KR20130011324A - Copolymer containing dicyanophenyl functional groups and phthalocyanine-based compound synthesised from the copolymer - Google Patents

Abstract

PURPOSE: A dicyanophenyl group-containing copolymer is provided to increase solubility to solvent and to improve dispersity and dispersion stability of a phthalocyanine-based compound. CONSTITUTION: A dicyanophenyl group-containing copolymer is represented by chemical formula 1. In chemical formula 1, each of R1 and R2 is a substituted or unsubstituted C1-10 alkyl group, C3 is a substituted or unsubstituted C1-10 alkyl group, a substituted or unsubstituted C5-10 aryl group, a substituted or unsubstituted C1-10 alkoxy group, a substituted or unsubstituted C5-10 aryloxy group, or an amino group, and each of m and n is a natural number from 50-1,000. A phthalocyanine-based compound is represented by chemical formula 2. In chemical formula 2, M is a divalent metal atom, a monosubstituted trivalent metal atom, disubstituted quadrivalent metal atom, or metal oxide, and each of L1, L2, L3 and L4 is indicated in chemical formula (a).

Description

Copolymer-containing dicyanophenyl functional groups and phthalocyanine-based compound synthesised from the copolymer}

The present invention relates to a copolymer containing a dicyanophenyl group and a phthalocyanine compound formed therefrom, and more particularly, to a copolymer obtained by copolymerizing a monomer containing a dicyanophenyl group, and a phthalocyanine containing the copolymer. By improving the solubility in a solvent and improving the dispersibility and coating properties of the dispersion composition relates to the synthesis of a phthalocyanine-based compound unnecessary to use a dispersant and a binder and a method for producing the same.

Phthalocyanine (Pc) and its derivatives have been extensively studied in various fields as materials giving excellent electrical and optical properties. The properties of phthalocyanines are caused by the electrical delocalization of macrocycles containing transition metals, and have many applications, particularly in nanotechnology and material science.

Phthalocyanine has a planar macrocyclic structure, and 18 π-electrons are delocalized throughout the ring. It exhibits a strong Q-band in the visible range of 620-700nm, with a unique color from dark green to blue. For this reason, phthalocyanine has attracted much attention as a dye for textiles and inks. It is also thermally chemically stable and can withstand strong electromagnetic radiation. But most of all, the phthalocyanine plays an important role in the field of materials due to the diversity created by replacing more than 70 different metals in the center of the ring.

In recent years, phthalocyanines have been used as semiconductors in organic solar cells because of their insulating properties or conductive properties in which orbitals overlap in the supermolecular unit set to create electron transfer paths. It has the property of reduction and is used as dye or photovoltaic window in dye-sensitized solar cells (DSSC). In the medical field, the optical properties of phthalocyanine are also applied to PDT (photodynamic therapy) to remove tumors and cancer. In addition, due to its inherent color characteristics, it is used as a color filter for liquid crystal displays (LCDs) that realize green and blue colors in TVs, mobile phones, and computer monitors.

As the application range of phthalocyanine is expanded, researches to adjust the structure and arrangement of phthalocyanine have been actively conducted in order to satisfy the required physical and chemical properties. In particular, research on supramolecular structures and nanostructures has emerged as a very interesting topic.

Japanese Patent Laid-Open No. Hei 2-008256 discloses that a titanyl phthalocyanine compound exhibiting high sensitivity in a long wavelength region and having a specific crystalline form exhibits excellent sensitivity.

Korean Unexamined Patent Publication No. 10-2007-0048460 discloses crystalline titanyl phthalocyanine, a manufacturing method thereof, and an electrophotographic photosensitive member and an electrophotographic imaging apparatus using the same.

In addition, Korean Patent Publication No. 10-2010-0079819 discloses a copper phthalocyanine compound and a near infrared absorption filter using the same. This document discloses a phthalocyanine compound and a near-infrared absorption filter for use in a plasma display panel having a low absorption rate in the visible light region and an excellent absorption efficiency in the near infrared region.

As such, phthalocyanine-based nano-compounds are used in all of those used in plasma display panels (PDPs), LCDs, organic light-emitting displays (OLEDs), electronic paper displays (EPDs), organic photoconductive (OPC) drums, PDTs, and organic solar cells. To this end, dispersants and binders are used together with phthalocyanine-based nanocompounds, and as these dispersants and binders, acrylic polymers, urethane and urethane acrylic polymers, epoxy polymers, styrene polymers, polyvinyl butyral polymers, etc. may be used. Can be.

The dispersion composition of the nano compound may be applied after the thin film layer is formed by a dyeing method, printing method, electrodeposition method, pigment dispersion method, inkjet method and the like.

In the dyeing method, an image having a dye-based substrate such as a natural photosensitive resin such as gelatin, an amine modified polyvinyl alcohol, an amine modified acrylic resin, or the like is formed on a substrate, and then dyed with a dye such as a direct dye to form a colored thin film. In order to form a multi-colored thin film on the same substrate, it is necessary to perform flameproof processing every time the color is changed, so that the process becomes very complicated and the time is delayed. In addition, although the clarity and dispersibility of the dyes and resins generally used are good, there are disadvantages in that light resistance, moisture resistance, and most importantly, heat resistance are poor.

In the printing method, after printing using the ink which disperse | distributed a nano compound to thermosetting or photocurable resin, a colored thin film is formed by hardening with heat or light. According to this method, the material cost can be reduced compared to other methods, but it is difficult to form highly precise and detailed images, and there is a problem that the thin film layer formed is not uniform.

In the method of manufacturing a color filter using the inkjet method, since the color resist composition sprayed from the nozzle is a dye type for printing a fine and accurate pigment, durability and heat resistance are inferior as in the dyeing method.

