JP2012255150A - Phthalocyanine compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phthalocyanine compound having a maximum absorption wavelength in a shorter wavelength region, particularly at nearly 640 to 750 nm.SOLUTION: The phthalocyanine compound has a specific structure. Substituents of α-position of the phthalocyanine nucleus are each independently a halogen atom or a 2,6-substituted phenoxy group by formula, and 4 substituents out of 8 ones denote a halogen atom. R3 and R4 each independently denote a methyl group, an ethyl group or a halogen atom. Substituents of β-position of the phthalocyanine nucleus each independently have a halogen atom-substituted phenoxy group. The central metal of the phthalocyanine compound may be no metal, a metal, a metal oxide or a metal halide.

Description

  The present invention relates to a novel filter for a flat panel display and a novel phthalocyanine compound. Specifically, the present invention relates to a light-cutting flat panel display filter having a wavelength of 640 to 750 nm, which contains a dye having a maximum absorption wavelength in the wavelength range of 640 to 750 nm, particularly a plasma display filter and a wavelength range of 640 to 750 nm. Relates to a phthalocyanine compound having a maximum absorption wavelength.

  In recent years, flat panel displays have attracted attention as displays that can be made thin and have a large screen. Among them, a plasma display panel (PDP), a liquid crystal display (LCD), and the like are widely spread and attract attention. However, PDP generates near-infrared light during plasma discharge, and this near-infrared light induces malfunctions in peripheral electronic devices such as remote controls such as televisions for home appliances, coolers, video decks, and transmission optical communications. Therefore, it is necessary to install an infrared absorption filter that cuts near infrared rays on the front surface.

  For the above purpose, the visible light transmittance is high, and the near-infrared light in a relatively long wavelength region of 800 to 1000 nm emitted from the display can be efficiently cut without impairing the sharpness of the display. Various studies have been made on phthalocyanine dyes excellent in selective absorption ability (for example, Patent Document 1).

  However, in recent years, the flow of increase in information amount has become very fast, and there is a demand for a shorter recording wavelength so that, for example, a CD-R is changing to a DVD ± R as a large capacity optical disk. For this reason, it is considered that the optical communication system currently used in the same manner at a wavelength of 800 to 900 nm used for mobile phones and game machines will be shortened to a wavelength of around 700 nm in the future. However, although the current PDP has extra light emission at a wavelength of 700 to 750 nm, a filter that cuts the wavelength of 700 to 750 nm is not installed, and there is a possibility of causing malfunction of transmission optical communication. It is thought that it will be necessary in the future to install a filter on the front side that cuts off the light in the area.

At the same time, light having a wavelength of 640 to 700 nm may be used for some LCDs that have a weak red color. However, unlike pure red having a wavelength range of 610 to 635 nm, the color tone is called “crimson”. For this reason, it is not necessarily a light with a preferable color tone in the field of flat panel displays and liquid crystal displays. Especially in a PDP with strong red light emission, a filter that cuts light in this wavelength range to reproduce pure red. Is becoming necessary.
JP 2001-264532 A

  As described above, in spite of increasing demand for a pigment capable of efficiently cutting near infrared light in the wavelength range of 640 to 750 nm, for example, as described in Patent Document 1, a longer wavelength is conventionally used. Research has focused on dyes that cut the light in the region. Moreover, even if a pigment capable of efficiently cutting near infrared light in such a wavelength range of 640 to 750 nm has been reported, it has not been considered to use it for a filter for a flat panel display or a liquid crystal display. .

  Therefore, in view of the above circumstances, an object of the present invention is to provide a phthalocyanine compound having a maximum absorption wavelength in a shorter wavelength region, particularly in the vicinity of 640 to 750 nm, and having an excellent cutting effect.

  Another object of the present invention is to provide a filter for a flat panel display and a phthalocyanine compound that can efficiently cut near infrared light having a wavelength range of 640 to 750 nm that is emitted from the display without damaging the visibility of the display with high visible light transmittance. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a phthalocyanine compound having a specific structure exhibits a maximum absorption wavelength in a short wavelength region, particularly around 640 to 750 nm. It came to be completed.

  That is, the above object is achieved by the following formula (1):

In the formula, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ each independently represent a halogen atom; Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are each independently a halogen atom or the following formula:

In this case, 0 to _{6 of} Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ represent a halogen atom; M represents metal-free, metal, metal oxide or metal halide,
It is achieved by the phthalocyanine compound (1) represented by

  In addition, the above object is achieved by the following formula (2):

In the formula, Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ each independently represent a hydrogen atom or a halogen atom; ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′ are each independently a hydrogen atom, a halogen atom or the following formula:

-COOR ¹ OR ² -containing phenoxy group represented by the formula, wherein R ¹ represents — (CH ₂ ) _p — (p is an integer of 1 to 5), and R ² represents the number of carbon atoms. Represents an alkyl group of 1 to 5, R ⁷ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a is 1 or 2, and in this case, Z ₂ ′, Z ₃ ′, Z ₆ ′ , Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′, 4 are halogen atoms and the remaining 4 represent a —COOR ¹ OR ² -containing phenoxy group, and 4 are 4 is and the remaining hydrogen atoms represents -COOR ¹ oR ² containing phenoxy group, or 8 represents a -COOR ¹ oR ² containing phenoxy groups; M is a metal-free, metal, metal oxides or metal halides Represents
It can also be achieved by the phthalocyanine compound (2) represented by the formula (1) or a hydrolyzate thereof.

  Furthermore, the above object is achieved by the following formula (3):

In the formula, Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ each independently represent a halogen atom or the following formula:

In this case, _{4 of} Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are represented. Each represents a halogen atom, and R ³ and R ⁴ each independently represent a methyl group, an ethyl group or a halogen atom; Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″. , Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ are independently selected from the following formulas:

In this case, R ⁵ represents a halogen atom, and when a plurality of R ⁵ are present, each R ⁵ may be the same or different. , N is an integer from 1 to 5; M represents a metal-free, metal, metal oxide or metal halide,
It is also achieved by the phthalocyanine compound (3) represented by

Furthermore, the above object is achieved by the following formula (4):
Following formula (4):

In the formula, Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ are independently hydrogen Represents an atom or a halogen atom; Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are each independently A hydrogen atom, a halogen atom or the following formula:

-COOR ⁶ -containing phenoxy group represented by the formula: wherein R ⁶ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁸ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. In this case, four of Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are a halogen atom and the remaining four represents a -COOR ⁶ containing a phenoxy group, 4 represents a is and the remaining four are -COOR ⁶ containing phenoxy group hydrogen atom, or 8 is -COOR ⁶ containing phenoxy M represents a metal-free, metal, metal oxide or metal halide;
It can also be achieved by the phthalocyanine compound (4) represented by the formula (1) or a hydrolyzate thereof.

  Furthermore, the above object is achieved by the following formula (5):

In the formula, Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y ₁₃ and Y ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula:

In represents -COOR ⁹ containing phenoxy group represented, this time, ^{R 9} represents an alkyl group having 1 to 20 carbon atoms, this _{time, Y 1, Y 4, Y} 5, Y 8, Y 9, Y ₁₂ , Y ₁₃ and Y ₁₆ are 4 halogen atoms and the remaining 4 represent a —COOR ^9- containing phenoxy group, or 4 are hydrogen atoms and the remaining 4 represent —COOR ^9- containing Represents a phenoxy group; Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ each independently represents a hydrogen atom or a halogen atom; Represents a metal oxide or metal halide,
It can also be achieved by a phthalocyanine compound (5) represented by the formula (1) or a hydrolyzate thereof.

  Since the filter for a flat panel display and the phthalocyanine compound of the present invention exhibit a maximum absorption wavelength particularly in the vicinity of 640 to 750 nm, light in an unnecessary near infrared region (700 to 750 nm) emitted from a flat panel display, particularly PDP or LCD, For example, light of an impure red wavelength (640 to 700 nm) called so-called crimson is cut to prevent, for example, the malfunction of the optical communication system from being induced, and at the same time, the effect of reproducing a clear red color can be exhibited.

  The first of the present invention is the following formula (1):

In the formula, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ each independently represent a halogen atom; Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are each independently a halogen atom or the following formula:

In this case, 0 to _{6 of} Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ represent a halogen atom; M represents metal-free, metal, metal oxide or metal halide,
It is related with the phthalocyanine compound (1) shown by these. In the present specification, the phthalocyanine compound (1) of the above formula (1) is also simply referred to as “phthalocyanine compound (1)”.

  The second of the present invention is the following formula (2):

In the formula, Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ each independently represent a hydrogen atom or a halogen atom; ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′ are each independently a hydrogen atom, a halogen atom or the following formula:

-COOR ¹ OR ² -containing phenoxy group represented by the formula, wherein R ¹ represents — (CH ₂ ) _p — (p is an integer of 1 to 5), and R ² represents the number of carbon atoms. Represents an alkyl group of 1 to 5, R ⁷ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a is 1 or 2, and in this case, Z ₂ ′, Z ₃ ′, Z ₆ ′ , Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′, 4 are halogen atoms and the remaining 4 represent a —COOR ¹ OR ² -containing phenoxy group, and 4 are 4 is and the remaining hydrogen atoms represents -COOR ¹ oR ² containing phenoxy group, or 8 represents a -COOR ¹ oR ² containing phenoxy groups; M is a metal-free, metal, metal oxides or metal halides Represents
It is related with the phthalocyanine compound (2) shown by these, or its hydrolyzate. In the present specification, the phthalocyanine compound (2) of the above formula (2) is also simply referred to as “phthalocyanine compound (2)”.

  The third of the present invention is the following formula (3):

In the formula, Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ each independently represent a halogen atom or the following formula:

In this case, _{4 of} Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are represented. Each represents a halogen atom, and R ³ and R ⁴ each independently represent a methyl group, an ethyl group or a halogen atom; Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″. , Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ are independently selected from the following formulas:

In this case, R ⁵ represents a halogen atom, and when a plurality of R ⁵ are present, each R ⁵ may be the same or different. , N is an integer from 1 to 5; M represents a metal-free, metal, metal oxide or metal halide,
It is related with the phthalocyanine compound (3) shown by these. In the present specification, the phthalocyanine compound (3) of the above formula (3) is also simply referred to as “phthalocyanine compound (3)”.

  The fourth of the present invention is the following formula (4):

In the formula, Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ are independently hydrogen Represents an atom or a halogen atom; Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are each independently A hydrogen atom, a halogen atom or the following formula:

-COOR ⁶ -containing phenoxy group represented by the formula: wherein R ⁶ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁸ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. In this case, four of Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are a halogen atom and the remaining four represents a -COOR ⁶ containing a phenoxy group, 4 represents a is and the remaining four are -COOR ⁶ containing phenoxy group hydrogen atom, or 8 is -COOR ⁶ containing phenoxy M represents a metal-free, metal, metal oxide or metal halide;
It is related with the phthalocyanine compound (4) shown by these, or its hydrolyzate. In the present specification, the phthalocyanine compound (4) of the above formula (4) is also simply referred to as “phthalocyanine compound (4)”.

  The fifth of the present invention is the following formula (5):

In the formula, Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y ₁₃ and Y ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula:

In represents -COOR ⁹ containing phenoxy group represented, this time, ^{R 9} represents an alkyl group having 1 to 20 carbon atoms, this _{time, Y 1, Y 4, Y} 5, Y 8, Y 9, Y ₁₂ , Y ₁₃ and Y ₁₆ are 4 halogen atoms and the remaining 4 represent a —COOR ^9- containing phenoxy group, or 4 are hydrogen atoms and the remaining 4 represent —COOR ^9- containing Represents a phenoxy group; Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ each independently represents a hydrogen atom or a halogen atom; Represents a metal oxide or metal halide,
It is related with the phthalocyanine compound (5) shown by these, or its hydrolyzate. In the present specification, the phthalocyanine compound (5) of the above formula (5) is also simply referred to as “phthalocyanine compound (5)”.

  Since the phthalocyanine compound having a specific structure as described above exhibits a maximum absorption wavelength in a specific wavelength region of 640 to 750 nm, it is possible to selectively cut light in these regions. For this reason, the flat panel display and liquid crystal display filter using the phthalocyanine compound of the present invention prevents, for example, the malfunction of the optical communication system corresponding to the flow of information increase, and at the same time reproduces a clear red color. Useful to do. In addition, the phthalocyanine compound having a specific structure as described above efficiently cuts light having a wavelength of 640 to 700 nm, which is not necessarily a light of a preferable color tone in the field of flat panel displays and liquid crystal displays that emit strong red light. Therefore, a filter using such a compound can be suitably used for a flat panel display or a liquid crystal display that reproduces pure red.

Hereinafter, preferred embodiments in the first aspect of the present invention will be described. In the present specification, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z _{16 in} formula (1); Z ₁ ′, Z ₄ ′ in formula (2) , Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′; in formula (3), Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″ , Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″; in formula (4), Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ and Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y _13, and Y ₁₆ in formula (5) are the eight α-positions of the phthalocyanine nucleus, respectively. These substituents are also referred to as α-position substituents. Similarly, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z _{15 in} formula (1); Z ₂ ′, Z ₃ ′ in formula (2), Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′; in the formula (3), Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″; Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z _{14 in the} formula (4) “′ And Z ₁₅ ” ”and Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ in the formula (5) are respectively at eight β positions of the phthalocyanine nucleus. In order to represent a substituent to be substituted, these substituents are also referred to as β-position substituents.

In the above formula (1), Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z _{16 which} are α-position substituents of the phthalocyanine nucleus represent halogen atoms. At this time, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ may be the same or different. The α-position halogen atom of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferably, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ are a fluorine atom and a chlorine atom, and particularly preferably a fluorine atom.

In the above formula (1), Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ which are substituents at the β-position of the phthalocyanine nucleus are a halogen atom or the following formula: :

2 represents a 2-methylphenoxy group (also simply referred to as “2-methylphenoxy group” in the present specification). At this time, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ may be the same or different. In addition, 0 to 6 substituents at the β-position of the phthalocyanine nucleus are halogen atoms. More preferably, 0 to 5, more preferably 0 to 3, and most preferably 2.4 of the β-position substituents of the phthalocyanine nucleus are halogen atoms. The phthalocyanine compound (1) of the present invention includes a case where a plurality of types of compounds are present in the form of a mixture in addition to the case of being a kind of compound. For this reason, in such a case, the number of halogen atoms in the β-position substituent in the above formula (1) is not necessarily an integer because it is expressed as an average of halogen atoms in each phthalocyanine compound. In addition, since the sum total of the halogen atoms and 2-methylphenoxy groups which are substituents at the β-position is 8, when the number of halogen atom substitutions is not an integer, the number of 2-methylphenoxy group substitutions is the same. Is not an integer. The phthalocyanine compound (1) in the case where the number of halogen atoms in the β-position substituent in the formula (1) is not an integer will be described in detail below. It can manufacture by the method etc. which cyclize-react this and a metal salt using what was mixed by ratio. The halogen atom at the β-position of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferably, Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are a fluorine atom and a chlorine atom, and particularly preferably a fluorine atom.

  In the above formula (1), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Vanadyl and zinc. In particular, when the phthalocyanine compound (1) is used in a flat panel display, particularly a PDP filter, it must be stable against the heat generated from the PDP panel, so that it has excellent heat resistance. Since the case added to the adhesion layer at the time of sticking to PDP front filter glass can be considered, durability is required. For this reason, in the said use, it is preferable that a center metal is copper. Further, when used in a filter of a liquid crystal display, heat from the panel is not generated as much as PDP, and therefore, higher optical properties (transparency) are required rather than heat resistance. Therefore, for the above-mentioned use, phthalocyanine whose central metal having excellent optical properties (transparency) is zinc is preferable.

  Accordingly, preferred examples of the phthalocyanine compound (1) of the present invention include the following compounds. The following formula represents that an average of 2.4 fluorine atoms and an average of 5.6 2-methylphenoxy groups are bonded to the β-position of the phthalocyanine nucleus. This also applies to other examples of phthalocyanine compounds. It is the same.

