thereof (e.g. In the preparation of the photosensitive thin film using the phthalocyanine polymer described below, in order to increase the mechanical strength, 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 It is preferable to use a mixed solvent mixed with butyl alcohol) polymer composition comprising a solution dissolved in a phthalocyanine polymer of the formula (1) and / or (2);

A polymer composition comprising sulfuric acid, hydrochloric acid, Nafion, AsF ₆ , iodine and a phthalocyanine polymer of Formulas 1 and / or 2 above.

The component ratio of each component of the polymer composition of the present invention may be different depending on the use of the composition, but when the composition is used to prepare a photosensitive thin film as described below, the phthalocyanine copolymer of the present invention is based on the total weight of the composition. It is preferable to use in the ratio of 1 to 90 weight%, and to use other components in the ratio of 99 to 10 weight%. When each component of the composition of the present invention is out of the component ratio, it is not preferable because the mechanical properties of the resulting photosensitive polymer thin film is not good. The proportion of phthalocyanine copolymer in the polymer composition is preferably 2 to 50% by weight, more preferably 3 to 30% by weight.

In order to improve heat resistance, mechanical properties, processing properties, and the like, the above-described polymer composition of the present invention may be added various additives, lubricants, thickeners and the like which are obvious to those skilled in the art.

According to this invention, the photosensitive thin film which has photosensitivity to the ultraviolet-ray, visible ray, and near-infrared ray of 300-900 nm region using the polymer composition mentioned above is provided.

As described above, when the phthalocyanine copolymer of the present invention prepared under solvent-free conditions is coated on a general support such as an aluminum plate, a mylar film, or a conductive glass, the metal oxide exhibiting good absorption in a wavelength range of 600 to 800 nm. Phthalocyanine polymer thin films are provided. The coating may be a method such as roll coating or spin coating. For this purpose, poly (phthalocyanine) carboxylic acids of the formula (2) or esters thereof are preferred.

In addition, the phthalocyanine copolymer according to the present invention is dissolved in a polar solvent selected from the group consisting of acetone, acetonitrile, lower alcohol, DMF, DMSO, pyridine, sulfolane, NMP, sulfuric acid, water, and a mixed solvent thereof, and A conductive electrode support selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, mylar film, copper plate, conductive glass and conductive plastic, or an insulating support selected from the group consisting of plastic and glass and coated on the support Thereafter, drying the solvent provides a photosensitive thin film having photosensitivity between 300 and 900 nm.

In addition, the phthalocyanine copolymer of the present invention is processed by dissolving in one or more solvents selected from the group consisting of ethers, alcohols, aromatic hydrocarbons, monoterpene hydrocarbons and liquid paraffins, or polyvinylbutyral (PVB), polycarbonate (PC) A photosensitive thin film is also provided by the method of mixing with the general purpose polymers, such as these, and milling, and apply | coating on the said support body.

The phthalocyanine copolymer and the phthalocyanine copolymer thin film provided in the present invention are capable of solution processing, but exhibit absorption peaks in the region of 600 to 900 nm, and have a thermal stability of 200 ° C. or more, so that color filters for display elements, visible light, The application potential of copiers, color copiers, photosensitive drums of laser printers, solar cells, sensors, and the like, and other recording elements and optical elements using near infrared rays is very high, and these also belong to the scope of the present invention.

Although the thickness of a thin film is not specifically limited, When used for an electrophotographic copying machine, a laser printer, etc., it is preferable that the thickness of a thin film is 0.2-2 micrometers.

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 only to the following examples.