Electrodeposition using electroprecipitation can form precise colored nets and has excellent heat and light resistance due to the use of pigments.However, when the pixel size is precise and the electrode pattern is fine, It is difficult to apply to color filters that require high precision due to the appearance of staining or thickening of the film thickness.

Pigment dispersion is a method in which a colored thin film is formed by repeating a series of processes of coating, exposing, developing and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. Pigment dispersion method has the advantage of improving the heat resistance and durability of the coating film and maintaining the thickness of the film uniformly, excellent implementation of the fine pattern and relatively easy manufacturing method is widely adopted.

However, the method requires a process of coating, exposing, developing, and curing the pixels, respectively, which makes it difficult to manage yield as the manufacturing process line becomes too long and the inter-process control factors increase. In addition, there is a problem in the actual production process, such as the need to increase the thickness of the coating film as a high color reproduction ratio and high contrast ratio is required.

In order to overcome this problem, a number of new process methods are recently used to replace the conventional pigment dispersion method, and an inkjet printing method is representative. In the inkjet printing method, a light blocking layer such as a black matrix is formed on a glass substrate and ink is injected into the pixel space. Since the inkjet printing method does not require a separate coating, exposure, or development process in manufacturing the pixel of the color filter, the material required for the process can be reduced and the process can be simplified.

In the ink jet method, each coating film must be uniformly formed. This means that when the ink is ejected from the head, there should be no clogging of the nozzles and it should fall in the same amount and drop within the pixel. Therefore, the interaction between the nozzle surface of the head and the nano compound is a factor that greatly influences the injection performance.

In addition, the coating film formed by using the inkjet method requires high reliability similar to the pattern formed by the pigment dispersion method, and heat resistance, chemical resistance, film strength and storage stability should be considered. If this characteristic is not satisfied, problems such as color change or pattern infringement may occur in a post process of the color filter.

Generally, practically useful pigments that exhibit vivid color tones and high coloring power are composed of fine particles. Pigment dispersion compositions formed by dispersing such pigments have been used in various fields because of their excellent color development and light resistance. However, if the pigment particles are made finer in order to obtain high coloring power, the pigment dispersion tends to become highly viscous due to various factors, which makes it difficult to acquire the dispersion from the disperser and transport it by pipeline, and also causes gelation during storage. There is a fear that use becomes difficult. In addition, the photosensitive composition cured by light may contain a pigment as a coloring material and is known to be useful as an image forming material. Although a pigment | dye and a high coloring power are calculated | required by a pigment as a coloring material, when using it as a photosensitive composition, the problem described below arises and it is difficult to refine | miniaturize a pigment.

In order to form a colored image using a coloring photosensitive composition, the layer of the photosensitive composition is formed on a board | substrate, and it exposes and develops. In this case, the alkaline layer is preferably soluble in the alkaline aqueous solution because the alkaline solution is preferably used as the developer rather than the organic solvent due to environmental problems.

As the dispersion medium for the coating solution of the colored photosensitive composition, it is preferable to use an organic solvent from the standpoint of drying after coating, and the binder (binder) used in the colored photosensitive composition needs to have an acidic group and also be dissolved in a suitable organic solvent . Organic pigments are dispersed in such an acidic binder.

However, since it is difficult to disperse the organic pigment in the acidic binder soluble in the organic solvent, there is a problem that it is not easy to obtain a colored photosensitive composition having a sufficiently fine pigment, high coloring power, and developable with an alkaline aqueous solution.

The present invention has been newly proposed to solve the problems of the prior art, and an object thereof is to provide a copolymer compound capable of improving the dispersibility and dispersion stability of the compound.

In addition, the present invention improves the dispersibility and coating properties of the dispersion composition by increasing the solubility in the solvent of the copolymer compound and imparts the function of the conventional dispersant and binder to the copolymer compound enables thin film coating without dispersant and binder It is an object to provide a phthalocyanine-based compound.

It is another object of the present invention to provide a monomer containing a dicyanophenyl group for producing the copolymer compound.

In addition, the present invention improves the dispersibility and coating properties of the dispersion composition by increasing the solubility in the solvent of the copolymer compound and imparts the function of the conventional dispersant and binder to the copolymer compound enables thin film coating without dispersant and binder It is an object to provide a method for producing a phthalocyanine-based compound.

In order to achieve the above object,

It provides a copolymer comprising a dicyanophenyl group represented by the following formula (1):

[Formula 1]

Where

R1 and R2 are each a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,

R3 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 5 to 10 carbon atoms It is an aryloxy group or an amino group.

m and n are natural numbers of 50-1,000, respectively.

To achieve these and other objects,

It provides a phthalocyanine compound represented by the formula (2):

[Formula 2]

Where

M is a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom or a metal oxide,

L1, L2, L3, and L4 are each independently represented by formula (a):

(a)

(a)

In the formula (a),

R4 and R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,

R 6 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 5 to 10 carbon atoms An aryloxy group or an amino group,

m and n are natural numbers of 50-1,000, respectively.

According to another aspect of the present invention,

It provides a monomer compound represented by the formula (3):

(3)

R 7 is independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon number 5 To aryloxy group or amino group.

According to another aspect of the present invention,

Synthesizing a monomer compound represented by Formula 3;

(3)

[R7 is independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon number 5 to 10 aryloxy group or amino group;

Reacting and copolymerizing the compound represented by Formula 3 with formula (b) to form a copolymer including a dicyanophenyl group represented by Formula 1;

(b)

(b)

[Wherein R8 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R9 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, substituted or unsubstituted Alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group or amino group having 5 to 10 carbon atoms; and

It provides a method for producing a phthalocyanine compound represented by the formula (2) comprising the step of reacting the copolymer with a metal chloride and a solvent to form a metallophthalocyanine.