  The following formula representing the phthalocyanine compound (A) is intended to be a mixture in which an average of 2.4 fluorine atoms and an average of 5.6 2-methylphenoxy groups are bonded to 8 β-positions of the phthalocyanine nucleus. The number of bonds of each fluorine atom and 2-methylphenoxy group of each phthalocyanine compound is arbitrary, and the bonding position of each substituent is also arbitrary. The same applies to other examples of phthalocyanine compounds. Further, in the following, the parentheses described together with each exemplary compound indicate the maximum absorption wavelength (λmax) and the magnification of the absorbance at the maximum absorption wavelength with respect to the absorbance at 460 nm.

  Of the above compounds, the phthalocyanine compound (A) is particularly preferred in the present invention.

  Next, a preferred embodiment in the second aspect of the present invention will be described below.

In the above formula (2), Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ which are α-position substituents of the phthalocyanine nucleus are Represents a hydrogen atom or a halogen atom. At this time, Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ may be the same or different. The α-position halogen atom of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Z ₁ ′, Z ₄ ′, Z ₅ ^′ , Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ are preferably a hydrogen atom, a fluorine atom or a chlorine atom, particularly preferably It is a hydrogen atom or a fluorine atom. Most preferably, the α-position substituents, Z ₁ ′, Z ₄ ′, Z ₅ ^′ , Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ are all hydrogen atoms, or It is a fluorine atom.

In the above formula (2), Z ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′, and Z ₁₅ , which are substituents at the β-position of the phthalocyanine nucleus. 'Is a hydrogen atom, a halogen atom or the following formula:

-COOR ¹ OR ² -containing phenoxy group (hereinafter, also simply referred to as “—COOR ¹ OR ² -containing phenoxy group”) having a substituent represented by At this time, Z ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′ may be the same or different. In the β-position substituent of the phthalocyanine nucleus, four are halogen atoms and the remaining four represent a —COOR ¹ OR ² -containing phenoxy group, four are hydrogen atoms, and the remaining four are — Either represents a COOR ¹ OR ² containing phenoxy group or 8 represent a —COOR ¹ OR ² containing phenoxy group. That is, the β position of the phthalocyanine nucleus is occupied by 4 hydrogen atoms or halogen atoms and 4 —COOR ¹ OR ² -containing phenoxy groups, or all 8 are occupied by —COOR ¹ OR ² -containing phenoxy groups. The position where four hydrogen atoms or halogen atoms and four —COOR ¹ OR ² -containing phenoxy groups occupy the β-position of the phthalocyanine nucleus is arbitrary and is not particularly limited. For example, when a hydrogen atom or a halogen atom and a —COOR ¹ OR ² -containing phenoxy group are bonded to two residues of the benzene ring (for example, Z ₂ ′ and Z ₃ ′); Zan'i (e.g., _{Z 2} 'and _{Z 3')} in -COOR ¹ oR ² when containing phenoxy groups are two bond; halogen two remaining position of the benzene ring (e.g., _{Z 2} 'and _{Z 3')} Any may be used, such as when two atoms are bonded. Preferably, one hydrogen atom or halogen atom and ^one —COOR ¹ OR ² -containing phenoxy group are bonded to two remaining positions (eg, Z ₂ ′ and Z ₃ ′) of each benzene ring. In any of the above cases, the β position of the phthalocyanine nucleus is occupied by a total of 4 hydrogen atoms or halogen atoms and a total of 4 —COOR ¹ OR ² -containing phenoxy groups.

In the above formula representing a —COOR ¹ OR ² -containing phenoxy group, R ¹ represents a divalent group of — (CH ₂ ) _p — (p is an integer of 1 to 5, preferably 1 to 3). . Examples of such groups include a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), a trimethylene group (—CH ₂ CH ₂ CH ₂ —), and a propylene group (—CH (CH ₃ ) CH. ₂ -), tetramethylene _{(-CH 2} CH ₂ CH 2 _CH 2 -), isobutylene group _{(-C (CH 3) 2 CH} 2 -), sec- butylene _{(-CH 2 CH 2 CH (CH} 3) -), pentamethylene group _{(-CH 2 CH 2 CH 2 CH} 2 CH 2 -), isopentylene _{(-C (CH 3) 2 CH} 2 CH 2 -) include straight chain and branched chain groups such as. Among these, an ethylene group and a propylene group are preferable, and an ethylene group is most preferable. R ² represents an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of such alkyl groups include linear and branched alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, pentyl, neopentyl, sec-butyl, and tert-butyl. Is mentioned. Of these, a methyl group and an ethyl group are preferable, and a methyl group is most preferable. A represents the number of —COOR ¹ OR ² groups bonded to the phenoxy group, and is 1 or 2. That is, the —COOR ¹ OR ² -containing phenoxy group has a structure in which a total of two —COOR ¹ OR ² groups or R ⁷ groups are bonded to the phenoxy group, but the —phenoxy group or R ⁷ group of —COOR ¹ OR ² groups The bonding position to the benzene ring is not particularly limited, but is preferably 2,6, 2,4, 2,5, etc., particularly preferably 2,6.

In the above formula (2), R ⁷ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. When a is 1 and R ⁷ is a hydrogen atom, the —COOR ¹ OR ² -containing phenoxy group has a structure in which one —COOR ¹ OR ² group is bonded to the phenoxy group.

  In the above formula (2), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Vanadyl and zinc. In particular, when the phthalocyanine compound (2) is used in a flat panel display, particularly a filter for PDP, it must be stable against heat generated from the PDP panel, so that it has excellent heat resistance, and the PDP panel. Since the case added to the adhesion layer at the time of sticking to PDP front filter glass can be considered, durability is required. For this reason, in the said use, it is preferable that a center metal is copper. Further, when used in a filter of a liquid crystal display, heat from the panel is not generated as much as PDP, and therefore, higher optical properties (transparency) are required rather than heat resistance. Therefore, for the above-mentioned use, phthalocyanine whose central metal having excellent optical properties (transparency) is zinc is preferable. Further, compatibility with the resin and coating require solubility in a solvent. From the viewpoint of solubility, the central metal is preferably vanadyl. Also, phthalocyanine whose central metal is vanadyl is excellent in durability.

The second embodiment of the present invention includes a hydrolyzate of the phthalocyanine compound (2) in addition to the phthalocyanine compound (2). Here, “the hydrolyzate of the phthalocyanine compound (2)” means that the ester portion (—COOR ¹ OR ² in the formula (2)) in the phthalocyanine compound ( ² ) is converted into a carboxyl group (—COOH) by hydrolysis. Means to be converted.

In the present invention, the ratio of the ester moiety in the phthalocyanine compound (2) (—COOR ¹ OR ² in the formula (2)) converted to a carboxyl group (—COOH) by hydrolysis (hereinafter simply referred to as “hydrolysis rate”) Is also preferably 3 to 80%, more preferably 5 to 50%, and particularly preferably 10 to 30%. Thus, it is preferable to convert the ester moiety to a carboxyl group because solubility in a lower alcohol such as methanol or ethanol or a hydrophilic solvent such as an aqueous solution thereof can be improved and the extinction coefficient can be improved. Moreover, by using a hydrolyzate, the compatibility with a resin having a hydroxyl group such as a butyral resin can also be improved, and the range of resins that can be preferably used as a matrix can be expanded. In the above, the hydrolysis rate means that the ester moiety (—COOR ¹ OR ² in the formula (2)) present in the phthalocyanine compound (2) before hydrolysis is converted into a carboxyl group (—COOH) by hydrolysis. Means the percentage of More specifically, the hydrolysis rate is converted by hydrolysis with respect to the number (A) of ester moieties (—COOR ¹ OR ² in formula (2)) present in the phthalocyanine compound (2) before hydrolysis. It is a value [(B / A) × 100 (%)] in which the ratio of the number of carboxyl groups (—COOH) (B) is expressed as a percentage.

In the present invention, the hydrolysis method is not particularly limited, and a known ester portion hydrolysis method can be applied similarly or appropriately modified. Usually, a method of hydrolyzing the phthalocyanine compound (2) under alkaline conditions can be used. In the above method, the number of —COOR ¹ OR ² -containing phenoxy groups present in the phthalocyanine compound (2) is not particularly limited, but preferably the —COOR ¹ OR ² -containing phenoxy group is one phthalocyanine compound (2). Among them, 1 to 8, more preferably 4 to 8 are present, and it is most preferable that 4 or all (8) of the substituents at the β-position are —COOR ¹ OR ² -containing phenoxy groups. If it is such a range, since the obtained phthalocyanine compound has a high extinction coefficient and is excellent in compatibility with a resin having a hydroxyl group such as a butyral resin, the range of resins that can be used as a matrix is expanded.

  In the above method, the alkali is not particularly limited as long as it can favorably hydrolyze the phthalocyanine compound (2). Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Of these, sodium hydroxide and potassium hydroxide are preferred. Moreover, the addition amount of an alkali will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (2) favorably. Specifically, it is preferable to add the alkali in an amount of 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the phthalocyanine compound (2).

  In view of reaction efficiency, the hydrolysis is preferably performed in a solvent. The solvent that can be used in this case is not particularly limited as long as it is a solvent capable of dissolving an alkali. Specifically, water; alcohols such as methanol, ethanol, propanol, and isopropanol; dimethyl sulfoxide, pyridine, N, N-dimethyl. Examples include aprotic polar solvents such as formamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, sulfolane; and acetone, acetonitrile, benzonitrile, and the like. Of these, water, ethanol, dimethyl sulfoxide, and N, N-dimethylformamide are preferably used. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  The usage-amount of the said solvent will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (2) favorably. Specifically, such an amount that the concentration of the phthalocyanine compound (2) in the solvent is 5 to 40% by mass, more preferably 10 to 25% by mass is preferable.

  In the above method, the hydrolysis conditions are not particularly limited as long as the phthalocyanine compound (2) can be hydrolyzed satisfactorily, but can be appropriately selected according to the hydrolysis rate. Specifically, the mixture of the phthalocyanine compound (2), the alkali, and the solvent is preferably at a temperature of 30 to 100 ° C., more preferably 40 to 80 ° C., preferably 1 to 10 hours, more preferably 2 to 6 Let react for hours. At this time, the mixture is preferably reacted with stirring so that hydrolysis can proceed more easily.

  In this way, the phthalocyanine compound (2) is hydrolyzed, but after the hydrolysis reaction is completed, an acid is added to acidify and precipitate the hydrolyzate of the phthalocyanine compound (2) as crystals. Is preferred. The acid that can be used in this case is not particularly limited as long as it can acidify the hydrolysis reaction solution as appropriate to crystallize the hydrolyzate of the phthalocyanine compound (2). Specific examples include concentrated hydrochloric acid, hydrochloric acid, concentrated sulfuric acid, sulfuric acid, concentrated nitric acid, nitric acid, and acetic acid. Of these, concentrated hydrochloric acid, hydrochloric acid, and acetic acid are preferred. Further, the amount of acid added is not particularly limited as long as it is an amount capable of satisfactorily crystallizing the hydrolyzate of the phthalocyanine compound (2). Specifically, the acid is added in such an amount that the pH of the hydrolysis reaction solution is preferably 5 to 1, more preferably 3 to 1.

  The hydrolyzate of the phthalocyanine compound (2) thus precipitated as crystals can be separated by a known method such as filtration, suction filtration, and pressure filtration. Moreover, after the separation, it is preferable to stir and wash the hydrolyzate of the phthalocyanine compound (2) with an appropriate washing solvent. In this way, a highly pure phthalocyanine compound (2) is obtained. Here, the washing solvent is not particularly limited as long as impurities can be appropriately separated from the liquid containing the hydrolyzate of the phthalocyanine compound (2). Specific examples include water; alcohols such as methanol, ethanol, propanol, and isopropanol; acetonitrile. Of these, water, methanol, and acetonitrile are preferably used. In addition, the said washing | cleaning solvent may be used independently or may be used with the form of 2 or more types of mixtures.

Accordingly, preferred examples of the phthalocyanine compound (2) and the hydrolyzate thereof according to the present invention include the following compounds. The following formula representing the phthalocyanine compound (a) represents that 4 fluorine atoms and 4 —COOR ¹ OR ² -containing phenoxy groups are bonded to 8 β-positions of the phthalocyanine nucleus, The bonding position of each substituent is arbitrary. The same applies to other examples of phthalocyanine compounds.

  Among the above compounds, phthalocyanine compounds (a), (e), (g), (h), (i), (j), (k) are preferred in the present invention, and phthalocyanine compounds (a), (h), (I) and (j) are more preferred in the present invention.

  Further, a preferred embodiment in the third aspect of the present invention will be described below.

In the above formula (3), Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″, which are α-position substituents of the phthalocyanine nucleus, are , Halogen atom or the following formula:

2 represents a 2,6-substituted phenoxy group (also simply referred to as “2,6-substituted phenoxy group” in the present specification). In this case, Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ may be the same or different. Further, four of the α-position substituents of the phthalocyanine nucleus are halogen atoms, that is, the β-position of the phthalocyanine nucleus is occupied by four halogen atoms and four 2,6-substituted phenoxy groups. In this case, the position where the four halogen atoms and the four 2,6-substituted phenoxy groups occupy the α-position of the phthalocyanine nucleus is arbitrary and not particularly limited, but the two remaining positions of the benzene ring (for example, Z ₁ ″ and Z ₄ ″) are each bonded with a halogen atom and a 2,6-substituted phenoxy group; two residual groups of the benzene ring (for example, Z ₁ ″ and Z ₄ ″) have 2,6- In the case where two substituted phenoxy groups are bonded; in the case where two halogen atoms are bonded to the two remaining positions of the benzene ring (for example, Z ₁ ″ and Z ₄ ″), any may be used, but preferably each benzene ring Are bonded to one of the remaining residues (for example, Z ₁ ″ and Z ₄ ″) one by one, a halogen atom and a 2,6-substituted phenoxy group. In any of the above cases, the α-position of the phthalocyanine nucleus is occupied by a total of four halogen atoms and a total of four 2,6-substituted phenoxy groups.

In the above formula (3), the α-position halogen atom of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom. is there.

In the above formula showing a 2,6-substituted phenoxy group, R ³ and R ⁴ represent a methyl group, an ethyl group or a halogen atom. At this time, R ³ and R ⁴ may be the same or different. The halogen atom represented by R ³ and R ⁴ is not particularly limited and may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom, particularly preferably Is a chlorine atom. Of the above, R ³ and R ⁴ are preferably a methyl group or an ethyl group, and most preferably R ³ and R ⁴ are both methyl groups.

In the above formula (3), Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ which are β-position substituents of the phthalocyanine nucleus. "Is the following formula:

Represents a substituted phenoxy group represented by (also referred to simply as “substituted phenoxy group” in the present specification). At this time, Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″, Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ may be the same or different.

In the above formula showing a substituted phenoxy group, R ⁵ represents a halogen atom. At this time, when a plurality of R ⁵ are present (n is 2 or more), R ⁵ may be the same or different. Note that R ⁵ in the above formula means that n hydrogen atoms at any position of the remaining position of the benzene ring (position where no oxygen atom is present) are substituted with n R ⁵ . The halogen atom as R ⁵ is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected, but preferably a fluorine atom, a chlorine atom or a bromine atom. And particularly preferably a chlorine atom. N represents the number of the substituent R ⁵ bonded to the remaining position of the phenoxy group, and is an integer of 1 to 5, preferably an integer of 2 to 3, and most preferably 2. Position substituent R ⁵ is attached to the remainder position phenoxy group is not particularly limited, is suitably selected depending on the number of bonds (n) and the type of the substituents R ⁵ substituents R ^5. For example, when n is 2, preferred are 2,6, 2,3, 2,5, etc., and 2,6 is most preferred. In addition, when n is 3, preferred are 2,4,6, 2,3,6, etc., and 2,4,6 is most preferred.

  In the above formula (3), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Vanadyl and zinc. In particular, when the phthalocyanine compound (3) is used in a flat panel display, particularly a filter for PDP, it must be stable against heat generated from the PDP panel, so that it has excellent heat resistance, and the PDP panel. Since the case added to the adhesion layer at the time of sticking to PDP front filter glass can be considered, durability is required. For this reason, in the said use, it is preferable that a center metal is copper. Further, when used in a filter of a liquid crystal display, heat from the panel is not generated as much as PDP, and therefore, higher optical properties (transparency) are required rather than heat resistance. Therefore, for the above-mentioned use, phthalocyanine whose central metal having excellent optical properties (transparency) is zinc is preferable.