Examples 1 to 13 Preparation of Poly (oxytitanium phthalocyanine) imide

Example 1

Commercially available 4,4- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA) 6 mmol, phthalic anhydride (PA) 15 mmol, urea 100 mmol, molybdenum ammonium tetraoxide ((NH ₄ ) ₂ MoO ₄ ) 0.08 5 mmol of mmol and tetrabutoxytitanium salt (Ti (OBu) ₄ ) were placed in a 250 mL reaction vessel, stirred in a nitrogen atmosphere, and then reacted at 215 ° C. to 250 ° C. for 2 hours. After cooling to room temperature, the product was washed with distilled water, acetone, 1 M hydrochloric acid solution, and then dried in a vacuum oven for at least 1 day at 60 ° C., and oxytitanium phthalocyanine having a maximum absorption peak at 700 nm as shown in FIG. 1. The polymer is obtained in a yield of 91% by weight. The infrared absorption spectrum result of this compound is as shown in FIG. In addition, the prepared poly (oxytitanium phthalocyanine) imide exhibits thermal stability up to 350 ° C., and thermogravimetric analysis results are shown in FIG. 3.

Example 2

Commercially available 4,4- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA) 5 mmol, phthalic anhydride (PA) 15 mmol, urea 150 mmol, molybdenum ammonium tetrachloride ((NH ₄ ) ₂ MoO ₄ ) 0.08 7 mmol of mmol and tetrabutoxytitanium salt (Ti (OBu) ₄ ) were placed in a 250 mL reaction vessel, stirred in a nitrogen atmosphere, and then reacted at 250 ° C. to 260 ° C. for 3 hours. After cooling to room temperature, the product was washed with distilled water, acetone, 1 M hydrochloric acid solution, and then dried in a vacuum oven at 70 ° C. for at least 1 day to obtain poly (oxytitanium phthalocyanine) imide in a yield of 80% by weight.

Examples 3 and 4

The hexafluoroisopropylidene oxytitanium phthalocyanine polymer was prepared by changing the content of the reactants, solvent, temperature and time as summarized in Table 1. In the case of 1,2,4-trichlorobenzene (1,2,4-TCB), it was obtained by yield of 85% when using 65% and sulfolane (TMS) as a solvent.

Examples 5 to 13

4,4- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA) or 3,3 ', 4,4'-(benzophenonetetracarboxylic acid) dianhydride (BTDA), 3,3 ', 4,4 '-(Biphenyltetracarboxylic acid) dianhydride (BPDA) or 3,3', 4,4 '-(diphenylsulfontetracarboxylic acid) dianhydride (DSDA) was added and summarized in Table 1 without phthalic anhydride or phthalic anhydride. When the oxytitanium phthalocyanine polymer is prepared by reacting under the conditions described above, a polymer having heat resistance characteristics as summarized in Table 1 is prepared.

Examples 14-22 Preparation of Poly (oxytitanium phthalocyanine) carboxylic Acid

Example 14

After dissolving 3.444 g of sodium hydroxide (NaOH) and 15.17 g of sodium chloride (NaCl) in 15 mL of distilled water, 1.608 g of the oxytitanium phthalocyanine polymer imide prepared in Example 1 is added. After stirring at 90 ° C. for 3 hours and cooling to room temperature, 150 ml of distilled water was added to the reaction mixture, diluted, and filtered with a filter. The filtrate was neutralized with an aqueous 1 M HCl solution, adjusted to pH = 2 left and right, and the precipitate was filtered through a filter, washed several times with MeOH / acetone, and then dried in a 100 ° C. oven to give 0.377 g of oxytitanium phthalocyanine. Polymer carboxylic acids are prepared. The polymer prepared by the above method has increased solubility in organic solvents, solubility and heat resistance are summarized in Table 2. Infrared spectral absorption spectra are shown in FIG.

Example 15

After dissolving 5 ml of concentrated acid (H ₂ SO ₄ ) in 30 ml of distilled water, 2.5 g of oxytitanium phthalocyanine polymer imide prepared in Example 13 was added to the solution, followed by heating and stirring at 80 ° C. After 2 hours, the reactant was slowly injected into 500 mL of distilled water at 4 to 8 ° C., and the resulting precipitate was separated by filtration, washed with distilled water three times and with chloroform, dissolved in acetone, and dissolved in MeOH to separate the precipitate. Upon drying, 1.2 g of polymer is produced.