According to the present invention, by dissolving a phthalocyanine-based compound in a solvent, it is possible to increase the dispersibility by maintaining a small particle size without using a dispersant. In addition, by using a polymer copolymerized in the same series as a dispersant and a binder suitable for each application, it is possible to improve productivity by using a single material without using a dispersant and a binder as well as improving microdispersion and coating properties.

1 is an overall scheme of phthalocyanine from copolymers containing dicyanophenyl groups prepared according to the present invention.
2 is a chemical structure and ¹ H-NMR spectrum of the DCPM monomer according to an embodiment of the present invention.
3 is pMMA-co-pDCPM chemical structure and ¹ H-NMR spectrum according to an embodiment of the present invention.
4 is a chemical structure and ¹ H-NMR spectrum of pDCPM-co-pBMA according to an embodiment of the present invention.
5 is a chemical structure and ¹ H-NMR spectrum of a high conversion pDCPM-co-pBMA according to an embodiment of the present invention.
Figure 6 is a UV / Vis of pDCPM-co-pMMA-CuPc in accordance with an embodiment of the present invention. Spectrum.
7 is UV / Vis of pDCPM-co-pBMA-CuPc according to an embodiment of the present invention. Spectrum.
8 shows the GPC results of pDCPM-co-pBMA and pDCPM-co-pBMA-CuPc according to an embodiment of the present invention.
9 is UV / Vis of pDCPM-co-pBMA-ZnPc according to an embodiment of the present invention. Spectrum.
10 shows GPC results of pDCPM-co-pBMA-ZnPc according to an embodiment of the present invention.

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

The present invention provides a copolymer comprising a dicyanophenyl group represented by Formula 1 below:

[Formula 1]

Where

R1 and R2 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and R3 is a substituted or unsubstituted carbon group An alkyl group of 1 to 10, a substituted or unsubstituted aryl group of 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group of 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group of 5 to 10 carbon atoms, or an amino group, m and n are natural numbers of 50-1,000, respectively.

The copolymer of Formula 1 is a random copolymer in which two repeat units are optionally mixed and polymerized.

Here, m, n indicating the repeating unit is a natural number of 50 to 1,000, respectively, which can be formed by adjusting the repeating unit in order to secure the desired physical properties, if m, n exceeds 1,000 because the molecular weight is too large Not desirable

Substituted or unsubstituted C1-C10 alkyl groups include straight, branched or cyclic alkyl groups, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, iso-propyl, sec -Butyl, t-butyl, neo-pentyl, 1,2-dimethylpropyl, cyclohexyl, 1,3-dimethylbutyl, 1-iso-propylpropyl, 1,2-dimethylbutyl, 1,4-dimethylpentyl, 2 -Methyl-1-iso-propylpropyl, 1-ethyl-3-methylbutyl, 3-methyl-1-iso-propylbutyl, 2-methyl-1-iso-propylbutyl, 1-t-butyl-2-methyl Unsubstituted alkyl groups such as propyl, 2-methylpentyl and 2-ethylhexyl; Halogen-substituted alkyl groups such as 2-chloroethyl, 3-bromopropyl, 2,2,3,3-tetrafluoropropyl and 1,1,1,3,3,3-hexafluoro-2-propyl ; 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 1-ethoxy-2-propyl, 3-methoxypropyl, 3-methoxybutyl, 2,2-dimethyl-1,3-diox Alkoxy-substituted alkyl groups such as solan-4-ylmethyl and 1,3-diethoxy-2-propyl; Amino-substituted alkyl groups such as 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-dibutylaminoethyl and 2-diethylaminopropyl; And alkylthio-substituted alkyl groups such as 1,3-diethylthio-2-propyl.

The substituted or unsubstituted aryl group having 5 to 10 carbon atoms is, for example, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl , 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chloro-3-methyl-petyl, 3-chloro-4-ethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 4-chloro-3-methoxyphenyl, 4-methyl-3-methoxyphenyl, 2-methylaminophenyl, 2-dimethylaminophenyl, 2-ethylaminophenyl, 2- (methylethylamino) phenyl, 2-di Ethylaminophenyl, 2-propylaminophenyl, 2-dipropylaminophenyl, 3-methylaminophenyl, 3-dimethylaminophenyl, 3-ethylaminophenyl, 3- (methylethylamino) phenyl, 3-diethylaminophenyl , 3-propylaminophenyl, 3-dipropylaminophenyl, 4-methylaminophenyl, 4-dimethylaminophenyl, 4-ethylaminophenyl, 4- (methylethylamino) phenyl, 4-diethylaminophenyl, 4- Propylaminophenyl and 4-dipro At least one selected from the group consisting of philaminophenyl.

Substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms include linear, branched or cyclic alkyl groups, for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyl Oxy, nonyloxy, iso-propoxy, sec-butoxy, t-butoxy, neo-pentyloxy, 1,2-dimethylpropoxy, cyclohexyloxy, 1,3-dimethylbutoxy, 1-iso- Propylpropoxy, 1,2-dimethylbutoxy, 1,4-dimethylpentyloxy, 2-methyl-1-iso-propylpropoxy, 1-ethyl-3-methylbutoxy, 3-methyl-1-iso- Unsubstituted alkoxy groups such as propylbutoxy, 2-methyl-1-iso-propylbutoxy, 1-t-butyl-2-methylpropoxy, 2-methylpentyloxy and 2-ethylhexyloxy; Halogen-substituted such as chloroethoxy, 3-bromopropoxy, 2,2,3,3-tetrafluoropropoxy and 1,1,1,3,3,3-hexafluoro-2-propoxy Alkoxy group; 2-methoxyethoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 1-ethoxy-2-propoxy, 3-methoxypropoxy, 3-methoxybutoxy, 2,2-dimethyl Alkoxy-substituted alkoxy groups such as -1,3-dioxolan-4-ylmethoxy and 1,3-diethoxy-2-propoxy; Amino-substituted alkoxy groups such as 2-dimethylaminoethoxy, 2-diethylaminoethoxy, 2-dibutylaminoethoxy and 2-diethylaminopropoxy; And alkylthio-substituted alkoxy groups such as 1,3-diethylthio-2-propoxy.