  Accordingly, preferred examples of the phthalocyanine compound (3) of the present invention include the following compounds. The following formula representing the phthalocyanine compound (a) indicates that four fluorine atoms and four substituted phenoxy groups are bonded to the eight α-positions of the phthalocyanine nucleus. The position is arbitrary. The same applies to other examples of phthalocyanine compounds.

  Of the above compounds, the phthalocyanine compound (a) is particularly preferred in the present invention.

  Next, a preferred embodiment in the fourth aspect of the present invention will be described below.

In the above formula (4), Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ′ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ , which are α-position substituents of the phthalocyanine nucleus. "'and _{Z 16'"} represents a hydrogen atom or a halogen atom. In this case, Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ may be the same or It may be different. The α-position halogen atom of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferably, Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ are a hydrogen atom, a fluorine atom, A chlorine atom, particularly preferably a hydrogen atom or a fluorine atom. Most preferably, the α-position substituents Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ are All are hydrogen atoms or fluorine atoms.

In the above formula (4), Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ′ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, which are substituents at the β-position of the phthalocyanine nucleus, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are a hydrogen atom, a halogen atom or the following formula:

-COOR ⁶ -containing phenoxy group represented by (also referred to simply as “—COOR ⁶ -containing phenoxy group” in the present specification). In this case, Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ may be the same or It may be different. Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are 4 halogen atoms. And the remaining 4 represent a -COOR ⁶ -containing phenoxy group, 4 are hydrogen atoms and the remaining 4 represent a -COOR ⁶ -containing phenoxy group, or 8 represent a -COOR ⁶ -containing phenoxy group, One of them. That is, the β position of the phthalocyanine nucleus is occupied by 4 hydrogen atoms or halogen atoms and 4 —COOR ⁶ -containing phenoxy groups, or all 8 are occupied by —COOR ⁶ -containing phenoxy groups. In this case, the position where the four hydrogen atoms or halogen atoms and the four —COOR ⁶ -containing phenoxy groups occupy the β-position of the phthalocyanine nucleus is arbitrary and is not particularly limited. For example, when a hydrogen atom or a halogen atom and a —COOR ⁶ -containing phenoxy group are bonded to two residues of the benzene ring (for example, Z ₂ ″ ′ and Z ₃ ″ ′); Zan'i (e.g., _{Z 2} "', and _{Z 3"')} when -COOR ⁶ containing phenoxy groups are two bond; two remaining position of the benzene ring (e.g., _{Z 2} "', and _{Z 3"')} In any case, for example, when two halogen atoms are bonded to each other, hydrogen atoms or halogen atoms and —COOR ⁶ are preferably present at the two remaining positions (for example, Z ₂ ″ ′ and Z ₃ ″ ′) of each benzene ring. The contained phenoxy groups are bonded one by one. In any of the above cases, the β position of the phthalocyanine nucleus is occupied by a total of 4 hydrogen atoms or halogen atoms and a total of 4 —COOR ⁶ -containing phenoxy groups.

In the above formula representing a —COOR ⁶ -containing phenoxy group, R ⁶ represents an alkyl or phenyl group having 1 to 20, preferably 1 to 8, more preferably 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. 1,2-dimethylpropyl group, n-hexyl 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-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-t -Linear and branched alkyl groups such as -butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group Of these, a methyl group and an ethyl group are preferable, and a methyl group is most preferable.

In the above formula (4), R ⁸ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. When R ⁸ is a hydrogen atom, the —COOR ⁶ -containing phenoxy group has a structure in which only one —COOR ⁶ group is bonded to the phenoxy group. The bonding position of R ^{8 to} the benzene ring is not particularly limited. For example, when R ⁸ represents a halogen atom, a methyl group or a methoxy group, the bonding position of the —COOR ⁶ -containing phenoxy group and R ^{8 to} the benzene ring is not particularly limited, but the 2, 6-position, 2, 4-position 2, 5th, 3rd, 6th, etc. are preferred, especially the 3rd, 6th and 2nd, 5th positions. Further, when ^{R 8} is a hydrogen atom, ^{-COOR 6} containing phenoxy groups have the structure -COOR ⁶ group is attached one phenoxy group on the benzene ring of the phenoxy group -COOR ⁶ group The bonding position is not particularly limited and may be any of 2-position, 3-position, and 4-position, but 2-position and 3-position are preferable in consideration of solubility.

  In the above formula (4), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Vanadyl and zinc. In particular, when the phthalocyanine compound (4) is used for a flat panel display, particularly a filter for PDP, it must be stable against heat generated from the PDP panel, so that it has excellent heat resistance, and the PDP panel. Since the case added to the adhesion layer at the time of sticking to PDP front filter glass can be considered, durability is required. For this reason, in the said use, it is preferable that a center metal is copper. Further, when used in a filter of a liquid crystal display, heat from the panel is not generated as much as PDP, and therefore, higher optical properties (transparency) are required rather than heat resistance. Therefore, for the above-mentioned use, phthalocyanine whose central metal having excellent optical properties (transparency) is zinc is preferable. Further, compatibility with the resin and coating require solubility in a solvent. From the viewpoint of solubility, the central metal is preferably vanadyl. Also, phthalocyanine whose central metal is vanadyl is excellent in durability.

In addition to the said phthalocyanine compound (4), the 4th aspect of this invention also includes the hydrolyzate of the said phthalocyanine compound (4). Here, “hydrolyzate of phthalocyanine compound (4)” means that the ester moiety (—COOR ⁶ in formula (4)) in phthalocyanine compound (4) is converted to a carboxyl group (—COOH) by hydrolysis. Means that.

In the present invention, the proportion of the ester moiety in the phthalocyanine compound (4) (—COOR ⁶ in the formula (4)) converted to a carboxyl group (—COOH) by hydrolysis (hereinafter also simply referred to as “hydrolysis rate”). ) Is preferably 3 to 80%, more preferably 5 to 50%, and particularly preferably 10 to 30%. Thus, it is preferable to convert the ester moiety to a carboxyl group because solubility in a lower alcohol such as methanol or ethanol or a hydrophilic solvent such as an aqueous solution thereof can be improved and the extinction coefficient can be improved. Moreover, by using a hydrolyzate, the compatibility with a resin having a hydroxyl group such as a butyral resin can also be improved, and the range of resins that can be preferably used as a matrix can be expanded. In the above, the hydrolysis rate is the ratio of the ester moiety (—COOR ⁶ in formula (4)) present in the phthalocyanine compound (4) before hydrolysis converted to a carboxyl group (—COOH) by hydrolysis. Means. More specifically, the hydrolysis rate is the carboxyl converted by hydrolysis with respect to the number (A) of ester moieties (—COOR ⁶ in formula (4)) present in the phthalocyanine compound (4) before hydrolysis. It is a value [(B / A) × 100 (%)] in which the ratio of the number (B) of the group (—COOH) is expressed as a percentage.

In the present invention, the hydrolysis method is not particularly limited, and a known ester portion hydrolysis method can be applied similarly or appropriately modified. Usually, a method of hydrolyzing the phthalocyanine compound (4) under alkaline conditions can be used. In the above method, the number of —COOR ⁶ -containing phenoxy groups present in the phthalocyanine compound (4) is not particularly limited, but preferably the —COOR ⁶ -containing phenoxy group is 1 in one phthalocyanine compound (4). There are ˜8, more preferably 4-8, and it is most preferred that 4 or all (8) of the β-position substituents are —COOR ⁶ -containing phenoxy groups. If it is such a range, since the obtained phthalocyanine compound has a high extinction coefficient and is excellent in compatibility with a resin having a hydroxyl group such as a butyral resin, the range of resins that can be used as a matrix is expanded.

  In the above method, the alkali is not particularly limited as long as it can favorably hydrolyze the phthalocyanine compound (4). Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Of these, sodium hydroxide and potassium hydroxide are preferred. Moreover, the addition amount of an alkali will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (4) favorably. Specifically, it is preferable to add the alkali in an amount of 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the phthalocyanine compound (4).

  In view of reaction efficiency, the hydrolysis is preferably performed in a solvent. The solvent that can be used in this case is not particularly limited as long as it is a solvent capable of dissolving an alkali. Specifically, water; alcohols such as methanol, ethanol, propanol, and isopropanol; dimethyl sulfoxide, pyridine, N, N-dimethyl. Examples include aprotic polar solvents such as formamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, sulfolane; and acetone, acetonitrile, benzonitrile, and the like. Of these, water, ethanol, dimethyl sulfoxide, and N, N-dimethylformamide are preferably used. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  The usage-amount of the said solvent will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (4) favorably. Specifically, the amount is preferably such that the concentration of the phthalocyanine compound (4) in the solvent is 5 to 40% by mass, more preferably 10 to 25% by mass.

  In the above method, the hydrolysis conditions are not particularly limited as long as the phthalocyanine compound (4) can be hydrolyzed satisfactorily, but preferably can be appropriately selected according to the hydrolysis rate. Specifically, the mixture of the phthalocyanine compound (4), the alkali, and the solvent is preferably at a temperature of 30 to 100 ° C., more preferably 40 to 80 ° C., preferably 1 to 10 hours, more preferably 2 to 6 Let react for hours. At this time, the mixture is preferably reacted with stirring so that hydrolysis can proceed more easily.

  In this way, the phthalocyanine compound (4) is hydrolyzed, but after the hydrolysis reaction is completed, an acid is added to acidify and the hydrolyzate of the phthalocyanine compound (4) is precipitated as crystals. Is preferred. The acid that can be used in this case is not particularly limited as long as the hydrolysis reaction solution can be appropriately acidified to crystallize the hydrolyzate of the phthalocyanine compound (4). Specific examples include concentrated hydrochloric acid, hydrochloric acid, concentrated sulfuric acid, sulfuric acid, concentrated nitric acid, nitric acid, and acetic acid. Of these, concentrated hydrochloric acid, hydrochloric acid, and acetic acid are preferred. Further, the amount of acid added is not particularly limited as long as it is an amount capable of satisfactorily crystallizing the hydrolyzate of the phthalocyanine compound (4). Specifically, the acid is added in such an amount that the pH of the hydrolysis reaction solution is preferably 5 to 1, more preferably 3 to 1.

  The hydrolyzate of the phthalocyanine compound (4) thus precipitated as crystals can be separated by a known method such as filtration, suction filtration, and pressure filtration. Moreover, after separating in this way, it is preferable to stir and wash the hydrolyzate of the phthalocyanine compound (4) with an appropriate washing solvent. In this way, a highly pure phthalocyanine compound (4) is obtained. Here, the washing solvent is not particularly limited as long as impurities can be appropriately separated from the liquid containing the hydrolyzate of the phthalocyanine compound (4). Specific examples include water; alcohols such as methanol, ethanol, propanol, and isopropanol; acetonitrile. Of these, water, methanol, and acetonitrile are preferably used. In addition, the said washing | cleaning solvent may be used independently or may be used with the form of 2 or more types of mixtures.

Accordingly, preferred examples of the phthalocyanine compound (4) of the present invention include the following compounds. The following formula representing the phthalocyanine compound (i) represents that 4 fluorine atoms and 4 —COOR ⁶ -containing phenoxy groups are bonded to 8 β-positions of the phthalocyanine nucleus. The bonding position of the group is arbitrary. The same applies to other examples of phthalocyanine compounds.

  Among the above compounds, the phthalocyanine compounds (i), (ii), (vi), (vii), (viii), (ix), (x), (xi), (xii), (xiii), (xiv) , (Xvi), (xviii) are preferred in the present invention, and phthalocyanine compounds (i), (ii), (vii), (viii), (ix), (xviii) are particularly preferred in the present invention.

  Next, a preferred embodiment in the fifth aspect of the present invention will be described below.

In the above formula (5), Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ which are substituents at the β-position of the phthalocyanine nucleus represent a hydrogen atom or a halogen atom. . At this time, Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ may be the same or different. The halogen atom at the β-position of the phthalocyanine nucleus is not particularly limited, and any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be selected. Preferably, Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ are a hydrogen atom, a fluorine atom or a chlorine atom, and particularly preferably a hydrogen atom or a fluorine atom. Most preferably, the β-position substituents Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ are all hydrogen atoms or fluorine atoms.

In the above formula (5), Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y _13, and Y _{16 which} are α-position substituents of the phthalocyanine nucleus are a hydrogen atom or a halogen atom. Or the following formula:

-COOR ^9- containing phenoxy group represented by (also referred to herein simply as “—COOR ^9- containing phenoxy group”). At this time, Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y ₁₃ and Y ₁₆ may be the same or different. Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y ₁₃ and Y _{16 each} represents 4 halogen atoms and the remaining 4 represent a —COOR ⁹ containing phenoxy group, or 4 are hydrogen atoms and the remaining 4 represent a —COOR ⁹ containing phenoxy group. That is, the α-position of the phthalocyanine nucleus is occupied by four hydrogen atoms or halogen atoms and four —COOR ^9- containing phenoxy groups. In this case, the position where the four hydrogen atoms or halogen atoms and the four —COOR ⁹ -containing phenoxy groups occupy the α-position of the phthalocyanine nucleus is arbitrary and is not particularly limited. For example, when _two hydrogen atoms or halogen atoms and one —COOR ^9- containing phenoxy group are bonded to two residues of the benzene ring (for example, Y ₂ and Y ₃ ); , Y ₂ and Y ₃ ) when _two —COOR ^9- containing phenoxy groups are bonded; and when two halogen atoms are bonded to two remaining positions of the benzene ring (for example, Y ₁ and Y ₄ ). However, preferably, one hydrogen atom or halogen atom and one —COOR ^9- containing phenoxy group are bonded to two remaining positions (for example, Y ₂ and Y ₃ ) of each benzene ring. In any of the above cases, the α-position of the phthalocyanine nucleus is occupied by a total of 4 hydrogen atoms or halogen atoms and a total of 4 —COOR ^9- containing phenoxy groups.

In the above formula showing a —COOR ^9- containing phenoxy group, R ⁹ represents an alkyl group having 1 to 20, preferably 1 to 8, more preferably 1 to 5 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, isoamyl group, 1,4-dimethylpentyl Group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, Linear and branched alkyl such as 1-t-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group And the like. Of these, an isoamyl group, a methyl group, and an ethyl group are preferable. The —COOR ^9- containing phenoxy group has a structure in which one —COOR ⁹ group is bonded to the phenoxy group, but the bonding position of the —COOR ⁹ group to the benzene ring is not particularly limited, Any of the 3rd and 4th positions may be used, but the 2nd and 3rd positions are preferred in consideration of solubility.

  In the above formula (5), M represents a metal-free, metal, metal oxide or metal halide. Here, metal-free means an atom other than a metal, for example, two hydrogen atoms. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin (II) chloride, tin (IV) chloride, and silicon chloride. Preferably, it is a metal, metal oxide or metal halide, specifically, copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, tin (II) chloride, more preferably copper, Vanadyl and zinc. In particular, when the phthalocyanine compound (5) is used in a flat panel display, particularly a filter for PDP, it must be stable against heat generated from the PDP panel, so that it has excellent heat resistance, and the PDP panel. Since the case added to the adhesion layer at the time of sticking to PDP front filter glass can be considered, durability is required. For this reason, in the said use, it is preferable that a center metal is copper. Further, when used in a filter of a liquid crystal display, heat from the panel is not generated as much as PDP, and therefore, higher optical properties (transparency) are required rather than heat resistance. Therefore, for the above-mentioned use, phthalocyanine whose central metal having excellent optical properties (transparency) is zinc is preferable. Further, compatibility with the resin and coating require solubility in a solvent. From the viewpoint of solubility, the central metal is preferably vanadyl. Also, phthalocyanine whose central metal is vanadyl is excellent in durability.

The fifth aspect of the present invention includes a hydrolyzate of the phthalocyanine compound (5) in addition to the phthalocyanine compound (5). Here, the “hydrolyzate of the phthalocyanine compound (5)” means that the ester moiety (—COOR ⁹ in the formula (5)) in the phthalocyanine compound (5) is converted into a carboxyl group (—COOH) by hydrolysis. Means that.