Examples 16-22

When the poly (oxytitanium phthalocyanine) imide prepared in Examples 2 to 12 was hydrated by the method of Example 14 or Example 15, poly (oxytitanium phthalocyanine) carboxylic acid was produced in the yield as summarized in Table 2. The heat resistance characteristics are summarized in Table 2, and the spectral absorption spectra of the poly (oxytitanium phthalocyanine) carboxylic acid produced in Examples 20 and 22 are shown in Figs.

Preparation of poly (oxytitanium phthalocyanine) carboxylic acid Example Imide (g) Raw material input Reaction conditions Yield, g (%) Solubility in DMF TGA T _10% ℃ T _30% ℃ 14 Example 11.608 NaOH: 3.444 gNaCl: 15.17 gH ₂ O: 15 ml 90 ℃ / 3h 0.377 (23.5) +++ 200 ℃ 346 ℃ 15 Example 132.5 Concentrated H ₂ SO ₄ : 5 ml Distilled water (H ₂ O): 30 ml 80 ℃ / 2h 1.2 (44) + 16 Example 20.5 Bass _{H 2 SO 4: 8 ㎖H 2} O: 40 ㎖ 88 ℃ / 2.5h 0.23 (46) +++ 17 Example 20.46 NaOH: 2.5 gNaCl: 15 gH ₂ O: 20 ml 90 ℃ / 5h 0.05 (10) 18 Example 20.15 Bass _{H 2 SO 4: 4 ㎖H 2} O: 20 ㎖ 90 ℃ / 3h 0.06 (40) +++ 19 Example 121.5 KOH: 6 gNaCl: 30 gH ₂ O: 30 ml 90 ℃ / 5h 0.69 (50) ++ 267 ℃ 667 ℃ 20 Example 90.58 KOH: 3.07 gNaCl: 15.3 gH ₂ O: 15 ml 90 ℃ / 5h 0.52 (90) +++ 215 ℃ 529 ℃ 21 Example 612.1 KOH: 20 gNaCl: 100 gH ₂ O: 120 ml 90 ℃ / 5h 7.04 (59) 22 Example 120.9 KOH: 3 gNaCl: 15 gH ₂ O: 15 ml 90 ℃ / 5h 0.60 (66) ++ 277 ℃ 516 ℃ + 1 to 2 wt% of solubility, ++ 1 to 10 wt% of solubility, +++ 10 wt% of solubility

Example 23 Preparation of Poly (oxyvanadium phthalocyanine) imide

250 ml of 4,4- (hexafluoroisopropylidene) diphthalic dianhydride 8.89 g, phthalic acid 10 g, urea 12 g, 0.03 g molybdenum ammonium tetraoxide and 3.40 g vanadium pentoxide (V ₂ O ₅ ) It put in a container, it stirred in nitrogen atmosphere, and made it react at 200 degreeC for 1 hour. After cooling to room temperature, the product is washed with distilled water, acetone, 1 M hydrochloric acid solution and dried to produce an oxyvanadium phthalocyanine polymer imide in a yield of 55%. The maximum absorption peak of the resulting oxytitanium phthalocyanine polymer was 684 nm and was soluble in DMSO, DMF, pyridine, NMP, sulfuric acid and the like.

Example 24 Preparation of Poly (oxyvanadium phthalocyanine) carboxylic Acid

When the poly (oxyvanadium phthalocyanine) imide prepared in Example 23 was hydrated by the method of Example 15, a poly (oxyvanadium phthalocyanine) carboxylic acid was prepared in a yield of 70%. The solubility in DMSO was more than 10% by weight, and the UV / vis absorption spectrum dissolved in DMSO showed a maximum absorption peak at 697 nm.