The substituted or unsubstituted aryloxy group having 5 to 10 carbon atoms is, for example, phenyloxy, 2-chlorophenyloxy, 3-chlorophenyloxy, 4-chlorophenyloxy, 2-bromophenyloxy, 3-bromophenyl Oxy, 4-bromophenyloxy, 2-methylphenyloxy, 3-methylphenyloxy, 4-methylphenyloxy, 2-chloro-3-methyl-petyloxy, 3-chloro-4-ethylphenyloxy, 2-methoxyphenyl Oxy, 3-methoxyphenyloxy, 4-methoxyphenyloxy, 4-chloro-3-methoxyphenyloxy, 4-methyl-3-methoxyphenyloxy, 2-methylaminophenyloxy, 2-dimethylaminophenyl Oxy, 2-ethylaminophenyloxy, 2- (methylethylamino) phenyloxy, 2-diethylaminophenyloxy, 2-propylaminophenyloxy, 2-dipropylaminophenyloxy, 3-methylaminophenyloxy, 3 -Dimethylaminophenyloxy, 3-ethylaminophenyloxy, 3- (methylethylamino) phenyloxy, 3-diethylaminophenyloxy, 3-propylaminophenyloxy, 3-dipropylaminofe Nyloxy, 4-methylaminophenyloxy, 4-dimethylaminophenyloxy, 4-ethylaminophenyloxy, 4- (methylethylamino) phenyloxy, 4-diethylaminophenyloxy, 4-propylaminophenyloxy and 4 At least one selected from the group consisting of dipropylaminophenyloxy.

According to one embodiment, the present invention provides a phthalocyanine compound represented by Formula 2:

[Formula 2]

In the above formula, M is a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom or a metal oxide, and L1, L2, L3, and L4 may be each independently represented by formula (a).

(a)

(a)

In the formula (a),

R4 and R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and R6 is substituted or unsubstituted An alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 10 carbon atoms, m, n is a natural number of 50-1,000, respectively. In the above formula, the alkyl group, aryl group, alkoxy group, and aryloxy group are as defined above.

Examples of divalent metals denoted by M include Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Bi (II), Ca (II), Ba (II), Cd (II), Hg (II), Pb (II), Examples of monovalent trivalent metals selected from the group consisting of Sn (II) include Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, GaBr, In-Cl, In-Br, In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F, Al-C ₆ H ₅ , Al-C ₆ H ₄ (CH ₃ ), In-C ₆ H ₅ , In-C ₆ H ₄ (CH ₃ ), In-C ₁₀ H ₇ , Mn (OH), Mn (0C ₆ H ₅ ), Mn [OSi (CH ₃ ) ₃ ], FeCl and RuCl is selected from the group consisting of. An example of a disubstituted tetravalent metal include _{CrCl 2, SiCl 2, SiBr 2} , SiF 2, SiI 2, ZrCl 2, GeCl 2, GeBr 2, GeI 2, GeF 2, SnCl 2, SnBr 2, SnI 2, SnF 2, TiCl _2, TiBr _2, TiF ₂ and _{Si (OH) 2, Ge (} OH) 2, Zr (OH) 2, Mn (OH) 2, Sn (OH) 2, TiR 1 2, CrR 1 2, SiR 1 2 , SnR ¹ ₂ , GeR ¹ ₂ (wherein R ¹ is an alkyl group, a phenyl group, a naphthyl group and derivatives thereof), Si (0R ² ) ₂ , Sn (0R ² ) ₂ , Ge (0R ² ) ₂ , Ti (0R ² ) ₂ and Cr (0R ² ) ₂ , wherein R ² is an alkyl group, an alkylcarbonyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkylalkoxysilyl group and derivatives thereof; Examples are at least one selected from VO, MnO and TiO. Preferably M is Cu (II) or Zn (II) in the divalent metal.

The phthalocyanine compound of the present invention represents the form of a copolymer in which L1, L2, L3, and L4 each include various types of dicyanophenyl groups, and the repeating units of the copolymer may be polymerized with each other. Crosslinking may occur. It is a feature of the phthalocyanine-based nano-compound of the present invention that each repeating unit in L1, L2, L3, and L4 is bonded in various forms.

Since the primary particle size of the formed phthalocyanine-based nano compound may be prepared in about 20 to 100nm, it is possible to keep the dispersed particle size small after dispersion. This can maintain the dispersion by introducing a functional group that can adhere to the surface of the pigment to adjust the pigment particles and the particles at regular intervals using a steric hindrance effect. In addition, since the phthalocyanine-based nano-compound of the present invention not only facilitates dissolution in a solvent but also controls the molecular structure of the copolymer, the physical properties of the coating film can be easily adjusted by adjusting each substituent.

According to another embodiment of the present invention, a monomer compound represented by the following Chemical Formula 3 is provided:

(3)

R7 is substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C5-10 aryl group, substituted or unsubstituted C1-10 alkoxy group, substituted or unsubstituted C5-10 Is an aryloxy group. Here, the alkyl group, the aryl group, and the alcohol group, and the aryloxy group may be exemplified by the above-mentioned compounds. Preferably, R7 is a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms.

The monomer compound is a repeating unit monomer constituting the copolymer of Formula 1 necessary to form the phthalocyanine-based compound of the present invention. That is, starting from the monomer compound represented by the formula (3) to form a copolymer of the formula (1) and four such copolymers can be formed to form a phthalocyanine compound represented by the formula (2).