In the present invention, the proportion of the ester moiety in the phthalocyanine compound (5) (—COOR ⁹ in the formula (5)) converted to a carboxyl group (—COOH) by hydrolysis (hereinafter, also simply referred to as “hydrolysis rate”). ) Is preferably 3 to 80%, more preferably 5 to 50%, and particularly preferably 10 to 30%. Thus, it is preferable to convert the ester moiety to a carboxyl group because solubility in a lower alcohol such as methanol or ethanol or a hydrophilic solvent such as an aqueous solution thereof can be improved and the extinction coefficient can be improved. Moreover, by using a hydrolyzate, the compatibility with a resin having a hydroxyl group such as a butyral resin can also be improved, and the range of resins that can be used as a matrix is expanded. In the above, the hydrolysis rate is the ratio of the ester moiety (—COOR ⁹ in formula (5)) present in the phthalocyanine compound (5) before hydrolysis converted to a carboxyl group (—COOH) by hydrolysis. Means. More specifically, the hydrolysis rate is a carboxyl converted by hydrolysis with respect to the number (A) of ester moieties (—COOR ⁹ in formula (5)) present in the phthalocyanine compound (5) before hydrolysis. It is a value [(B / A) × 100 (%)] in which the ratio of the number (B) of the group (—COOH) is expressed as a percentage.

In the present invention, the hydrolysis method is not particularly limited, and a known ester portion hydrolysis method can be applied similarly or appropriately modified. Usually, a method of hydrolyzing the phthalocyanine compound (5) under alkaline conditions can be used. In the above method, the number of —COOR ⁹ -containing phenoxy groups present in the phthalocyanine compound (5) is not particularly limited, but preferably the —COOR ⁹ -containing phenoxy group is 1 in one phthalocyanine compound (5). There are ˜8, more preferably 4-8, and it is most preferred that 4 or all (8) of the β-position substituents are —COOR ⁹ -containing phenoxy groups. If it is such a range, since the obtained phthalocyanine compound has a high extinction coefficient and is excellent in compatibility with a resin having a hydroxyl group such as a butyral resin, the range of resins that can be used as a matrix is expanded.

  In the above method, the alkali is not particularly limited as long as it can favorably hydrolyze the phthalocyanine compound (5). Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide and the like. Of these, sodium hydroxide and potassium hydroxide are preferred. Moreover, the addition amount of an alkali will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (5) favorably. Specifically, it is preferable to add the alkali in an amount of 0.1 to 30% by mass, more preferably 1 to 20% by mass with respect to the phthalocyanine compound (5).

  In view of reaction efficiency, the hydrolysis is preferably performed in a solvent. The solvent that can be used in this case is not particularly limited as long as it is a solvent capable of dissolving an alkali. Specifically, water; alcohols such as methanol, ethanol, propanol, and isopropanol; dimethyl sulfoxide, pyridine, N, N-dimethyl. Examples include aprotic polar solvents such as formamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, sulfolane; and acetone, acetonitrile, benzonitrile, and the like. Of these, water, ethanol, dimethyl sulfoxide, and N, N-dimethylformamide are preferably used. In addition, the said solvent may be used independently or may be used with the form of a 2 or more types of mixture.

  The usage-amount of the said solvent will not be restrict | limited especially if it is the quantity which can hydrolyze a phthalocyanine compound (5) favorably. Specifically, such an amount that the concentration of the phthalocyanine compound (5) in the solvent is 5 to 40% by mass, more preferably 10 to 25% by mass is preferable.

  In the above method, the hydrolysis conditions are not particularly limited as long as the phthalocyanine compound (5) can be hydrolyzed satisfactorily, but can be appropriately selected according to the hydrolysis rate. Specifically, the mixture of the phthalocyanine compound (5), the alkali, and the solvent is preferably at a temperature of 30 to 100 ° C., more preferably 40 to 80 ° C., preferably 1 to 10 hours, more preferably 2 to 6 Let react for hours. At this time, the mixture is preferably reacted with stirring so that hydrolysis can proceed more easily.

  In this way, the phthalocyanine compound (5) is hydrolyzed, but after the hydrolysis reaction is completed, an acid is added to acidify and the hydrolyzate of the phthalocyanine compound (5) is precipitated as crystals. Is preferred. The acid that can be used in this case is not particularly limited as long as it can acidify the hydrolysis reaction solution as appropriate to crystallize the hydrolyzate of the phthalocyanine compound (5). Specific examples include concentrated hydrochloric acid, hydrochloric acid, concentrated sulfuric acid, sulfuric acid, concentrated nitric acid, nitric acid, and acetic acid. Of these, concentrated hydrochloric acid, hydrochloric acid, and acetic acid are preferred. Further, the amount of acid added is not particularly limited as long as it is an amount capable of satisfactorily crystallizing the hydrolyzate of the phthalocyanine compound (5). Specifically, the acid is added in such an amount that the pH of the hydrolysis reaction solution is preferably 5 to 1, more preferably 3 to 1.

  The hydrolyzate of the phthalocyanine compound (5) thus precipitated as crystals can be separated by a known method such as filtration, suction filtration, and pressure filtration. Moreover, after separating in this way, it is preferable to stir and wash the hydrolyzate of the phthalocyanine compound (5) with an appropriate washing solvent. Here, the washing solvent is not particularly limited as long as impurities can be appropriately separated from the liquid containing the hydrolyzate of the phthalocyanine compound (5). Specific examples include water; alcohols such as methanol, ethanol, propanol, and isopropanol; acetonitrile. Of these, water, methanol, and acetonitrile are preferably used. In addition, the said washing | cleaning solvent may be used independently or may be used with the form of 2 or more types of mixtures.

Accordingly, preferred examples of the phthalocyanine compound (5) of the present invention include the following compounds. In addition, the formula showing the following phthalocyanine compound (I) is that four hydrogen atoms (that is, unsubstituted state) and four —COOR ^9- containing phenoxy groups are bonded to eight α positions of the phthalocyanine nucleus. And the bonding position of each substituent is arbitrary. The same applies to other examples of phthalocyanine compounds.

Phthalocyanine compounds (I)
3 or 6-tetrakis (2-isoamyloxycarbonylphenoxy) oxyvanadium phthalocyanine (hereinafter also referred to as VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₄ H ₄ )
(Λmax: 652.5 nm; 15.9 times); and phthalocyanine compound (II)
25% hydrolyzate of 3 or 6-tetrakis (2-isoamyloxycarbonylphenoxy) oxyvanadium phthalocyanine (hereinafter referred to as VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₃ (2-HOOCChO) H ₄ )
(Λmax: 653.5 nm; 16.4 times).

The production method of the phthalocyanine compounds (1) to (5) of the present invention is not particularly limited, and a conventionally known method can be appropriately used. Preferably, the phthalocyanine compounds (1) to (5) are preferably used in a molten state or in an organic solvent. A method of cyclizing a nitrile compound and a metal salt is particularly preferably used. Hereinafter, taking the phthalocyanine compound (1) of the present invention as an example, a particularly preferred embodiment of the production method will be described. However, the present invention is not limited to the following preferred embodiments.

  That is, the following formula (I):

A phthalonitrile compound (1) represented by the following formula (II):

A phthalonitrile compound (2) represented by the following formula (III):

A phthalonitrile compound (3) represented by formula (IV):

And a phthalonitrile compound (4) represented by formula (1) selected from the group consisting of metal oxides, metal carbonyls, metal halides, and organic acid metals (also collectively referred to as “metal salts” in the present specification) By carrying out the cyclization reaction, the phthalocyanine compound of the present invention can be produced.

In the above formulas (I) to (IV), Z _{1 to} Z ₁₆ are defined by the structures of the desired phthalocyanine compounds (1) to (5). Specifically, in the above formula _{(I) ~ (IV),} Z 1 ~Z 16 , respectively, _{Z 1} of _Z 1 _{to Z 16} in the formula (1), the formula (2) 'to Z ₁₆ ′, Z ₁ ″ to Z ₁₆ ″ in the above formula (3), Z ₁ ″ ′ to Z ₁₆ ″ ′ in the above formula (4), and Y ₁ to Y _{16 in} the above formula (5). Therefore, the description is omitted here.

  In the above embodiment, the starting phthalonitrile compounds of formulas (I) to (IV) can be synthesized by a conventionally known method such as the method disclosed in JP-A No. 64-45474, or commercially available. Can be used, but preferably, the following formula (V):

In the formula, X ₁ , X ₂ , X ₃ and X ₄ are each independently a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom and a chlorine atom, particularly preferably a fluorine atom. Represents
Is obtained by reacting with a HOX. Specifically, the substituent “X” in the above formula is a 2-methylphenoxy group in the above formula (1), a —COOR ¹ OR ² containing phenoxy group in the above formula (2), or the above formula (3). Among them, it corresponds to a 2,6-substituted phenoxy group, —COOR ⁶ containing phenoxy group in the above formula (4), and —COOR ⁹ containing phenoxy group in the above formula (5). The ratio of HOX is appropriately selected depending on the structure of the target phthalonitrile compound. The amount of HOX used is not particularly limited as long as these reactions can proceed to produce a desired phthalonitrile compound. For example, in the phthalocyanine compound (A), 2-methylphenol is a phthalonitrile derivative. It is usually used in an amount of 0.5 to 5 mol, preferably 0.8 to 3 mol, relative to 1 mol. It is defined by the structure of the desired phthalocyanine compounds (1) to (5).

  In the above preferred embodiment, the reaction between the phthalonitrile derivative and HOX may be performed in the absence of a solvent or in an organic solvent, but is preferably performed in an organic solvent. Examples of the organic solvent that can be used in this case include nitriles such as acetonitrile and benzonitrile; polar solvents such as acetone and 2-butanone. Of these, acetonitrile, benzonitrile and acetone are preferred. The amount of the organic solvent used when the solvent is used is such an amount that the concentration of the phthalonitrile derivative is usually 2 to 40 (w / v)%, preferably 10 to 30 (w / v)%. . In the reaction of this phthalonitrile derivative and HOX, it is preferable to use these trapping agents in order to remove hydrogen halide (for example, hydrogen fluoride) generated during the reaction. Specific examples of the trapping agent when using the trapping agent include calcium carbonate, calcium hydroxide, magnesium hydroxide, magnesium chloride and magnesium carbonate. Among these, calcium carbonate and calcium hydroxide are preferable. . The amount of the trapping agent used when using the trapping agent is not particularly limited as long as it is an amount capable of efficiently removing hydrogen halide and the like generated during the reaction, but is usually 1 with respect to 1 mol of the phthalonitrile derivative. It is 0.0-4.0 mol, Preferably it is 1.1-2.0 mol.

  Alternatively, the phthalonitrile compounds of the formulas (I) to (IV) as starting materials are converted into the following formula (VI):

The nitrophthalonitrile compound (hereinafter, also simply referred to as “nitrophthalonitrile compound”) may be obtained by reacting with HOX. Specifically, the substituent “X” in the above formula is a 2-methylphenoxy group in the above formula (1), a —COOR ¹ OR ² containing phenoxy group in the above formula (2), or the above formula (3). Among them, it corresponds to a 2,6-substituted phenoxy group, —COOR ⁶ containing phenoxy group in the above formula (4), and —COOR ⁹ containing phenoxy group in the above formula (5). Thus, when the nitrophthalonitrile compound of the formula (VI) is reacted with HOX, the nitro group (—NO ₂ ) and HOX in the nitrophthalonitrile compound react preferentially, and the nitro group (—NO ₂ ) may be selectively substituted with -X. Therefore, according to the method, by selecting a nitro group in the nitrophthalonitrile compound, a 2-methylphenoxy group in the above formula (1), a -COOR ¹ OR ² containing phenoxy group in the above formula (2) 2,6-substituted phenoxy group in the above formula (3), -COOR ⁶ containing phenoxy group in the above formula (4), and -COOR ⁹ containing phenoxy group in the above formula (5) to the phthalonitrile compound. The introduction position can be easily defined.

  The ratio of HOX is appropriately selected depending on the structure of the target phthalonitrile compound. The amount of HOX used is not particularly limited as long as these reactions can proceed to produce the desired phthalonitrile compound. For example, in the phthalocyanine compound (A), 2-methylphenol is represented by the formula (VI ) Is usually used in an amount of 0.5 to 5 mol, preferably 0.8 to 3 mol, per 1 mol of the nitrophthalonitrile compound. It is defined by the structure of the desired phthalocyanine compounds (1) to (5).

  Further, in the above formula (VI), the binding position of the nitro group to phthalonitrile is appropriately selected depending on the structure of the target phthalonitrile compound, and may be either the 3rd or 4th position. Considering this, the fourth position is preferable.

In the above method, the reaction between the nitrophthalonitrile compound and HOX may be carried out in the absence of a solvent or in an organic solvent, but is preferably carried out in an organic solvent. Examples of organic solvents that can be used include amides such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone. And nitriles such as acetonitrile and benzonitrile. Of these, dimethylformamide, acetonitrile, and benzonitrile are preferable. The amount of the organic solvent used when using the solvent is such an amount that the concentration of the nitrophthalonitrile compound is usually 10 to 80 (w / v)%, preferably 20 to 50 (w / v)%. is there. In addition, the reaction of this nitrophthalonitrile compound and HOX is performed using 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), potassium fluoride (KF), potassium carbonate (K ₂ CO ₃ ), and the like. It is preferable to be carried out in the presence of the catalyst. At this time, the amount of the catalyst used is not particularly limited as long as the above reaction proceeds satisfactorily. Specifically, the catalyst is usually usually added in an amount of 1.0 to 4.0 mol, more preferably 1.1 to 2.0 mol, per 1 mol of the nitrophthalonitrile compound.

  Moreover, the reaction conditions of the said nitrophthalonitrile compound and HOX will not be restrict | limited especially if the said reaction advances favorably. Specifically, the nitrophthalonitrile compound and HOX are preferably reacted at a temperature of 30 to 150 ° C., more preferably 40 to 100 ° C., preferably 2 to 12 hours, more preferably 3 to 8 hours.

  In the above embodiment, the cyclization reaction is carried out by melting one kind selected from the group consisting of the phthalonitrile compounds of formulas (I) to (IV) and a metal, a metal oxide, a metal carbonyl, a metal halide, and an organic acid metal in a molten state or organic. It is preferable to react in a solvent. Examples of the metal, metal oxide, metal carbonyl, metal halide, and organic acid metal (hereinafter collectively referred to as “metal compound”) that can be used at this time include the phthalocyanine compound (1) of the formula (1) obtained after the reaction. If it can obtain what corresponds to M, there is no particular limitation. For example, iron, copper, zinc, vanadium, titanium, indium and tin enumerated in the section of M in the above formula (1) Metals such as chlorides, bromides and iodides, metal oxides such as vanadium oxide, titanyl oxide and copper oxide, organic acid metals such as acetates, and complexes such as acetylacetonate Examples include compounds and metal carbonyls such as carbonyl iron. Of these, metals, metal oxides and metal halides are preferred.

  In the above embodiment, the cyclization reaction can be carried out in the absence of a solvent, but is preferably carried out using an organic solvent. The organic solvent may be any inert solvent that has a low reactivity with the phthalonitrile compound as a starting material, and preferably does not exhibit any reactivity. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dioxybenzene, Inert solvents such as chlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol, and benzonitrile; and pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethyl Examples include aprotic polar solvents such as acetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide, and sulfolane. Of these, 1-chloronaphthalene, 1-methylnaphthalene and benzonitrile are preferably used, and benzonitrile is more preferably used.

  The reaction conditions for the phthalonitrile compound of formulas (I) to (IV) and the metal compound in the above embodiment are not particularly limited as long as the reaction proceeds, but for example, 100 parts by weight of organic solvent. On the other hand, the phthalonitrile compounds (1) to (4) are added in a total amount in the range of 2 to 40 parts by weight, preferably 20 to 35 parts by weight, and the metal compound is added in an amount of 1 to 4 moles of the phthalonitrile compound. It is charged in a range of 2 mol, preferably 1.1 to 1.5 mol, and reacted at a reaction temperature of 30 to 250 ° C., preferably 80 to 200 ° C. After the reaction, a phthalocyanine derivative that can be used in the next step can be efficiently and highly purified by filtration, washing, and drying according to a conventionally known method for synthesizing phthalocyanine compounds.