Examples 25-28 Preparation of Poly (oxytitanium phthalocyanine) esters

Example 25

0.5 g of K ₂ CO _{3 and} 0.5 g of CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl were dissolved in 30 ml of butyl ether and 30 ml of distilled water. 0.5 g of oxytitanium phthalocyanine) carboxylic acid is added, and 0.7 g of CH ₃ (CH ₂ ) ₁₁ Br is mixed and stirred at 89 ° C by heating. After 12 hours, the reaction was cooled, extracted and washed with hexane and distilled water, the filtrate was concentrated, washed again with a mixed solvent of distilled water and ethanol (1: 1) and dried to give poly (oxytitanium phthalocyanine) deca Noyl ester derivatives are provided. The prepared polymer shows solubility of 10 wt% or more in DMF and chloroform, the UV-Vis absorption spectrum shows the maximum absorption band at 690 nm, and the infrared spectral absorption spectrum is shown in FIG. 7.

Example 26

Prepared in the same manner as in Example 25, except that 0.5 g of 18-crown-6-ether was used instead of 0.5 g of CH ₃ N [(CH ₂ ) ₇ CH ₃ ] ₃ Cl, and hexane was used instead of butyl ether. .

Example 27

0.4 g of poly (oxytitanium phthalocyanine) carboxylic acid prepared in Example 22 was dissolved in 20 ml of n-octanol, and then 3 ml of hydrochloric acid (34.36% aqueous solution) was added, followed by heating and stirring at 90 ° C. After 3 hours, n-octanol was distilled off, washed with a mixed solvent of distilled water and ethanol (1: 1), then washed again with isopropanol and dried to give 0.25 g of poly (oxytitanium phthalocyanine) octyl ester derivative. Is provided. The UV-Vis absorption spectrum of the prepared polymer shows the maximum absorption band at 690 nm.

Example 28

0.5 g of poly (oxytitanium phthalocyanine) carboxylic acid prepared in Example 20 was dissolved in 10 g of poly (propylene glycol), 1.5 ml of hydrochloric acid (34.36% aqueous solution) was added, followed by heating and stirring at 120 ° C. After 3 hours, it is cooled and the reaction is precipitated with a mixed solvent of distilled water and ethanol (1: 1) and then washed with hexane. The solid product is dissolved in isopropanol, concentrated, reprecipitated with chloroform and dried to give 0.5 g of oxytitanium phthalocyanine polymer ester derivative. The UV-Vis absorption spectrum of the prepared polymer shows the maximum absorption band at 690 nm.

Examples 29 to 34 (Film Compositions and Thin Films of Phthalocyanine Polymers)

Example 29

After adding 1 g of poly (oxytitanium phthalocyanine) imide prepared in Example 1 to 10 ml of DMSO and stirring for 1 hour, a dark green solution is prepared. After applying the prepared solution to the conductive glass (ITO glass), and dried for 6 hours in an oven at 80 ℃, a 0.5 micron thick phthalocyanine polymer thin film is prepared. At this time, the maximum absorption peak of the thin film was 700 nm.

Example 30

In Example 29, the same method as in Example 29 was used except that DMF was used instead of DMSO.

Example 31

In Example 29, the same method as in Example 29 was used except that NMP was used instead of DMSO.

Example 32

The same method as in Example 29 was used, except that in Example 29, a 1: 1 mixed solvent of sulfolane and xylene was used instead of DMSO.

Example 33

0.543 ml of concentrated sulfuric acid solution was cooled to 0-2 degreeC, and then it stirred rapidly, 0.1 g of the phthalocyanine polymer obtained in Example 1 was added little by little, and the range of temperature increase and fall did not exceed 2 degreeC. The mixture was stirred for 1 hour to form an overall uniform paste, then acetone was added, mixed with an ultrasonic mixer and then applied onto the conductive glass. The thickness of the thin film was 1 micron and the UV / vis absorption spectrum was similar to that of FIG. 5.

Examples 34-54

The same method as in Example 29 was used except that in Example 29 the oxytitanium phthalocyanine polymer prepared in Examples 2 to 22 was used.