The manufacturing method of the other phthalocyanine type compound of this invention is demonstrated. First, a monomer compound represented by Formula 3 is synthesized:

(3)

R7 is substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C5-10 aryl group, substituted or unsubstituted C1-10 alkoxy group, substituted or unsubstituted C5-10 Is an aryloxy group.

Subsequently, the compound represented by the formula (3) and the compound (b) are reacted and copolymerized to form a copolymer including a dicyanophenyl group represented by the formula (1).

(b)

(b)

Wherein R 8 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R 9 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, substituted or unsubstituted An alkoxy group having 1 to 10 carbon atoms and a substituted or unsubstituted aryloxy group having 5 to 10 carbon atoms.

The monomer compound containing the dicyanophenyl group was introduced into the flask together with the initiator material, the air was removed using a pump, and then substituted with nitrogen, and the substance represented by the above formula (b), preferably methyl methacrylate, Put together and polymerize at a temperature of 50-70 ° C. Precipitating the copolymer solution in alcohol (methanol) to take only the polymer, and then remove the solvent in a dryer to form a copolymer containing a dicyanophenyl group represented by the formula (1).

Next, the formed copolymer, a metal chloride, a solvent, and the like are added to a flask substituted with nitrogen, and the reaction is performed under reflux conditions. The reaction solution is precipitated in alcohol / HCl solution, filtered, and the solid portion is extracted and continuously extracted. A phthalocyanine compound is formed by removing chloroform using a concentrator and removing a solvent remaining in the vacuum dryer.

When the resulting phthalocyanine compound / mixture is purified by recrystallization or column chromatography, a high purity phthalocyanine compound is obtained. The obtained high-purity phthalocyanine-based compound can be used in combination with other phthalocyanine-based compounds / mixtures, and it is possible to use phthalocyanine-based compounds / mixtures to which a high-purity phthalocyanine-based compound is added in the form of a mixture thereof.

Hereinafter, the use of the phthalocyanine-based nano compound of the present invention will be described in detail. The phthalocyanine-based nano compound of the present invention can be applied to a liquid crystal display (LCD). As one of the applications of the pigment dispersion composition, there is a color filter used for a liquid crystal display or the like. Important factors for increasing the resolution of the LCD display and reducing the residue include photoinitiators, types of monomers and binders, their composition ratios, and pigment dispersions. Among these elements, the pigment dispersion should have a small particle size in order to form a fine pattern, and should have a composition in which no residue is left during development. In order for the dispersion particle size of the pigment dispersion to be small, the primary particle size of the pigment used must be small, and the type and amount of the dispersant are also important items. When the phthalocyanine compound according to the present invention is used as a colorant as a colorant, the fineness of the pigment is sufficient, so that light is scattered and absorbed by the pigment particles, thereby improving light transmittance.

The phthalocyanine nano compound of the present invention can also be applied to a plasma display panel (PDP). In the case of PSA (Pressure Sensitive Adhesive) for display, a transparent acrylic adhesive is mainly used. In terms of adhesive properties, there is no significant difference from existing adhesives. However, due to the characteristics of the display material, the management standards for foreign materials and appearance defects are very strict. On the side. In addition, since expensive films are laminated, if a defect occurs during the lamination process, the film should be re-peeled without leaving a trace for regeneration of the film. Therefore, this re-workability is sometimes very important. That is, as well as the durability and adhesion stability of the existing pressure-sensitive adhesive, the perfect appearance, excellent re-peelability is an additional required characteristic that the pressure-sensitive adhesive for display should have. In the case of functional-PSA, optical function is added in addition to simple adhesive function. In the case of Color-PSA, all dyes such as Ne-cut or NIR dyes are mixed in the PSA layer, so the stability of the dye in the PSA should be the most basic. To this end, the stability of the dye itself is important, but a basic and systematic approach to the interaction between the dye and PSA is required, and the phthalocyanine compound according to the present invention is highly soluble and can realize high transmittance.

The phthalocyanine nano compounds of the present invention can also be applied to OPC drums. OPC drum is a core part of laser printer. The structure of general OPC drum is composed of charge transfer material (CTM) and polymer resin (CTL-) on charge generation layer (CGL) composed of charge generating material (CGM) and polymer resin (CG-Binder). It consists of a stacked type of charge transfer layer (GTL) made of Binder). Phthalocyanine-based nano compounds are mainly used as CGM, and Benzidine compound and Hydrazone compound are used as CTM. In addition, the charge generating layer (CGL) and the charge transfer layer (CTL) can be used as a single layer type consisting of one photosensitive layer. However, the material of each layer should be used in combination with a nano compound and a polymer binder and the phthalocyanine compound of the present invention can increase their suitability.

Phthalocyanine nano compound of the present invention can be applied to an organic light emitting device (OLED). OLEDs are divided into low molecules and polymers according to the light emitting material, and the manufacturing process is changed accordingly. Small molecules are generally coated in a thin film form by vacuum deposition, and polymer molecules are coated by a solution coating method such as spin coating or inkjet printing. Low molecules have the disadvantages of high efficiency, long life, easy color implementation, high reliability, and very high cost. High polymers have a relatively short lifespan, and materials and device technologies have been improved slowly but at low cost. It is expected that it will take more time to secure long-life, high-purity blue polymer light emitting materials and mass-produced patterning technology.

However, the advantage of forming a thin film by the solution process is a great advantage in the practical use of the polymer, it is expected that the development of the polymer will be further accelerated. The phthalocyanine compound of the present invention can be applied to a solution process useful for forming a thin film. Representative polymer luminescent materials that have been developed so far are mostly conjugated polymers that have been developed as conductive polymers. PAV), and it can be divided into copolymer and polymer blend and polymer phosphor using luminescence efficiency and phosphorescence emission.