  In the reaction of the phthalonitrile compound of the above formulas (I) to (IV) with the metal compound, 2 of the phthalocyanine compound (1) is used as the phthalocyanine compound (A) particularly preferable as the phthalocyanine compound (1) of the present invention. In the case of producing a phthalocyanine compound in the form of a mixture of more than one species, a mixture of a plurality of phthalonitrile compounds as raw materials is used, and the phthalocyanine compound is cyclized and reacted with such a phthalocyanine compound. Compounds can be produced. As an example, a method for producing the phthalocyanine compound (A) according to the present invention will be described. That is, the phthalonitrile compound (X) represented by the following formula and the phthalonitrile compound (Y) represented by the following formula are converted into a molar ratio of 4: 6 [molar ratio of phthalonitrile compound (X): phthalonitrile compound (Y). In the same manner as described above, one selected from the group consisting of metal, metal oxide, metal carbonyl, metal halide and organic acid metal is reacted in a molten state or in an organic solvent. .

  Since the phthalocyanine compound having a specific structure as described above exhibits a maximum absorption wavelength in a specific wavelength region of 640 to 750 nm, it is possible to selectively cut light in these regions. For this reason, when the phthalocyanine compound of the present invention is used in a filter for a flat panel display and a liquid crystal display, for example, it prevents a malfunction of an optical communication system corresponding to a flow of an increase in the amount of information, and at the same time, is clear. Red can be reproduced. In addition, the phthalocyanine compound having a specific structure as described above efficiently cuts light having a wavelength of 640 to 700 nm, which is not necessarily a light of a preferable color tone in the field of flat panel displays and liquid crystal displays that emit strong red light. Therefore, even if it is used for a filter for a flat panel display or a liquid crystal display, a pure red color can be reproduced. In addition, the phthalocyanine compound of the present invention is excellent in compatibility with the resin and excellent in properties such as heat resistance, light resistance, and weather resistance.

  As described above, conventionally, a compound that exhibits a maximum absorption wavelength in a specific wavelength range of 640 to 750 nm is used as a flat panel display or liquid crystal for the purpose of preventing malfunction of an optical communication system corresponding to a flow of increasing information content. There was no example used for a display filter. In the present invention, in consideration of the tendency of the increase in the amount of information, in view of the problem of malfunction of the optical communication system that can cope with such a large amount of information in the future, the maximum absorption in a specific wavelength region of 640 to 750 nm It was thought that the malfunction of the optical communication system corresponding to the flow of an increase in information can be significantly suppressed / prevented by using a compound exhibiting a wavelength for such a flat panel display and liquid crystal display filter.

  Accordingly, the sixth aspect of the present invention is a light having a wavelength of 640 to 750 nm, which contains a dye having a maximum absorption wavelength at least at 640 to 750 nm and having an absorbance at the maximum absorption wavelength of 10 times or more of the absorbance at 460 nm. The present invention relates to a flat panel display filter for cutting. The seventh aspect of the present invention has a wavelength of 640 to 750 nm, which contains a phthalocyanine dye having a maximum absorption wavelength of at least 640 to 750 nm and an absorbance at the maximum absorption wavelength of 10 times or more of the absorbance of 460 nm. The present invention relates to a filter for flat panel display for light cut.

  In the sixth and seventh aspects of the present invention, it is essential that the dye / phthalocyanine dye has a maximum absorption wavelength of at least 640 to 750 nm, and the absorbance at the maximum absorption wavelength is at least 10 times the absorbance at 460 nm. It is. Here, the light with a wavelength of 460 nm is blue (B) light. The blue light has a lower light emission rate than other red (R) light and green (G) light, particularly in the PDP. For this reason, particularly in the field of PDP, even if the transmittance for other red (R) light and green (G) light is slightly lowered, it is preferable to have a high transmittance for blue (B) light. In the present invention, in consideration of such points, the dye / phthalocyanine dye has “a maximum absorption wavelength of at least 640 to 750 nm and an absorbance at the maximum absorption wavelength of 10 times or more of the absorbance at 460 nm”. Thus, light having a wavelength of 640 to 750 nm, which has a low absorbance at 460 nm (that is, a high transmittance of blue light) and is preferably cut, can be efficiently absorbed. Identify a pigment. Such a dye / phthalocyanine dye, for example, as a filter for a flat panel display and a liquid crystal display in order to prevent malfunction of an optical communication system corresponding to the increase in information amount and to reproduce a clear red color at the same time. Useful. In particular, in the above embodiment, since the dye / phthalocyanine dye selectively cuts the color tone called crimson in the wavelength range of 640 to 700 nm, a filter containing such a dye / phthalocyanine dye is a PDP that emits particularly strong red light. A pure red color can be reproduced. For this reason, the sixth and seventh flat panel display filters of the present invention are particularly preferably plasma display filters. Further, as described above, the sixth and seventh flat panel display filters of the present invention are used in combination with an optical communication system that emits light with a wavelength of 640 to 750 nm, which has a particularly large amount of information. It is preferable. Even when used in combination with such a large-capacity optical communication system, the filter of the present invention highly absorbs light having a wavelength of 640 to 750 nm. Therefore, transmission optical communication from such an optical communication system. Malfunction can be suppressed / prevented.

  In the sixth and seventh aspects of the present invention, it is essential that the dye / phthalocyanine dye has an absorbance at the maximum absorption wavelength that is at least 10 times the absorbance at 460 nm. Within such a range, light having a wavelength of 640 to 750 nm to be cut can be efficiently transmitted while sufficiently absorbing blue light having a wavelength of 460 nm. In the present invention, the dye / phthalocyanine dye preferably has an absorbance at the maximum absorption wavelength in the order of 13 times or more, 15 times or more, 20 times or more, 30 times or more, 40 times or more, 50 times or more of the absorbance at 460 nm. The upper limit of the absorbance magnification at the maximum absorption wavelength with respect to the absorbance at 460 nm is preferably as low as possible for blue light at 460 nm and as high as possible for light at a wavelength of 640 to 750 nm. Although not particularly limited, it is usually preferably 10,000 times, more preferably 1000 times.

  The dye that can be used in the sixth aspect of the present invention is not particularly limited as long as it has a maximum absorption wavelength of at least 640 to 750 nm and the absorbance at the maximum absorption wavelength is 30 times or more the absorbance at 460 nm. Specifically, 1-ethyl-2- [3-chloro-5- (1-ethyl-2 (1H) -quinolinylidene) -1,3-pentadienyl] quinolium bromide (106 times as shown by the following formula) Λmax: 694.4 nm), 1,3,3-trimethyl-2- [5- (1,3,3-trimethyl-2 (1H) -benz [e] indolinylidene) -1,3-pentadienyl] -3H-benz [e] indolinium perchlorate (119 times; λmax: 675.6 nm), 3-ethyl-2- [5- (3-ethyl-2-benzothiazolinylidene) -1,3-pentadienyl And cyanine dyes such as benzothiazolium iodide (475 times; λmax: 651.6 nm). In the above, the magnification in parentheses is the magnification of absorbance at the maximum absorption wavelength with respect to the absorbance at 460 nm, and the maximum absorption wavelength (λmax) is shown in parentheses.

  In addition to the above, as shown in the sixth and seventh aspects of the present invention, the phthalocyanine dye that can be used particularly when the dye is a phthalocyanine dye has a maximum absorption wavelength of at least 640 to 750 nm and a maximum absorption wavelength. As long as the absorbance at is at least 30 times the absorbance at 460 nm, there is no particular limitation. Specific examples include the phthalocyanine compounds disclosed in the first aspect of the present invention.

The filter of the present invention must contain a dye having a maximum absorption wavelength of at least 640 to 750 nm and an absorbance at the maximum absorption wavelength of 30 times or more of the absorbance at 460 nm. A dye having a maximum absorption wavelength may further be included. Other dyes that can be used in such a case are appropriately selected according to the maximum absorption wavelength desired depending on the application. For example, a near-infrared absorbing dye of 800 to 1000 nm or an orange neon light of 570 to 600 nm is used. Examples include absorbing dyes. Among these, examples of the near infrared absorbing dye having a wavelength of 800 to 1000 nm include cyanine dyes, phthalocyanine dyes, nickel complex dyes, and diimonium dyes. Among these, phthalocyanine dyes include phthalocyanine dyes described in JP-A No. 2001-106869, particularly phthalocyanine [CuPc (2,5-Cl ₂₎ produced in Example 8 of JP-A No. 2001-106869. PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), phthalocyanine [VOPc (2,5-Cl ₂ PhO) produced in Example 7 of the publication ) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 870 nm), phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 912 nm); a film described in JP-A No. 2004-18561 Talocyanine dyes, especially phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ O (CH ₂ ), produced in Example 8 of JP-A-2004-18561 ₃ NH} ₄ ] (λmax: 928 nm), phthalocyanine [VOPc (4- (CH ₃ O) PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH produced in Example 17 of the publication ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λmax: 962 nm);

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F}] (λmax: 916 nm), represented by the following formula:

A phthalocyanine compound [hereinafter also referred to as {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ }] (λmax: 963 nm) or the like is preferably used. In this case, in consideration of durability and weather resistance, it is particularly preferable that the central metal of the phthalocyanine skeleton of the phthalocyanine dye having a wavelength of 800 to 1000 nm is copper. Moreover, the phthalocyanine compound described in the Example of Unexamined-Japanese-Patent No. 10-78509 can also be used. Examples of the diimonium dye include (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) hexafluoroantimonate, N, N, N ′, N′— Tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (bis (trifluoromethanesulfonyl) imidic acid) imonium salt (trade name: CIR-1085, manufactured by Nippon Cartridge Co., Ltd.), N, N, N ′, N '-Tetrakis (p-dibutylaminophenyl) -p-phenylenediamine-bis (hexafluoroantimonic acid) imonium salt (trade name: CIR-1081, manufactured by Nippon Cartridge Co., Ltd.), diimonium cation and bis (trifluoromethanesulfone) Diimonium dye consisting of imide anion (trade name: C, manufactured by Nippon Cartridge Co., Ltd.) R-RL) and the like are preferably used, and as the nickel complex dye, Bis (1,2-diphenylene-1,2-dithiol) nickel is preferably used. Cyanine dyes can be used, and the stabilized cyanine dye is a salt compound composed of a cyanine cation and a quencher anion, among which, for example, cation No. 1 shown below is used. No. 2 and the like, and as the quencher anion, for example, the following compounds of anions No. 11 and No. 22 can be preferably used, and a salt compound appropriately combining these is used as a stabilized cyanine dye. Preferably used.

  Examples of dyes that absorb orange neon light of 570 to 600 nm include tetraazaporphyrin dyes, cyanine dyes, squarylium dyes, anthraquinone dyes, subphthalocyanine dyes, phthalocyanine dyes, polymethyl dyes, polyazo dyes. System dyes and the like. Among these, tetra-t-butyl-tetraazaporphyrin / copper complex, tetra-t-butyl-tetraazaporphyrin / vanadium complex and the like are preferably used as the tetraazaporphyrin-based dye. Further, as the cyanine dye and squarylium dye, cyanine dyes and squarylium dyes described in JP-A No. 2002-189422 are preferably used. As the subphthalocyanine dye, a subphthalocyanine dye described in JP-A No. 2006-124593 is preferably used. In view of durability and weather resistance, it is particularly preferable that the central metal of the phthalocyanine skeleton of the 570-600 nm phthalocyanine dye is copper. In addition, the said other pigment | dye may be used independently or may be used with the form of 2 or more types of mixtures.

  A dye / phthalocyanine dye (hereinafter, also simply referred to as “dye / phthalocyanine dye”) that can be used in the sixth and seventh flat panel display filters of the present invention is contained in the substrate. The term “containing in the base material” means not only that it is contained in the base material, but also a state where it is applied to the surface of the base material, a state where it is sandwiched between the base material and the like. Examples of the substrate include a transparent resin plate, a transparent film, and transparent glass. A method for producing the flat panel display filter of the present invention using the phthalocyanine compound is not particularly limited, and for example, the following three methods can be used.

  That is, (1) A method of kneading a dye / phthalocyanine dye into a resin and thermoforming it to produce a resin plate or film; (2) A paint (liquid or pasty material) containing the dye / phthalocyanine dye; (4) A method of coating a transparent resin plate, a transparent film or a transparent glass plate; (3) A method of producing a laminated resin plate, a laminated resin film, a laminated glass or the like by containing a dye / phthalocyanine dye in an adhesive; and (4 ) Dye / phthalocyanine dye is contained in an adhesive, and this is applied to a film subjected to an antireflection treatment and attached to a PDP panel or PDP front filter glass.

  First, in the method of (1) in which a dye / phthalocyanine dye is kneaded and heat-molded in a resin, the resin material is preferably as transparent as possible when it is made into a resin plate or resin film. Polyethylene, polystyrene, polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl compounds, and addition polymers of these vinyl compounds, polymethacrylic acid, polymethacrylic acid esters , Vinyl compounds such as polyvinylidene chloride, polyvinylidene fluoride, poly (vinylidene fluoride), vinylidene fluoride / trifluoroethylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene cyanide / vinyl acetate copolymer, etc. Compounding Copolymers, fluorine-containing resins such as polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polyamides such as nylon 6 and nylon 66, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonates, Polyether, such as polyoxymethylene, polyethylene oxide, polypropylene oxide, epoxy resin, polyvinyl alcohol, polyvinyl butyral, etc. can be mentioned, but is not limited to these resins, high hardness to be a glass substitute, Highly transparent resin, thermosetting resin such as thiourethane, ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (manufactured by Nippon Zeon Co., Ltd.), OPTPOREZ (manufactured by Hitachi Chemical Co., Ltd.), O It is also preferable to use an optical resin such as PET (Kanebo Ltd.).

  As a method for producing a filter for a flat panel display according to the present invention, the processing temperature, filming conditions and the like differ slightly depending on the base resin to be used. Usually, (a) a dye / phthalocyanine dye is used as a base resin powder or pellet. After adding, heating to 150 to 350 ° C. and dissolving, molding to produce a resin plate, (a) forming a film with an extruder, and (c) producing an original fabric with an extruder, 30 The method of extending | stretching to a 1 axis thru | or 2 axis | shafts at -120 degreeC to 2-5 times, and making it a film of 10-200 micrometers thickness etc. is mentioned. In addition, when kneading, additives used for ordinary resin molding such as an ultraviolet absorber and a plasticizer may be added. The addition amount of the dye / phthalocyanine dye varies depending on the thickness of the resin to be produced, the target absorption intensity, the target visible light transmittance, and the like, but is usually 0.0005 to 20%. Moreover, the resin board and the resin film which used the casting method by block polymerization, such as pigment | dye / phthalocyanine pigment | dye and methyl methacrylate, can also be produced.

  Next, as a method of coating and coating (2), a method of dissolving a dye / phthalocyanine dye in a binder resin and an organic solvent to form a paint, and an acrylic emulsion by atomizing the dye / phthalocyanine dye to a few μm or less There is a method of dispersing in to form a water-based paint. In the former method, usually, aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl resin, polyvinyl alcohol resin, polyvinyl System modified resins (PVB, EVA, etc.) or copolymer resins thereof are used as the binder resin. Furthermore, optical resins such as ARTON (manufactured by Nippon Synthetic Rubber Co., Ltd.), ZEONEX (manufactured by Nippon Zeon Co., Ltd.), OPTPOREZ (manufactured by Hitachi Chemical Co., Ltd.) and O-PET (manufactured by Kanebo Co., Ltd.) can also be used. As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixture thereof can be used.

  The concentration of the dye / phthalocyanine dye varies depending on the thickness of the coating, the target absorption strength, the target visible light transmittance, etc., but is usually 0.01 to 40% by mass, 0.1 to 0.1% with respect to the mass of the binder resin. 30% by mass. Moreover, binder resin density | concentration is 1-50 mass% normally with respect to the whole coating material. Similarly, in the case of an acrylic emulsion water-based paint, it is obtained by dispersing a pigment / phthalocyanine dye finely pulverized in an uncolored acrylic emulsion paint (950 to 500 nm). In the coating material, additives such as ultraviolet absorbers, antioxidants and the like used in ordinary coating materials may be added. The coating material produced by the above method is coated on a transparent resin film, transparent resin plate, transparent glass, etc. with a bar coder, blade coater, spin coater, reverse coater, die coater or spray, etc. A display filter can be produced. A protective layer can be provided to protect the coating surface, or a transparent resin plate, a transparent resin film, or the like can be bonded to the coating surface. A cast film is also included in the method.