Examples 55-75

The same method as in Example 30 was used except that in Example 30 the oxytitanium phthalocyanine polymer prepared in Examples 2 to 22 was used.

Example 76

The same method as in Example 29 was used except that 1 g of the oxyvanadium phthalocyanine polymer prepared in Example 29 was used. The thickness of the prepared thin film was 0.5 to 1.2 microns, and the absorption region was 500 to 840 nm.

Example 77

20 ml of cooling water was added dropwise to the oxytitanium phthalocyanine polymer dough prepared in Example 10 to form a precipitate. Wash several times with distilled water to make the pH of the filtrate neutral, then wash with acetone and dry. 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.

Example 78

The composition of Example 29 is applied onto the mylar film. At this time, the thickness of the film is 1 μm or less, and the above film is dried in a vacuum oven. This thin film shows good absorbance at 700 nm.

Example 79

0.2 g of oxytitanium phthalocyanine polymer was added to a 125 ml Erlenmeyer flask, and 0.3 g of polyvinyl butyral was added, followed by adding 4.5 ml of a 1-butyl alcohol mixed solvent in the same proportion as toluene. Glass beads are added, the stopper is closed and stirred in a miller for at least 18 hours. This mixed solution is applied onto the mylar film using bar coating. At this time, the thickness of the film is 2 μm or less, and the above film is dried at 60 ° C. in a vacuum oven. This thin film shows good absorbance at 700 nm.

Example 80

0.2 g of phthalocyanine polymer of the present invention was added to a 125 mL Erlenmeyer flask, 0.5 mL of DMF was added, followed by 0.3 g of polyvinyl butyral, and 2 mL of a 1-butyl alcohol mixed solvent in the same proportion as toluene was added. Glass beads are added, the stopper is closed and stirred for at least 18 hours in a mixer.

The above mixed solution is applied onto the mylar film using bar coating. At this time, the thickness of the film is 1 μm or less, and the above film is dried in a vacuum oven. This thin film shows good absorbance at 600 to 800 nm.

As described above, the present invention enables the preparation of phthalocyanine polymers and photosensitive thin films having a very high solubility in organic solvents and showing good sensitivity to near infrared rays and visible light.

Claims (19)