Phthalocyanine nano compound of the present invention can be applied to electronic paper. Various types of electronic paper displays, including electrophoresis, have excellent readability due to high resolution, wide viewing angle, and high contrast ratio, and maintain a constant image with a bistable state where images are maintained even after the power is cut off. No power loss can be minimized. As a result, battery life is maintained for a long time, and thus, cost reduction and light weight can be achieved. In the case of using pigments and dyes in such electronic paper display, the phthalocyanine-based compound of the present invention may be used, and examples thereof include the following.

The display using the electrowetting phenomenon is driven by the principle that the insulating film is changed from hydrophobic to hydrophilic under the control of voltage by using the repulsive force of water and oil and the oil film is peeled off the surface of the insulating film. It is possible to realize colors close to natural colors by using dyes, and have high reflectance and fast response speed.

The Liquid Powder display is formed by the bridgestone method, forming a partition between the upper and lower transparent substrates, injecting positively charged black particles and negatively charged white particles, respectively, and then driving the particles by applying voltage to both electrodes. That's the way it is. The color can be divided into area color using two particles (Red / Yellow, Red / White) and full color using color filter for each zone. The filter array consists of RGBW.

Phthalocyanine nano compound of the present invention can be applied to organic solar cells. Representative materials that are currently used as donors and acceptors of organic thin film solar cells. In the case of semiconductor polymers, poly (para-phenylene vinylene) (PPV) -based materials and derivatives of polythiophene (PT) have been mainly studied. Recently, polyflourene (PF) -based materials and copolymers thereof have also been used as low-bandgap donor materials. In the case of an organic monomolecular substance, the phthalocyanine-based compound of the present invention can be used. The donor materials should primarily have a light absorption wavelength range well suited to the solar spectrum, have a very strong light absorption, and excellent electrical properties such as charge mobility. As the acceptor material, fullerene (C60) itself or C60 derivative (PCBM) designed to dissolve C60 in an organic solvent is used, and perylene, PTCBI and the like are also used as other single molecules. Among them, C60 derivatives are generally used as a BHJ structure material in combination with semiconductor polymers, but C60 is often used in bi-layer structure devices using vacuum deposition. It is ordered that the acceptor material has a particularly high electron affinity and charge mobility compared to the donor rather than the light absorption function.

Phthalocyanine nano compound of the present invention can be applied to biomaterials. Photodynamic therapy (PDT) is a technology that can treat intractable diseases such as cancer without surgery by using photosensitizer that is selective and sensitive to cancer cells or various tumors. It's a kind of cure without side effects. Photodynamic therapy involves administering the photosensitiser to a subject, for example, by intravenous injection, waiting for a certain time to wait for the photosensitiser to migrate to the tumor cells, and then depleting the cancer cells by irradiating red light of the appropriate wavelength. It is a treatment. Light-sensitized photosensitizers excite oxygen molecules and convert them into singlet oxygen, which directly destroys tumor tissue, or creates 2-3 new radicals to produce cancer cells or tumor tissue The bay will be selectively attacked or destroyed.

Suitable materials for this therapy should have a function as a photosensitizer, and representative materials are phthalocyanines. Not only can these materials be excited by red light (700-900 nm) with high transmission, but also the efficiency of interstation (ISC) in the excited state is high, and thus the triplet excited state can be efficiently generated. This triplet state here effectively transfers energy to the oxygen molecule, thus efficiently generating singlet oxygen. The partially reduced phthalocyanine-based compound of the present invention, which is a photosensitizer, selectively penetrates or accumulates in cancer cells or tumor tissues, and may be used for early diagnosis of tumors because it exhibits fluorescence or phosphorescence on the characteristics of the compound.

Hereinafter, the present invention will be described with reference to Examples. However, the scope of the present invention is not limited thereto.

Example

Example  One

Dicyanophenyl  Synthesis of Monomers Having Functional Groups

4-hydrooxyphthalonitrile (5.0 g, 0.0347 mol) was placed in a 250 mL round flask, and 100 mL of dried THF was added to dissolve the reaction. Triethylamine (5.8 mL, 0.04163 mol) was added to the solution, followed by cooling under an ice-bath. Methacryloyl chloride (4.07 mL, 0.04163 mol) was slowly added dropwise to the cooled mixture. After that, the temperature was gradually raised from 0 ° C. to room temperature, and the reaction proceeded under a nitrogen atmosphere. After 4 hours, the reaction was completed by TLC, and then filtered to remove the ammonium chloride salt. The filtrate is removed by an evaporator. As polymerization may occur in the process of removing the solvent, the filtrate is removed under reduced pressure at room temperature without raising the temperature. The concentrated solution was extracted three times with an aqueous NaCl solution and ethyl ether, and the ethyl ether layer was collected and removed by an evaporator. The residue was columned with hexanes: ethyl acetate = 3: 1 to give 2.5 g of the result in the form of a white solid. Figure 2 shows the chemical structure and ¹ H-NMR spectrum of the synthetic compound DCPM monomers.

¹ H NMR (CDCl ₃ ); delta = 2.07 (-C H ₃ ), 5.89-6.42 (C H ₂ -C (OOPh (CN) ₂ ) CH ₃ )), 7.55-7.86 (aromatic protons of phthalonitrile group).

Example  2

Dicyanophenyl methacrylate and Methyl methacrylate  Polymerization of Copolymers

DCPM (100 mg, 0.47 mmol) and AIBN (2.10mg, 0.01mmol) were added to a 10mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free methyl methacrylate (0.05 mL, 0.47 mmol) and solvent (THF, 1 mL) were added to the flask and polymerization was carried out at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the remaining solvent in a vacuum dryer.