  Furthermore, a dye / phthalocyanine dye is contained in an adhesive to produce a laminated resin plate, a laminated resin film, a laminated glass, etc. (3) or a dye / phthalocyanine dye is contained in an adhesive and subjected to an antireflection treatment. In the method (4), which is applied to the applied film and pasted to a PDP panel or PDP front filter glass, as an adhesive, for general silicon-based, urethane-based, acrylic-based resins or laminated glass A known transparent adhesive for laminated glass such as polyvinyl butyral adhesive (PVA) and ethylene-vinyl acetate adhesive (EVA) can be used. Adhesives between transparent resin plates, resin plates and resin films, resin plates and glass, resin films, resin films and glass, and glasses using an adhesive with 0.1 to 30% by mass of pigment / phthalocyanine pigment added Alternatively, a filter is produced by directly attaching (adhering) to a PDP panel or PDP front filter glass using an adhesive to which 0.1 to 30% by mass of a dye / phthalocyanine dye is added. There is also a method of thermocompression bonding. Furthermore, the film or plate produced by the above method can be attached to glass or a resin plate, if necessary. The thickness of the filter varies depending on the specifications of the plasma display to be produced, but is usually about 0.1 to 10 mm. Moreover, in order to raise the light resistance of a filter, the transparent film (UV cut film) containing a UV absorber can also be affixed on the outer side.

  In the present invention, as a malfunction prevention filter for flat panel display, it is installed in front of the display to cut off near-infrared light emitted from the display, and therefore, when the visible light transmittance is low, the sharpness of the image is lowered. The higher the visible light transmittance of the filter, the better. At least 30%, preferably 40% or more is necessary. The near infrared light cut region is 640 to 750 nm, preferably 645 to 730 nm, and the average light transmittance of the region is designed to be 20% or less, preferably 15% or less. Therefore, if necessary, two or more dyes / phthalocyanine dyes may be combined. It is also preferable to add another dye having absorption in the visible region in order to change the color tone of the filter. It is also possible to produce a filter containing only the color tone dye and to bond it later. In particular, when an electromagnetic wave cut layer such as sputtering is provided, the color tone is important because the hue may be greatly different from the original filter color.

In order to make the filter obtained by the above method more practical, an electromagnetic wave cut layer, an antireflection (AR) layer, and a non-glare (AG) layer that block electromagnetic waves emitted from the plasma spray can be provided. Their manufacturing method is not particularly limited. For example, for the electromagnetic wave cut layer, a sputtering method such as a metal oxide can be used. Usually, In ₂ O ₃ (ITO) to which Sn is added is generally used, but the dielectric layer and the metal layer are formed on the substrate. By alternately laminating by sputtering or the like, it is possible to cut light of 1100 nm or more from near infrared rays, far infrared rays to electromagnetic waves. The dielectric layer is a transparent metal oxide such as indium oxide or zinc oxide, and the metal layer is generally silver or a silver-palladium alloy, and usually three layers and five layers starting from the dielectric layer. 7 or 11 layers are laminated. In this case, the heat generated from the display can be cut at the same time, but since the dye / phthalocyanine dye has an excellent heat ray shielding effect, the heat resistance effect can be further improved. As the substrate, a filter containing a dye / phthalocyanine dye may be used as it is, or may be bonded to a filter containing the dye / phthalocyanine dye after sputtering on a resin film or glass. Moreover, when actually performing electromagnetic wave cutting, it is necessary to install an electrode for grounding. In order to suppress the reflection of the surface and improve the transmittance of the filter, the antireflection layer is made of an inorganic substance such as a metal oxide, fluoride, boride, carbide, nitride, sulfide, vacuum deposition method, sputtering method, There are a method of laminating a single layer or a multilayer by an ion plating method, an ion beam assist method, or the like, a method of laminating a resin having a different refractive index, such as an acrylic resin or a fluororesin, in a single layer or a multilayer. Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, if necessary, a non-glare (AG) layer can be provided. The non-glare (AG) layer can be formed by coating fine particles of silica, melamine, acrylic, etc. with ink in order to scatter transmitted light for the purpose of widening the viewing angle of the filter. The ink can be cured by thermal curing or photocuring. Further, a non-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  The configuration of the plasma spray spray filter can be changed as required. Usually, an antireflection layer is provided on a filter containing a near infrared absorbing compound, and if necessary, a non-glare layer is provided on the opposite side of the antireflection layer. In addition, when combining an electromagnetic wave cut layer, a filter containing a near infrared ray absorbing compound is used as a base material, and an electromagnetic wave cut layer is provided thereon, or a filter containing a near infrared ray absorbing compound and a filter having an electromagnetic wave cutting ability are provided. Can be made by pasting together. In that case, an antireflection layer can be further produced on both sides, or if necessary, an antireflection layer can be produced on one side and a non-glare layer can be produced on the opposite side. In addition, when adding a dye having absorption in the visible region for color correction, the method is not limited. The flat panel display filter of the present invention has a high visible light transmittance, so that the sharpness of the display is not impaired, and light near 640 to 750 nm emitted from the display is efficiently cut. The wavelength used by optical communication or the like is not adversely affected, and malfunctions thereof can be prevented.

  Hereinafter, examples and comparative examples will be described. However, the technical scope of the present invention is not limited only to the following examples.

Example 1: Synthesis of phthalocyanine compound (A): ZnPc {(2-methylphenoxy) _5.6 F _10.4 } In a 100 ml three-necked flask, 10 g of 3,4,5,6-tetrafluorophthalonitrile ( 0.05 mol), 4.88 g (0.084 mol) of potassium fluoride and about 30 g of benzonitrile as a solvent are added, and after dissolution, cooled to 0 ° C. with stirring. Thereafter, 7.54 g (0.07 mol) of o-cresol dissolved in about 10 g of benzonitrile was dropped over about 30 minutes while keeping at 0 ° C. Thereafter, the mixture was kept at 0 ° C. for 2 hours, then returned to room temperature, stirred overnight and reacted at room temperature. Then, after moving to a beaker and adding 100 ml of acetonitrile to dissolve the precipitate as much as possible, the KF / HF salt was suction filtered, and acetonitrile was distilled off from the resulting solution.

The obtained solution was again transferred to a 100 ml three-necked flask, 4.39 g (0.0137 mol) of zinc iodide was added, and the mixture was heated to 180 ° C. with stirring under a nitrogen stream. Thereafter, the reaction is carried out at 180 ° C. for about 12 hours, benzonitrile is distilled off, the mixture is poured into a mixed solution of 150 g of methanol and 30 g of water, stirred and washed for 1 hour, suction filtered and vacuum dried at 60 ° C. to obtain a phthalocyanine compound (A ) [ZnPc {(2-methylphenoxy) _5.6 F _10.4 }] about 15.6 g was obtained.

  About the obtained phthalocyanine, the maximum absorption wavelength in an acetone solution was measured using the spectrophotometer (the Shimadzu Corporation make: UV1650PC). Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 1 below.

Example 2: phthalocyanine compound (a): CuPc three-neck flask 50ml of _{{2,6- (CH 3 OC 2 H} 5 OOC) 2 PhO} 4 F 4 F 8, 4- (2,6- Dimethoxyethoxycarbonylphenoxy) -3,5,6-trifluorophthalonitrile 4 g (0.084 mol), copper chloride 0.25 g (0.0025 mol) and about 15 g of benzonitrile as a solvent were added, under a nitrogen stream. The temperature was raised to 175 ° C. with stirring. Thereafter, the reaction is carried out at 175 ° C. for about 4 hours, benzonitrile is distilled off, the mixture is poured into a mixture of 75 g of methanol and 15 g of water, stirred and washed for 1 hour, suction filtered, and vacuum dried at 60 ° C. to obtain a phthalocyanine compound (a _{) [CuPc {2,6- (CH 3} OC 2 H 5 OOC) 2 PhO} 4 F 4 F 8] to obtain about 3.24 g.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 1.

Example 3 Synthesis of Phthalocyanine Compound (A): ZnPc {(2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ F _{4 In} a 50 ml three-necked flask, 4,5 -10 g (0.017 mol) of bis (2,5-dichlorophenoxy) -3-dimethylphenoxy-6-fluorophthalonitrile, 1.49 g (0.047 mol) of zinc iodide and about 20 g of benzonitrile as a solvent The temperature was raised to 165 ° C. with stirring under a nitrogen stream. Thereafter, the reaction was carried out at 165 ° C. for about 16 hours, benzonitrile was distilled off, poured into 100 g of methanol, stirred and washed for 1 hour, suction filtered, vacuum dried at 60 ° C., and phthalocyanine compound (A) [ZnPc {(2, _{5-Cl 2 PhO) 8 {} 2,6- (CH 3) 2 PhO} 4 F 4] to obtain about 8.01 g.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 1.

Example 4: phthalocyanine compound (i): CuPc three-neck flask 50ml of _{(2-H 5 C 2 OOCPhO} ) 4 F 4 F 8, 4- (2- ethoxycarbonyl-phenoxy) -3,5,6 -11.7 g (0.034 mol) of trifluorophthalonitrile, 0.88 g (0.0089 mol) of copper chloride and about 25 g of octanol as a solvent were added, and the temperature was raised to 150 ° C. with stirring under a nitrogen stream. Thereafter, the mixture was reacted at 150 ° C. for about 2 hours, poured into 150 g of methanol, stirred and washed for 1 hour, suction filtered, and vacuum-dried at 60 ° C. to obtain a phthalocyanine compound (i) [CuPc (2-H ₅ C ₂ OOCPhO) ₄ F ₄ F ₈ ] about 9.54 g was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 1.

Example 5: phthalocyanine compound _{(ii): CuPc (4-} H 5 C 2 OOCPhO) 4 3-neck flask 50ml of _F 4 _{F 8,} 4- (4- ethoxycarbonyl-phenoxy) -3,5,6 -11.7 g (0.034 mol) of trifluorophthalonitrile, 0.88 g (0.0089 mol) of copper chloride and about 25 g of octanol as a solvent were added, and the temperature was raised to 150 ° C. with stirring under a nitrogen stream. Then reacted at 0.99 ° C. for about 2 hours, then poured into methanol 150g washed 1 hour stirring, and dried in vacuo at 60 ° C. After suction filtration, the phthalocyanine compound _{(ii) [CuPc (4-} H 5 C 2 OOCPhO) 4 F ₄ F ₈ ] about 10.43 g was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 1.

Example 6
10 parts by mass of a commercially available fluorene-based resin polyester copolymer and 0.024 of the phthalocyanine compound (A) [ZnPc {(2-methylphenoxy) _5.6 F _10.4 }] (λmax: 685 nm) described in Example 1 Part by mass, 0.03 part by mass of subphthalocyanine BClSubPcF12 described in Example 1 of JP-A-2006-124593, and phthalocyanine [CuPc (2,5- 0.1 part by mass of Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), phthalocyanine [VOPc produced in Example 7 of the publication] _{(2,5-Cl 2 PhO) 8} {2,6- (CH 3) 2 PhO} 4 (PhCH 2 NH) 4] (λmax 870 nm) 0.13 parts by weight, the publication Example phthalocyanine prepared in _{9 [VOPc (PhS) 8 {} 2,6- (CH 3) 2 PhO} 4 (PhCH 2 NH) 4] of (.lambda.max: 912 nm ) 0.09 parts by mass, phthalocyanine [VOPc (4- (CH ₃ O) PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ produced in Example 17 of JP-A-2004-18561 A resin coating solution prepared by dissolving and mixing 0.15 parts by mass of {CH ₃ (CH ₂ ) ₃ CH (C ₂ H ₅ ) CH ₂ NH} ₄ ] (λmax: 962 nm) in 89.44 parts by mass of dichloromethane, The film was coated on a commercially available polyethylene terephthalate film (about 50 μm) so that the dry film thickness was 10 μm, dried at room temperature and then dried at 80 ° C., and the near-infrared absorber and orange light were applied. To obtain a transparent coating film to absorb dye and crimson light to yield.

  Next, on the coating layer of this transparent coating film, an ultraviolet absorber (TINUVIN 384 manufactured by Ciba Specialty Chemicals Co., Ltd.): 2.7 parts by mass, an antioxidant (IRGANOX-1010 manufactured by Ciba Specialty Chemicals Co., Ltd.) ): 0.9 parts by mass, acrylic pressure-sensitive adhesive (Aron S-1601, manufactured by Toagosei Co., Ltd.): A mixture obtained by mixing 96.4 parts by mass was applied so that the thickness of the dried coating film was 15 μm. A transparent adhesive layer containing a UV absorber was laminated.

  The pressure-sensitive adhesive surface of the film subjected to the pressure-sensitive adhesive processing was attached to a reinforced glass substrate having a thickness of 3 mm using a roll laminator.

Example 7
In Example 6, instead of the phthalocyanine compound (A) [ZnPc {(2-methylphenoxy) _5.6 F _10.4 }], the phthalocyanine compound (a) [CuPc {2,6- (CH ₃ OC ₂ H ₅ OOC) ₂ PhO} ₄ F ₄ F ₈ ] (λmax: 689 nm) is used in an amount of 0.014 parts by mass, and as another dye, tetra-t-butyl- described in Example 5 of Japanese Patent No. 3311720 is used. 0.025 parts by mass of tetraazaporphyrin / copper complex, phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) produced in Example 8 of JP-A-2001-10689] _{2 PhO} 4 (PhCH 2 NH} ) 4] (λmax: 807nm) of 0.1 parts by weight, prepared in example 7 of the publication phthalocyanine [VOPc (2, _{-Cl 2 PhO) 8 {2,6- (} CH 3) 2 PhO} 4 (PhCH 2 NH) 4] (λmax: 870nm) 0.13 parts by weight in Example 8 of JP-A-2004-18561 Patent Publication 0.02 part by mass of the prepared phthalocyanine [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ O (CH ₂ ) ₃ NH} ₄ ] (λmax: 928 nm), Phthalocyanine [VOPc (4- (CH ₃ O) PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ (CH ₂ ) ₃ CH (C ₂ H) produced in Example 17 of the publication ₅ ) CH ₂ NH} ₄ ] (λmax: 962 nm) was operated in the same manner as in Example 6 except that 0.15 part by mass was used.

Example 8
In Example 7, the mixing ratio of the dye was changed to 0.014 for the phthalocyanine compound (a) [CuPc {2,6- (CH ₃ OC ₂ H ₅ OOC) ₂ PhO} ₄ F ₄ F ₈ ] (λmax: 689 nm). Parts by mass, 0.025 parts by mass of tetra-t-butyl-tetraazaporphyrin / copper complex, phthalocyanine [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), 0.1 part by mass, phthalocyanine [VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (.lambda.max: 870 nm) was 0.13 parts by mass, further phthalocyanine _{[VOPc (PhS) 8 {2,6-} (CH 3) 2 PhO} 4 {CH 3 CH 2 O (C _{2) 3 NH} 4]} and phthalocyanine _{[VOPc (4- (CH 3 O} ) PhS) 8 {2,6- (CH 3) 2 PhO} 4 {CH 3 (CH 2) 3 CH (C 2 H 5) In place of CH ₂ NH} ₄ ], a diimonium compound (N, N, N ′, N′-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (imonium) · hexafluoroantimonate) The same operation as in Example 7 was performed except that 25 parts by mass was used.

Example 9
In Example 8, instead of 10 parts by mass of fluorene-based polyester copolymer, 33 parts by mass of Hals Hybrid IR-G205 (acrylic resin manufactured by Nippon Shokubai Co., Ltd.) was used. Further, instead of 89.44 parts by mass of dichloromethane, toluene was used. The same operation as in Example 8 was carried out except that 66.44 parts by mass were used.