A poly (phthalocyanine) copolymer selected from the group consisting of poly (phthalocyanine) imide of Formula 1 and poly (phthalocyanine) carboxylic acid of Formula 2 or ester thereof. [Formula 1] [Formula 2] [Wherein R ¹ and R ² independently of one another are a hydrogen atom, a substitutable linear or branched C _1-20 alkyl or alkoxy group, a substitutable linear or branched C _1- having 1 to 10 oxygen atoms in the chain; _{A 20} alkyl or alkoxy group, or a substituted phenyl or phenoxy group (which may have from 1 to 5 C _1-6 alkyl or alkoxy groups as substituents); R ³ and R ⁴ have the same meaning as R ¹ ; X and Y independently represent a single bond, -O-, -S-,>CO,> SO ₂ ,> C (CF ₃ ) ₂ ,> CR ¹ ₂ ,> NH or> NR ¹ , or the tetra Two phenyl rings of the carboxylic anhydride may be fused to each other without a linking group X and Y to form a naphthyl ring, or may form a biphenyl structure in which only one of X or Y is connected by a single bond; p, q and r are each an integer of 0 or more, and p + q + r is an integer of 1 or more; W represents a hydrogen atom or the symbol M, where M represents a divalent metal, a trivalent or tetravalent substituted metal or a metal oxide group.] The poly (phthalocyanine) copolymer according to claim 1, wherein the polymer has a molecular weight range of 3,000 to 200,000. A poly (phthalocyanine) according to claim 1 characterized by reacting a substitutable phthalic anhydride of formula 3, a substitutable tetracarboxylic dianhydride of formula 4, a metal compound of formula 5 and urea in the presence or absence of a solvent Method of preparation of the copolymer: [Formula 3] (Wherein R ¹ is as defined in claim 1). [Formula 4] (Wherein R ² is as defined in claim 1). [Formula 5] M _a Z _b [Wherein M is a divalent metal, a trivalent or tetravalent substituted metal or metal oxide group, p, q and r are each an integer of 0 or more, a and b are an integer of 1 or more, Z is Cl, Br, I, OR ¹ , where R ¹ is as defined above.] 4. A poly (phthalocyanine) imide copolymer of formula (1) is reacted with an acidic or basic solution to convert R ⁴ to a poly (phthalocyanine) carboxylic acid of formula (2), all of which represent hydrogen atoms. Method for producing a poly (phthalocyanine) copolymer according to claim 1 The method according to claim 3, wherein the poly (phthalocyanine) imide copolymer of formula 1 is reacted with an acidic or basic solution to convert it to a poly (phthalocyanine) carboxylic acid of formula 2 wherein R ⁴ represents all hydrogen atoms, A method for producing a poly (phthalocyanine) copolymer according to claim 1, characterized in that a poly (phthalocyanine) ester of the formula (2) is prepared by esterification with an esterifying compound in an acidic aqueous solution or a basic K ₂ CO ₃ aqueous solution. A process for preparing a poly (phthalocyanine) copolymer according to claim 5, characterized in that it is esterified with hydrochloric acid or an aqueous solution of K ₂ CO ₃ to the compound of formula (6): [Formula 6] R^OneOH or R^OneZ (Wherein R ¹ and Z are as defined above). The solvent according to claim 3, wherein the solvent is selected from the group consisting of α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, sulfolane and xylene Method comprising the above high boiling point solvent. 4. A process according to claim 3, wherein the reaction is carried out at a temperature of from 100 ° C. to 400 ° C. for 0.5 to 10 hours. A polymer composition composed of at least one polar solvent and at least one poly (phthalocyanine) copolymer according to claim 1. The polymer composition according to claim 9, wherein the polar solvent is at least one polar solvent selected from the group consisting of acetone, acetonitrile, lower alcohol, dimethylformamide, dimethyl sulfoxide, pyridine, NMP, sulfolane, sulfuric acid and water. . 10. The method of claim 9, wherein at least one high boiling point selected from the group consisting of α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, sulfolane and xylene A polymer composition, further comprising a solvent. 10. The polymer composition of claim 9, further comprising at least one resin selected from the group consisting of polyvinylbutyral, polyolefins, polycarbonates, polyesters, polymethylmethacrylates and polyurethanes. 10. The compound of claim 9, selected from at least one resin selected from the group consisting of polyvinyl butyral, polycarbonate, polyolefin, polyester, polymethyl methacrylate and polyurethane, toluene, butyl alcohol and 1,2-dichloroethane. A polymer composition composed of at least one solvent and at least one poly (phthalocyanine) copolymer described above. _{10. The} polymer composition of claim 9, which is composed of sulfuric acid, Nafion hydrochloride, AsF ₆ , iodine, and one or more of the aforementioned poly (phthalocyanine) copolymers. A polymer thin film obtained by coating a polymer composition according to claim 9 on a support. The method of claim 15, wherein the support is selected from the group consisting of a conductive electrode support or plastic and glass selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, mylar film, copper plate, conductive glass and conductive plastic. Polymer thin film, characterized in that the insulating support. A method for producing a polymer thin film, comprising coating a polymer composition according to claim 9 on a support and drying the solvent. 18. The insulating support according to claim 17, wherein the support is a conductive electrode support selected from the group consisting of aluminum foil, aluminum drums, aluminum plates, platinum, mylar films, copper plates, conductive glass and conductive plastics or an insulating support selected from the group consisting of plastics and glass. Method characterized by that. An article such as a color filter, an organic photosensitive drum, a recording element or an optical element comprising the poly (phthalocyanine) copolymer according to claim 1.