Molecular weight of the copolymer ( M _n) = 26700 g / mol, M _w = 58100 g / mol) and polydispersity (PDI = 2.17) were measured by GPC, and the composition of each monomer (DCPM: MMA = 92: 70, based on DP) was determined using ¹ H NMR. Figure 3 shows the pMMA-co-pDCPM chemical structure and ¹ H-NMR spectrum.

Example  3

Dicyanophenyl methacrylate and Butyl methacrylate  Polymerization of Copolymers

3-1. pDCPM - co - pBMA Polymerization

DCPM (300mg, 1.42mmol) and AIBN (10.49mg, 0.05mmol) were added to a 15mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free butyl methacrylate (0.50 mL, 3.30 mmol) and a solvent (THF, 10 mL) were added to the flask and polymerization was carried out at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the solvent remaining in the vacuum dryer.

The molecular weight of the copolymer ( M _n = 24300 g / mol, M _w = 49700 g / mol) and polydispersity (PDI = 2.04) were determined by GPC, and the composition of each monomer (DCPM: MMA = 61: 80, based on DP). ) Was determined using ¹ H NMR. Figure 4 shows the chemical structure and ¹ H-NMR spectrum of pDCPM-co-pBMA.

3-2. High conversion rate pDCPM - co - pBMA Polymerization

DCPM (700mg, 3.30mmol) and AIBN (24.4mg, 0.11mmol) were added to a 20mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free butyl methacrylate (1.16 mL, 7.70 mmol) and a solvent (THF, 10 mL) were added to the flask and polymerization was carried out at 60 ° C. for 57 hours. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the solvent remaining in the vacuum dryer.

The copolymer was also measured using GPC for molecular weight (Mn = 14700 g / mol, Mw = 26900 g / mol) and polydispersity (PDI = 1.83), and the composition of each monomer (DCPM: BMA = 30: 59, based on DP) was determined by ¹ H NMR. Figure 5 shows the chemical structure and ¹ H-NMR spectrum of pDCPM-co-pBMA.

Example 4

Polymerization of Dicyanophenylmethacrylate and Styrene Copolymer

DCPM (100 mg, 0.47 mmol) and AIBN (2.10mg, 0.01mmol) were added to a 10mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free styrene (0.05 mL, 0.47 mmol) and solvent (THF, 1 mL) were added to the flask and polymerization was carried out at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the remaining solvent in a vacuum dryer.

Example 5

Polymerization of Dicyanophenylmethacrylate and Benzyl Methacrylate Copolymer

DCPM (100 mg, 0.47 mmol) and AIBN (2.10mg, 0.01mmol) were added to a 10mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free benzyl methacrylate (0.08 mL, 0.47 mmol) and solvent (THF, 1 mL) were added to the flask and polymerized at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the remaining solvent in a vacuum dryer.

Example 6

Polymerization of Dicyanophenylmethacrylate and 3- (dimethylamino) ethyl methacrylate copolymer

DCPM (100 mg, 0.47 mmol) and AIBN (2.10mg, 0.01mmol) were added to a 10mL round flask, and air was removed from the flask using a pump, and then replaced with nitrogen. Oxygen-free 3- (dimethylamino) ethyl methacrylate (0.08 mL, 0.47 mmol) and solvent (THF, 1 mL) were added to the flask and polymerization was carried out at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the remaining solvent in a vacuum dryer.

Example 7

Polymerization of Dicyanophenyl methacrylate with methyl methacrylate, butyl methacrylate, styrene, benzyl methacrylate copolymer

DCPM (100 mg, 0.47 mmol) and AIBN (2.10mg, 0.01mmol) were added to a 10mL round flask, and the pump was used to remove air from the flask and then replaced with nitrogen. Deoxygenated methyl methacrylate (0.01 mL, 0.12 mmol), butyl methacrylate (0.01 mL, 0.12 mmol), styrene (0.01 mL, 0.12 mmol), benzyl methacrylate (0.02 mL, 0.12 mmol) and solvent (THF, 1 mL) was added to the flask and polymerization was carried out at 60 ° C. The copolymer solution was precipitated in methanol to remove only the solid polymer and then remove the remaining solvent in a vacuum dryer.

Example  8

Copper phthalocyanine  Have pDCPM - co - pMMA Synthesis of

PDCPM-co-pMMA (30 mg, 0.001 mmol), CuCl (1 mg, 0.01 mmol), DBU (0.004 mL, 0.02 mmol) and solvent (pentanol, 2 mL / dimethyl sulfoxide, 1 mL) polymerized in Example 2 were substituted with nitrogen The flask was placed in a round 15 mL flask, and the reaction was performed under reflux conditions. The reaction solution was precipitated in methanol / HCl (11.8 M) and then filtered and only the solid portion was taken to remove the remaining solvent in the vacuum dryer.

The reaction was allowed to proceed for 6 hours and the reaction turned dark blue. UV / Vis. To evaluate optical properties. Measurements were made using spectroscopy and the results are shown in FIG. 6. GPC was used to determine the decrease in hydrodynamic volume caused by intra-ring-closing reaction, but could not be measured due to the low solubility in THF. For this reason, BMA was introduced in the following experiment.

Example  9

Copper Phthalocyanine  Have pDCPM - co - pBMA Synthesis of

PDCPM-co-pBMA (20 mg, 0.001 mmol), CuCl (1.22 mg, 0.01 mmol), DBU (0.007 mL, 0.05 mmol) and solvent (pentanol, 2 mL / dimethyl sulfoxide, 1 mL) polymerized in Example 3 were The reaction was carried out under reflux conditions in a 15 mL round flask substituted with. The reaction solution was precipitated in methanol / HCl (11.8M), filtered, and only the solid portion was taken and extracted continuously using chloroform. Chloroform was removed using a concentrator and the remaining solvent was removed in a vacuum dryer. After 24 hours it was confirmed that the color of the reaction turned dark blue, UV / Vis. Spectroscopy and GPC were measured to confirm the formation of CuPc.