Example 10
In Example 7, three types of phthalocyanines [CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 807 nm), [VOPc ( 2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ ] (λmax: 870 nm), and [VOPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {CH ₃ CH ₂ O (CH ₂ ) ₃ NH} ₄ ] (λmax: 928 nm) instead of Bis (1,2-diphenylene-1,2-dithiol) nickel in 0.074 parts by mass use the phthalocyanine _{[VOPc (4- (CH 3 O} ) PhS) 8 {2,6- (CH 3) 2 PhO} 4 {CH 3 (CH 2) 3 CH (C _{H 5) CH 2 NH) 4} ] (λmax: instead of 962 nm), diimmonium compound (N, N, N ', N'- tetrakis (p- diethylaminophenyl)-p-benzoquinone - bis (immonium) Hex The same operation as in Example 7 was conducted except that 0.25 part by mass of fluoroantimonate) was used.

Example 11
In Example 10, instead of 10 parts by mass of the fluorene-based polyester copolymer, 33 parts by mass of Hals Hybrid IR-G205 (acrylic resin manufactured by Nippon Shokubai Co., Ltd.) was used. Further, instead of 89.44 parts by mass of dichloromethane, toluene was used. The same operation as in Example 10 was performed except that 66.44 parts by mass were used.

Example 12
In Example 11, the phthalocyanine compound (a) [CuPc {2,6- (CH ₃ OC ₂ H ₅ OOC) ₂ PhO} ₄ F ₄ F ₈ ] (λmax: 689 nm) Example 11 except that it was added to 96.4 parts by mass of the acrylic adhesive (Aron S-1601 manufactured by Toagosei Co., Ltd.) of the adhesive layer instead of adding to IR-G205 (acrylic resin manufactured by Nippon Shokubai Co., Ltd.). Was operated in the same way.

Example 13
When the optical filter manufactured by the method described in Examples 6 to 12 was attached after removing the front filter of a commercially available plasma display, and red color development was observed, very beautiful red color development was observed for all the optical filters. Admitted.

  In addition, when an optical communication device having a light receiving sensor near 700 nm was approached to observe whether an erroneous signal was received, if a filter was not attached, reception of an unknown signal was seen. When it was attached to the front, no wrong signal was received.

Example 14: Synthesis of phthalocyanine compound: {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F} In a 50 ml three-necked flask, 4,5-bis (3-methoxycarbonylphenoxy)- 10 g (0.0215 mol) of 3,6-difluorophthalonitrile, 0.56 g (0.00565 mol) of copper chloride and about 15 g of octanol as a solvent were added, and the temperature was raised to 150 ° C. while stirring under a nitrogen stream. Thereafter, the reaction was carried out at 150 ° C. for about 2 hours, and after adding about 15 g of octanol, it was poured into 150 g of methanol, stirred and washed for 1 hour, suction filtered, and vacuum-dried at 60 ° C. to obtain an intermediate phthalocyanine compound {CuPc (3- Methoxycarbonylphenoxy) ₈ F ₈ } about 8.21 g was obtained.

2 g of the obtained intermediate phthalocyanine {CuPc (3-methoxycarbonylphenoxy) ₈ F ₈ } was transferred to a 50 ml three-necked flask, charged with about 18 g of 2-chlorobenzylamine, reacted at 140 ° C. for 2 hours, The reaction was carried out at 6 ° C for 6 hours. Thereafter, the mixture was cooled to room temperature and dropped into a mixed solution of 100 g of methanol, 45 g of water and about 15 g of concentrated hydrochloric acid. The obtained crystallized product was subjected to suction filtration, and washed with stirring with a mixed solution of 60 g of methanol and 40 g of water. The washed product was suction filtered again, and the obtained filter paper was vacuum dried at 60 ° C. to obtain about 3.4 g of a phthalocyanine compound {CuPc (3-methoxycarbonylphenoxy) ₈ (2-chlorobenzylamino) ₇ F}. It was.

  About the obtained phthalocyanine, when the maximum absorption wavelength in an acetone solution was measured using the spectrophotometer (made by Shimadzu Corporation: UV1650PC), the maximum absorption wavelength was 916 nm.

Example 15: Synthesis of phthalocyanine compound {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ } The intermediate phthalocyanine {CuPc (3-methoxycarbonylphenoxy) ₈ synthesized in the same manner as in Example 14 above. 2 g of F ₈ } was placed in a 50 ml three-necked flask, about 18 g of 2-ethylhexylamine was added, reacted at 120 ° C. for 12 hours, and reacted at 140 ° C. for about 10 hours. Thereafter, the mixture was cooled to room temperature and dropped into a mixed solution of 100 g of methanol, 45 g of water and about 15 g of concentrated hydrochloric acid. The obtained crystallized product was subjected to suction filtration, and washed with stirring with a mixed solution of 60 g of methanol and 40 g of water. The washed product was suction filtered again, and the obtained filter paper was vacuum-dried at 60 ° C. to obtain about 3.1 g of a phthalocyanine compound {CuPc (3-methoxycarbonylphenoxy) ₈ (2-ethylhexylamino) ₈ }.

  When the maximum absorption wavelength of the obtained phthalocyanine was measured in the same manner as in Example 14, the maximum absorption wavelength was 963 nm.

Example 16: Synthesis of phthalocyanine compound (vi) {ZnPc (3-PhOOCPhO) ₄ F ₄ F ₈ } In a 50 ml three-necked flask, 4- (3-phenoxycarbonylphenoxy) -3,5,6-trifluoro 10 g (0.025 mol) of phthalonitrile, 2.23 g (0.007 mol) of zinc iodide and 17 g of benzonitrile as a solvent were added, and the mixture was reacted at 190 ° C. for about 12 hours while stirring under a nitrogen stream. After cooling, it was poured into a mixed solution of about 250 ml of methanol and 40 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed again with stirring in a mixed solution of about 100 ml of methanol and 25 ml of water, whereby the target product was washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and ZnPc (3-PhOOCPhO) ₄ F ₄ F ₈ about 7.65 g {4- (3-phenoxycarbonylphenoxy) ) -3,5,6-trifluorophthalonitrile yield was about 74.5 mol%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 17: A three-necked flask 50ml of phthalocyanine compound _{(vii) {ZnPc (3-} CH 3 OOCPhO) 8 F 8}, 4,5- bis (3-methoxycarbonyl-phenoxy) -3,6-difluoro 10 g (0.0215 mol) of phthalonitrile, 1.89 g (0.006 mol) of zinc iodide and 17 g of benzonitrile as a solvent were added and reacted at 190 ° C. for about 12 hours with stirring under a nitrogen stream. After cooling, benzonitrile was distilled off at about 110 ° C. while reducing the pressure with a vacuum pump, and further vacuum-dried at about 80 ° C. overnight to obtain about 10.1 g of ZnPc (3-CH ₃ OOCPhO) ₈ F ₈ {4 , 5-bis (3-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile, yield about 97.4 mol%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 18: A three-necked flask 50ml of 25% hydrolyzate of the phthalocyanine compound _{(vii) (viii) {ZnPc} (3-CH 3 OOCPhO) 6 (3-HOOCPhO) 2 F 8}, Example 17 ZnPc (3-CH ₃ OOCPhO) ₈ F ₈ 5 g (0.0026 mol), sodium hydroxide 0.208 (0.0052 mol) and dimethyl sulfoxide 20 g, ethanol 5 g, water 0.5 g And the resulting mixture was reacted at 60 ° C. with stirring for about 3 hours. After cooling, it was poured into about 160 ml of water, and about 0.82 g of concentrated hydrochloric acid was added to make it acidic to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 80 ° C. overnight, and ZnPc (3-CH ₃ OOCPhO) ₆ (3-HOOCPhO) ₂ F ₈ about 4.65 g {ZnPc ( for _{3-CH 3 OOCPhO) 8 F} 8 was obtained yield of about 94.4 mole%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 19: A three-necked flask 50ml of phthalocyanine compound 15% hydrolyzate of _{(vii) (ix) {ZnPc} (3-CH 3 OOCPhO) 6.8 (3-HOOCPhO) 1.2 F 8} ZnPc (3-CH ₃ OOCPhO) ₈ F ₈ 5 g (0.0026 mol), sodium hydroxide 0.125 (0.0031 mol) and dimethyl sulfoxide 20 g, ethanol 4 g, synthesized in the same manner as in Example 17, 0.4 g of water was added, and the resulting mixture was reacted at 60 ° C. for about 3 hours with stirring. After cooling, the solution was poured into about 160 ml of water and made acidic by adding about 0.5 g of concentrated hydrochloric acid to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 80 ° C. overnight, and ZnPc (3-CH ₃ OOCPhO) _6.8 (3-HOOCCPhO) _1.2 F _{8 was} about 4. It was obtained _{72g {ZnPc (3-CH 3} OOCPhO) about the yield for the 8 _{F 8} 95.3 mole%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 20: A three-necked flask 50ml of phthalocyanine compound _{(x) {VOPc (3-} CH 3 OOCPhO) 8 F 8}, 4,5- bis (3-methoxycarbonyl-phenoxy) -3,6-difluoro 10 g (0.0215 mol) of phthalonitrile, 1.02 g (0.0065 mol) of vanadium trichloride and 35 g of benzonitrile as a solvent were added in a nitrogen stream, bubbling air and stirring at 175 ° C. for about 11 hours. Reacted. After cooling, it was poured into about 400 ml of methanol to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in about 300 ml of methanol. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and about 7.55 g of VOPc (3-CH ₃ OOCPhO) ₈ F ₈ {4,5-bis (3- Yield of about 72.8 mol% relative to (methoxycarbonylphenoxy) -3,6-difluorophthalonitrile.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 21: Synthesis of 15% hydrolyzate (xi) of phthalocyanine compound (x) {VOPc (3-CH ₃ OOCPhO) _6.8 (3-HOOCCPhO) _1.2 F ₈ } In a 50 ml three-necked flask VOPc (3-CH ₃ OOCPhO) ₈ F ₈ 5 g (0.0026 mol), sodium hydroxide 0.125 (0.0031 mol) and dimethyl sulfoxide 20 g, ethanol 4 g, synthesized in the same manner as in Example 20, 0.4 g of water was added and reacted at 60 ° C. for about 3 hours with stirring. After cooling, the solution was poured into about 160 ml of water, and about 0.5 g of concentrated hydrochloric acid was added to make it acidic to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 80 ° C. overnight, and VOPc (3-CH ₃ OOCPhO) _6.8 (3-HOOCPhO) _1.2 F ₈ about 4.46 g { Yield of about 89.9 mol% relative to VOPc (3-CH ₃ OOCPhO) ₈ F ₈ was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 22: A three-necked flask 50ml of phthalocyanine compound _{(g) {VOPc (2-} CH 3 OCH 2 CH 2 OOCPhO) 4 F 4 F 8}, 4- (2- methoxyethoxy carbonyl phenoxy) -3 , 5,6-trifluorophthalonitrile 10 g (0.0266 mol), vanadium trichloride 1.25 g (0.05 mol) and benzonitrile 35 g as a solvent were added in a nitrogen stream, and air was bubbled and stirred. The reaction was carried out at 175 ° C. for about 11 hours. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and then washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OCH ₂ CH ₂ OOCPhO) ₄ F ₄ F ₈ about 7.28 g {4- Yield of about 69.7 mol% relative to (2-methoxyethoxycarbonylphenoxy) -3,5,6-trifluorophthalonitrile.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 23: 3-necked flask 50ml of 25% hydrolyzate of phthalocyanine compound _{(g) (h) {VOPc} (2-CH 3 OCH 2 CH 2 OOCPhO) 3 (2-HOOCPhO) F 4 F 8} VOPc (2-CH ₃ OCH ₂ CH ₂ OOCPhO) ₄ F ₄ F ₈ 5 g (0.00319 mol) and sodium hydroxide 0.128 g (0.0032 mol) synthesized in the same manner as in Example 22 20 g of dimethyl sulfoxide, 4 g of ethanol and 0.4 g of water were added, and the resulting mixture was reacted at 60 ° C. for about 3 hours while stirring. After cooling, it was poured into about 160 ml of water, and about 0.5 g of concentrated hydrochloric acid was added to make it acidic to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried overnight at about 80 ° C., and VOPc (2-CH ₃ OCH ₂ CH ₂ OOCPhO) ₃ (2-HOOCPhO) F ₄ F _{8 was} about 4 It was obtained _{.42g {VOPc (2-CH 3} OCH 2 CH 2 OOCPhO) 4 F 4 about 91.8 mole percent yield based on _{F 8}.}

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 24: A three-necked flask 50ml of phthalocyanine compound _{(i) {VOPc (2-} CH 3 OCH 2 CH 2 OOC-6-CH 3 PhO) 4 F 4 F 8}, 4- (2- methoxy Ethoxycarbonyl-6-methylphenoxy) -3,5,6-trifluorophthalonitrile 10 g (0.0256 mol), vanadium trichloride 1.21 g (0.0077 mol) and 35 g of benzonitrile as a solvent under a nitrogen stream. The reaction was carried out at 175 ° C. for about 11 hours while bubbling air and stirring. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and then washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OCH ₂ CH ₂ OOC-6-CH ₃ PhO) ₄ F ₄ F ₈ about 6.86 g {yield of about 67.5 mol% based on 4- (2-methoxyethoxycarbonyl-6-methylphenoxy) -3,5,6-trifluorophthalonitrile} was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 25: 25% hydrolyzate of the phthalocyanine compound _{(i) (j) {VOPc} (2-CH 3 OCH 2 CH 2 OOC-6-CH 3 PhO) 3 (2-HOOC-6-CH 3 PhO) F Synthesis of ₄ F ₈ } VOPc (2-CH ₃ OCH ₂ CH ₂ OOC-6-CH ₃ PhO) ₄ F ₄ F ₈ 5 g (0) was synthesized in the same manner as in Example 24 in a 50 ml three-necked flask. .00307 mol), 0.123 g (0.00307 mol) of sodium hydroxide, 20 g of dimethyl sulfoxide, 4 g of ethanol, and 0.4 g of water were added, and the resulting mixture was reacted at 60 ° C. for about 3 hours with stirring. After cooling, it was poured into about 160 ml of water, and about 0.5 g of concentrated hydrochloric acid was added to make it acidic to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 80 ° C. overnight, and VOPc (2-CH ₃ OCH ₂ CH ₂ OOC-6-CH ₃ PhO) ₃ (2-HOOC— _{6-CH 3 PhO) F 4} F 8 to obtain about _{4.42g {VOPc (2-CH 3} OCH 2 CH 2 OOC-6-CH 3 PhO) 4 F 4 about 89.2 mole percent yield based on _{F 8}} It was.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 26: A three-necked flask 50ml of phthalocyanine compound _{(xii) {VOPc (2-} CH 3 OOC-5-CH 3 PhO) 4 H 4 H 8}, 4- (2- methoxy-5- Methylphenoxy) phthalonitrile (10 g, 0.0342 mol), vanadium trichloride (1.53 g, 0.0097 mol) and benzonitrile (35 g) as a solvent were charged in a nitrogen stream, and air was bubbled and stirred at about 175 ° C. The reaction was carried out for 11 hours. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and washed and purified. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OOC-5-CH ₃ PhO) H ₄ H ₈ about 9.33 g {4 A yield of about 88.5 mol% relative to-(2-methoxycarbonyl-5-methylphenoxy) phthalonitrile was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 27: phthalocyanine compound _{(xiv) {VOPc (3-} CH 3 CH 2 OOCPhO) 4 H 4 H 8} in three-necked flask 50ml of 4- (3-ethoxycarbonyl-aminophenoxy) phthalonitrile 10 g (0 0.0342 mol), 1.61 g (0.01 mol) of vanadium trichloride and 35 g of benzonitrile as a solvent were added in a nitrogen stream, and the reaction was carried out at 175 ° C. for about 11 hours while bubbling air and stirring. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (3-CH ₃ CH ₂ OOCPhO) ₄ H ₄ H ₈ about 9.33 g {4- (3 -Ethoxycarbonylphenoxy) phthalonitrile yield was about 89.6 mol%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 28: A three-necked flask 50ml of phthalocyanine compound _{(iv) {VOPc (2-} CH 3 OOCPhO) 4 H 4 H 8}, 4- (2- methoxycarbonyl-phenoxy) phthalonitrile 10 g (0.036 Mol), 1.70 g (0.011 mol) of vanadium trichloride and 35 g of benzonitrile as a solvent were added under a nitrogen stream, and the reaction was carried out at 175 ° C. for about 5 hours while bubbling air and stirring. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OOCPhO) ₄ H ₄ H ₈ about 10.3 g {4- (2-methoxy Yield of about 96.7 mol% relative to (carbonylphenoxy) phthalonitrile.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 29: A three-necked flask 50ml of phthalocyanine compound _{(e) {VOPc (2-} CH 3 OCH 2 CH 2 OOC-5-Cl-PhO) 4 H 4 H 8}, 4- (2- methoxy Ethoxycarbonyl-5-chlorophenoxy) phthalonitrile 10 g (0.028 mol), vanadium trichloride 1.32 g (0.0084 mol) and benzonitrile 35 g as a solvent were added under a nitrogen stream, and air was bubbled and stirred. The reaction was carried out at 175 ° C. for about 8 hours. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and then washed and purified. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OCH ₂ CH ₂ OOC-5-Cl-PhO) ₄ H ₄ H ₈ about 9.65 g {yield of about 92.2 mol% based on 4- (2-methoxyethoxycarbonyl-5-chlorophenoxy) phthalonitrile} was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 30: A three-necked flask 50ml of phthalocyanine compound _{(xvi) {VOPc (2-} CH 3 OOC-5-CH 3 OPhO) 4 H 4 H 8}, 4- (2- methoxy-5- Methoxyphenoxy) phthalonitrile (10 g, 0.0324 mol), vanadium trichloride (1.53 g, 0.0097 mol) and benzonitrile (35 g) as a solvent were added in a nitrogen stream, and air was bubbled and stirred at 175 ° C. The reaction was carried out for about 5 hours. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and then washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPc (2-CH ₃ OOC-5-CH ₃ OPhO) ₄ H ₄ H ₈ about 9.92 g { Yield of about 94.1 mol% relative to 4- (2-methoxycarbonyl-5-methoxyphenoxy) phthalonitrile.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 31 Synthesis of Phthalocyanine Compound (I) {VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₄ H ₄ } In a 50 ml three-necked flask, 3- (2-isoamyloxycarbonyl 10 g (0.0299 mol) of phenoxy) phthalonitrile, 1.41 g (0.009 mol) of vanadium trichloride and 35 g of benzonitrile as a solvent were added in a nitrogen stream, and about 11 at 175 ° C. while bubbling air and stirring. Reacted for hours. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and washed and purified. Thereafter, the crystals were taken out again by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₄ H ₄ about 5.70 g. A yield of about 54.3 mol% based on 3- (2-isoamyloxycarbonylphenoxy) phthalonitrile was obtained.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 32: Synthesis of 25% hydrolyzate (II) of phthalocyanine compound (I) {VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₃ (2-HOOCPhO) H ₄ }
In a 50 ml three-necked flask, 5 g (0.00356 mol) of VOPcH ₈ (2-CH ₃ CH ₂ (CH ₃ ) CHCH ₂ OOCPhO) ₄ H ₄ synthesized in the same manner as in Example 31 and sodium hydroxide 0 .232 g (0.00356 mol) and 20 g of dimethyl sulfoxide, 4 g of ethanol and 0.4 g of water were added, and the resulting mixture was reacted at 60 ° C. for about 3 hours with stirring. After cooling, it was poured into about 160 ml of water, and about 0.5 g of concentrated hydrochloric acid was added to make it acidic to precipitate crystals. The obtained crystals were subjected to suction filtration, and then washed and purified by stirring and washing again in a mixed solution of about 20 ml of methanol and 20 ml of water. Then again, it removed crystals by suction filtration, overnight extraction crystals at about 80 ° C., dried in _{vacuo, VOPcH 8 (2-CH 3} CH 2 (CH 3) CHCH 2 OOCPhO) 3 (2-HOOCPhO) H ₄ to obtain about _{4.42g {VOPcH 8 (2-CH} 3 CH 2 (CH 3) CHCH 2 OOCPhO) 4 H about 90.7 mole percent yield based on _4}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Example 33 Synthesis of 4- (3-ethoxycarbonylphenoxy) phthalonitrile {4- (3-CH ₃ CH ₂ OOCPhO) PN} In a 50 ml three-necked flask, 6 g (0.035 mol) of 4-nitrophthalonitrile was added. ), 6.43 g (0.038 mol) of ethyl 3-hydroxybenzoate, and 20 ml of dimethylformamide, and while maintaining the temperature at 30 ° C. with stirring, 1,8-diazabicyclo [5.4.0] -7 -5.81 g (0.038 mol) of undecene (DBU) was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C. and reacted for about 5 hours. After cooling to room temperature, about 150 ml of chloroform, 140 ml of water and 10 ml of concentrated hydrochloric acid are added and extracted into a chloroform layer. After further washing with 150 ml of water, chloroform was distilled off from the chloroform extract, 100 ml of methanol was added to dissolve the crystals, and then 20 g of water was added and cooled. After the resulting crystals were suction filtered, the extracted crystals were vacuum-dried overnight at about 60 ° C. to obtain about 8.59 g of 4- (3-CH ₃ CH ₂ OOCPhO) PN (yield against 4-nitrophthalonitrile). The rate was about 84.0 mol%}.

Example 34: Phthalocyanine Synthesis of Compound _{(xviii) {ZnPc (3-} H 5 C 2 OOCPhO) 4 H 4 H 8}
In a 50 ml three-necked flask, 10 g (0.0342 mol) of 4- (3-ethoxycarbonylphenoxy) phthalonitrile synthesized in the same manner as in Example 33, 3.0 g (0.0094 mol) of zinc iodide, and As a solvent, 35 g of benzonitrile was added under a nitrogen stream, and the reaction was carried out at 190 ° C. for about 10 hours while flowing nitrogen and stirring. After cooling, it was poured into a mixed solution of about 300 ml of methanol and 50 ml of water to precipitate crystals. The obtained crystals were subjected to suction filtration, then again put into a mixed solution of about 100 ml of methanol and 15 ml of water, washed with stirring, and then washed and purified. Thereafter, the crystals were again taken out by suction filtration, and the taken out crystals were vacuum-dried at about 60 ° C. overnight, and ZnPc (3-H ₅ C ₂ OOCPhO) ₄ H ₄ H ₈ about 7.34 g {4- (3 -Ethoxycarbonylphenoxy) phthalonitrile yield about 69.5 mol%}.

  About the obtained phthalocyanine, it carried out similarly to Example 1, and measured the maximum absorption wavelength in an acetone solution. Further, the absorbance at the maximum absorption wavelength and the absorbance at 460 nm were measured, and the absorbance was calculated by dividing the absorbance at the maximum absorption wavelength by the absorbance at 460 nm. The results are shown in Table 2.

Claims (14)

Following formula (1):

In the formula, Z ₁ , Z ₄ , Z ₅ , Z ₈ , Z ₉ , Z ₁₂ , Z ₁₃ and Z ₁₆ each independently represent a halogen atom; Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ are each independently a halogen atom or the following formula:

In this case, 0 to _{6 of} Z ₂ , Z ₃ , Z ₆ , Z ₇ , Z ₁₀ , Z ₁₁ , Z ₁₄ and Z ₁₅ represent a halogen atom; M represents metal-free, metal, metal oxide or metal halide,
The phthalocyanine compound (1) shown by these. Following formula:

The phthalocyanine compound (1) according to claim 1, which is represented by: Following formula (2):

In the formula, Z ₁ ′, Z ₄ ′, Z ₅ ′, Z ₈ ′, Z ₉ ′, Z ₁₂ ′, Z ₁₃ ′ and Z ₁₆ ′ each independently represent a hydrogen atom or a halogen atom; ₂ ′, Z ₃ ′, Z ₆ ′, Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′ are each independently a hydrogen atom, a halogen atom or the following formula:

-COOR ¹ OR ² -containing phenoxy group represented by the formula, wherein R ¹ represents — (CH ₂ ) _p — (p is an integer of 1 to 5), and R ² represents the number of carbon atoms. Represents an alkyl group of 1 to 5, R ⁷ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and a is 1 or 2, and in this case, Z ₂ ′, Z ₃ ′, Z ₆ ′ , Z ₇ ′, Z ₁₀ ′, Z ₁₁ ′, Z ₁₄ ′ and Z ₁₅ ′, 4 are halogen atoms and the remaining 4 represent a —COOR ¹ OR ² -containing phenoxy group, and 4 are 4 is and the remaining hydrogen atoms represents -COOR ¹ oR ² containing phenoxy group, or 8 represents a -COOR ¹ oR ² containing phenoxy groups; M is a metal-free, metal, metal oxides or metal halides Represents
Or a hydrolyzate thereof. 4 or 5-tetrakis (2,6-dimethoxyethoxycarbonylphenoxy) dodecafluorocopper phthalocyanine;
4 or 5-tetrakis (5-chloro-2-methoxyethoxycarbonylphenoxy) oxyvanadium phthalocyanine;
4 or 5-tetrakis (2-methoxyethoxycarbonyl-6-methylphenoxy) -5 or 4-tetrafluoro-3,6-octafluorooxyvanadium phthalocyanine;
25% hydrolyzate of 4 or 5-tetrakis (2-methoxyethoxycarbonyl-6-methylphenoxy) -5 or 4-tetrafluoro-3,6-octafluorooxyvanadium phthalocyanine;
4. The phthalocyanine compound (2) or a hydrolyzate thereof according to claim 3, selected from the group consisting of 4 or 5-tetrakis (2-methoxyethoxycarbonyl-5-methoxyphenoxy) oxyvanadium phthalocyanine. Following formula (3):

In the formula, Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ each independently represent a halogen atom or the following formula:

In this case, _{4 of} Z ₁ ″, Z ₄ ″, Z ₅ ″, Z ₈ ″, Z ₉ ″, Z ₁₂ ″, Z ₁₃ ″ and Z ₁₆ ″ are represented. Each represents a halogen atom, and R ³ and R ⁴ each independently represent a methyl group, an ethyl group or a halogen atom; Z ₂ ″, Z ₃ ″, Z ₆ ″, Z ₇ ″, Z ₁₀ ″. , Z ₁₁ ″, Z ₁₄ ″ and Z ₁₅ ″ are independently selected from the following formulas:

In this case, R ⁵ represents a halogen atom, and when a plurality of R ⁵ are present, each R ⁵ may be the same or different. , N is an integer from 1 to 5; M represents a metal-free, metal, metal oxide or metal halide,
The phthalocyanine compound (3) shown by these. Following formula:

The phthalocyanine compound (3) of Claim 5 shown by these. Following formula (4):

In the formula, Z ₁ ″ ′, Z ₄ ″ ′, Z ₅ ″ ′, Z ₈ ″ ′, Z ₉ ″ ′, Z ₁₂ ″ ′, Z ₁₃ ″ ′ and Z ₁₆ ″ ′ are independently hydrogen Represents an atom or a halogen atom; Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are each independently A hydrogen atom, a halogen atom or the following formula:

-COOR ⁶ -containing phenoxy group represented by the formula: wherein R ⁶ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁸ represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group. In this case, four of Z ₂ ″ ′, Z ₃ ″ ′, Z ₆ ″ ′, Z ₇ ″ ′, Z ₁₀ ″ ′, Z ₁₁ ″ ′, Z ₁₄ ″ ′ and Z ₁₅ ″ ′ are a halogen atom and the remaining four represents a -COOR ⁶ containing a phenoxy group, 4 represents a is and the remaining four are -COOR ⁶ containing phenoxy group hydrogen atom, or 8 is -COOR ⁶ containing phenoxy M represents a metal-free, metal, metal oxide or metal halide;
Or a hydrolyzate thereof. 4 or 5-tetrakis (2-ethoxycarbonylphenoxy) dodecafluorocopper phthalocyanine;
4 or 5-tetrakis (4-ethoxycarbonylphenoxy) dodecafluorocopper phthalocyanine;
4 or 5-tetrakis (3-methoxycarbonylphenoxy) dodecafluorocopper phthalocyanine;
4 or 5-tetrakis (2-methoxycarbonylphenoxy) oxyvanadium phthalocyanine;
4 or 5-tetrakis (3-methoxycarbonyl-6-methylphenoxy) oxyvanadium phthalocyanine;
4 or 5-tetrakis (3-phenoxycarbonylphenoxy) -5 or 4-tetrafluoro-3,6-octafluorozinc phthalocyanine;
4,5-octakis (3-methoxycarbonylphenoxy) -3,6-octafluorozinc phthalocyanine;
25% hydrolyzate of 4,5-octakis (3-methoxycarbonylphenoxy) -3,6-octafluorozinc phthalocyanine;
15% hydrolyzate of 4,5-octakis (3-methoxycarbonylphenoxy) -3,6-octafluorozinc phthalocyanine;
4,5-octakis (3-methoxycarbonylphenoxy) -3,6-octafluorooxyvanadium phthalocyanine;
15% hydrolyzate of 4,5-octakis (3-methoxycarbonylphenoxy) -3,6-octafluorooxyvanadium phthalocyanine;
4 or 5-tetrakis (5-methyl-2-methoxycarbonylphenoxy) oxyvanadium phthalocyanine;
25% hydrolyzate of 4 or 5-tetrakis (5-methyl-2-methoxycarbonylphenoxy) oxyvanadium phthalocyanine;
4 or 5-tetrakis (3-ethoxycarbonylphenoxy) oxyvanadium phthalocyanine;
25% hydrolyzate of 4 or 5-tetrakis (3-ethoxycarbonylphenoxy) oxyvanadium phthalocyanine;
4 or 5-tetrakis (5-methoxy-2-methoxycarbonylphenoxy) oxyvanadium phthalocyanine;
25% hydrolyzate of 4 or 5-tetrakis (5-methoxy-2-methoxycarbonylphenoxy) oxyvanadium phthalocyanine;
The phthalocyanine compound (4) or a hydrolyzate thereof according to claim 7, which is selected from the group consisting of: Following formula (5):

In the formula, Y ₁ , Y ₄ , Y ₅ , Y ₈ , Y ₉ , Y ₁₂ , Y ₁₃ and Y ₁₆ are each independently a hydrogen atom, a halogen atom or the following formula:

In represents -COOR ⁹ containing phenoxy group represented, this time, ^{R 9} represents an alkyl group having 1 to 20 carbon atoms, this _{time, Y 1, Y 4, Y} 5, Y 8, Y 9, Y ₁₂ , Y ₁₃ and Y ₁₆ are 4 halogen atoms and the remaining 4 represent a —COOR ^9- containing phenoxy group, or 4 are hydrogen atoms and the remaining 4 represent —COOR ^9- containing Represents a phenoxy group; Y ₂ , Y ₃ , Y ₆ , Y ₇ , Y ₁₀ , Y ₁₁ , Y ₁₄ and Y ₁₅ each independently represents a hydrogen atom or a halogen atom; Represents a metal oxide or metal halide,
Or a hydrolyzate thereof. Selected from the group consisting of 3 or 6-tetrakis (2-isoamyloxycarbonylphenoxy) oxyvanadium phthalocyanine; and 25% hydrolyzate of 3 or 6-tetrakis (2-isoamyloxycarbonylphenoxy) oxyvanadium phthalocyanine; The phthalocyanine compound (5) according to claim 9 or a hydrolyzate thereof.   A filter for light-cutting flat panel display having a wavelength of 640 to 750 nm, which contains a dye having a maximum absorption wavelength at least at 640 to 750 nm and an absorbance at the maximum absorption wavelength that is 10 times or more of the absorbance at 460 nm.   A filter for light-cutting flat panel display having a wavelength of 640 to 750 nm, comprising a phthalocyanine dye having a maximum absorption wavelength at least at 640 to 750 nm and having an absorbance at the maximum absorption wavelength of 10 times or more of the absorbance at 460 nm.   The filter for flat panel displays of Claim 11 or 12 used in combination with the optical communication system which light-emits the light of a wavelength of 640-750 nm.   The flat panel display filter according to any one of claims 11 to 13, wherein the flat panel display filter is a plasma display filter.