7 is UV / Vis according to Example 5. FIG. The spectral results are shown, and FIG. 8 shows the GPC results according to Example 5. FIG. GPC results showed that the molecular weight decreased by about 10000 g / mol due to the decrease of the hydrodynamic volume due to the intra-ring-closing reaction. The formation of high molecular weight after the ring-closing reaction is due to the inter-ring-closing reaction between the copolymer chains. The obtained product was well dissolved in organic solvents such as THF, chloroform and DMSO, and was more soluble in nonpolar solvent than pDCPM-co-pMMA-CuPc.

Example  10

zinc Phthalocyanine  Branch pDCPM - co - pBMA Synthesis of

PDCPM-co-pBMA (360 mg, 0.02 mmol), ZnCl ₂ (23.3 mg, 0.17 mmol), DBU (0.10 mL, 0.69 mmol) and solvent (pentanol, 3 mL / dimethyl sulfoxide, 2 mL polymerized in Example 3-2) ) In a 15 mL round flask substituted with nitrogen and reacted under reflux. The reaction solution was precipitated in methanol / HCl (11.8M), filtered, and only the solid portion was taken and extracted continuously using tetrahydrofuran. Chloroform was removed using a concentrator and the solvent remaining in the vacuum dryer was removed. After 24 hours it was confirmed that the color of the reaction turned dark blue, UV / Vis. Spectroscopy and GPC were measured to confirm the formation of ZnPc.

9 is UV / Vis according to Example 6. FIG. The spectral results are shown, and FIG. 10 shows the GPC results according to Example 6. FIG. From the GPC results, it was confirmed that the molecular weight decreased about 6000 g / mol due to the decrease of the hydrodynamic volume due to the intra-ring-closing reaction. The formation of high molecular weight after the ring-closing reaction is due to the inter-ring-closing reaction between the copolymer chains. The obtained product was well dissolved in organic solvents such as THF, chloroform, and DMSO like pDCPM-co-pBMA-CuPc.

Example 11

Synthesis of pDCPM-co-pBMA with Metal Free Phthalocyanine

In a 15 mL round flask in which pDCPM-co-pBMA (20 mg, 0.001 mmol), DBU (0.007 mL, 0.05 mmol) and solvent (pentanol, 2 mL / dimethyl sulfoxide, 1 mL) polymerized in Example 3 were replaced with nitrogen. The reaction was carried out at 130 ℃ reflux conditions. The reaction solution was precipitated in methanol / HCl (11.8M), filtered, and only the solid portion was taken and extracted continuously using chloroform. Chloroform was removed using a concentrator and the remaining solvent was removed in a vacuum dryer. After 24 hours it was confirmed that the color of the reaction turned dark blue, UV / Vis. Spectroscopy and GPC were measured to confirm the formation of Pc.

Claims (15)

Copolymer comprising a dicyanophenyl group represented by the formula (1):
[Formula 1]

In this formula,
R1 and R2 are each a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
R3 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 5 to 10 carbon atoms An aryloxy group or an amino group,
m and n are natural numbers of 50-1,000, respectively.
The method of claim 1,
R 1 and R 2 are copolymers containing dicyanophenyl groups, each of which is an alkyl group having 1 to 4 carbon atoms.
Phthalocyanine compound represented by the following formula (2):
(2)

In this formula,
M is a divalent metal atom, a trivalent monosubstituted metal atom, a tetravalent disubstituted metal atom or a metal oxide,
L1, L2, L3, and L4 are each independently represented by formula (a):

(a)
In the formula (a),
R4 and R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms,
R 6 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 5 to 10 carbon atoms An aryloxy group or an amino group,
m and n are natural numbers of 50-1,000, respectively.
The method of claim 3,
M is a phthalocyanine compound, characterized in that copper (Cu) or zinc (Zn).
The method of claim 3,
R4 and R5 are phthalocyanine compounds, characterized in that each of the alkyl group having 1 to 4 carbon atoms.
Monomer compound represented by the following formula (3):
(3)

R7 is substituted or unsubstituted C1-10 alkyl group, substituted or unsubstituted C5-10 aryl group, substituted or unsubstituted C1-10 alkoxy group, substituted or unsubstituted C5-10 Is an aryloxy group or an amino group.
Synthesizing a monomer compound represented by Formula 3;
(3)

[R7 is a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C5-10 aryl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C5-C10 10 aryloxy group or amino group]
Reacting and copolymerizing the compound represented by Formula 3 with formula (b) to form a copolymer including a dicyanophenyl group represented by Formula 1; And

(b)
[Wherein R8 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, R9 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 5 to 10 carbon atoms, substituted or unsubstituted Alkoxy group having 1 to 10 carbon atoms, substituted or unsubstituted aryloxy group or amino group having 5 to 10 carbon atoms]
Method of preparing a phthalocyanine compound represented by the formula (2) comprising the step of reacting the copolymer with a metal chloride and a solvent to form a metallophthalocyanine.
The method of claim 7, wherein
R7 is a method for producing a phthalocyanine compound, characterized in that an alkyl group having 1 to 2 carbon atoms.
A liquid crystal display (LCD) comprising the phthalocyanine compound according to any one of claims 3 to 5.
Plasma display panel (PDP) comprising a phthalocyanine-based compound according to any one of claims 3 to 5.
An OPC drum comprising a phthalocyanine compound according to any one of claims 3 to 5.
An organic light emitting device (OLED) comprising a phthalocyanine compound according to any one of claims 3 to 5.
An electronic paper comprising the phthalocyanine-based compound according to any one of claims 3 to 5.
An organic solar cell comprising a phthalocyanine compound according to any one of claims 3 to 5.
A photosensitizer in photodynamic therapy comprising the phthalocyanine compound according to any one of claims 3 to 5.

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